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RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/097,277, filed Nov. 14, 2014; the disclosures of which is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention is directed in general to biological based supercapacitors, their methods of manufacture, and methods of use. More specifically, the invention is directed to biological supercapacitors comprising any biological capable of providing transfer of electrons between the fuel fluid and electron conductor and their method of manufacture and use.
BACKGROUND
[0003] Mitochondria are the organelles of the living cell that contain several (but not all) of the protein pathways of metabolism, including the citric acid cycle and the electron transport chain. They are responsible for a variety of metabolic processes including fatty acid metabolism and pyruvate oxidation, while pyruvate is produced outside of the mitochondria from glycolytic pathway oxidation of sugars.
[0000] The citric acid cycle is a key metabolic pathway that unifies carbohydrate, fat, and protein metabolism. The reactions of the cycle are carried out by enzymes that completely oxidize acetate, in the form of acetyl-CoA, into two molecules each of carbon dioxide and water. Through catabolism of sugars, fats, and proteins, a two-carbon organic product acetate in the form of acetyl-CoA is produced which enters the citric acid cycle.
[0004] The reactions of the cycle also convert three equivalents of nicotinamide adenine dinucleotide (NAD + ) into three equivalents of reduced NAD + (NADH), one equivalent of flavin adenine dinucleotide (FAD) into one equivalent of FADH 2 , and one equivalent each of guanosine diphosphate (GDP) and inorganic phosphate (P i ) into one equivalent of guanosine triphosphate (GTP).
[0005] Biological supercapacitors harness the catalytic activity of living cells, which are able to conduct electrochemical reactions and produce electrical energy. When using biological materials as catalysts at the anode or cathode of a biological supercapacitor, the catalyst needs to be immobilized at the surface of the electrode.
[0006] In its most general aspect, a biological supercapacitor consists of paired electrodes and on one side of the interface a layer of electrons forms. On the opposite side of the interface, a layer of positive ions forms. Together, these two layers are the double layer, which store energy.
[0007] The voltage across the interface increases with charge accumulation. In connection with the double layer capacitance phenomenon, no charge transfer (Faradaic) process occurs at the electrode/electrolyte interface. During discharge, the charge stored at the interface is released. The charge/discharge rate is generally determined by the nature and type of the material, its thickness, and the electrolyte.
BRIEF SUMMARY OF THE INVENTION
[0008] Biocompatible and “micro” energy sources are critical to the development of novel commercial bioelectronics, such as health monitoring devices (rapid analysis of DNA, RNA, metabolites—i.e. biomolecule to biosensors, disease treatment devices, nanoscale delivery vehicles that require biocompatibility to interface with tissues or single cells, and neural and biochemical prosthesis, i.e. artificial sensory organs that require tissue integration or wireless networks), and consumer portable electronics. Conventional battery size and weight are the key technical limitations in the bioelectronics field. Additionally, though many of the current power sources are rechargeable, the recharging process itself involves interaction with an external electrical energy source.
[0009] There is a clear need to reduce the Size and Weight of energy storage devices and conserve Power (SWaP). The present disclosure illustrates an apparatus and methods of use thereof to harness the power of biochemical reactions to generate electrochemical potential in a bio(logical) supercapacitor. The biosupercapacitor of the instant disclosure provides the energy density of a battery combined with the power density of a supercapacitor in order to reduce the size and weight of the energy storage devices.
[0010] The biological supercapacitor of the instant disclosure comprises at least one pair of electrodes, a bioanode and a biocathode. Each electrode comprises immobilized biological materials that include enzymes. The supercapacitor further comprises a barrier positioned between the bioanode and biocathode, and an ionic conductor that also contains organic fuel(s). The barrier may comprise a separator, which functions as an electronic insulator. The biological electron donor or acceptor of the bioanode is capable of reacting with a fuel fluid to produce an oxidized form of the fuel fluid, and capable of releasing electrons to the electron conductor. The biological electron donor or acceptor of the biocathode is capable of reacting with an oxidant to produce water, and capable of gaining electrons from the electron conductor. The biological electron donor or acceptor immobilization material present on both the bioanode and the biocathode is capable of immobilizing the biological electron donor or acceptor, thereby adhering it to the bioelectrodes, and is permeable to the fuel fluid and/or the oxidant. In various embodiments, the biological electron donor or acceptor immobilization material is further capable of stabilizing the biological agents.
[0011] At least one novel feature of the capacitor resides in the enzymatic electrode structure. The electrodes may be manufactured by immobilizing biological enzyme cascades, either isolated or contained in whole cells or parts of cells, with various materials which possess non faradic or faradic charge transfer characteristics to form the electrode pairs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
[0013] FIG. 1 is a schematic view of a supercapacitor that has biological anode and cathode design.
[0014] FIG. 2 depicts a schematic diagram of a bioelectrode of the instant disclosure.
[0015] FIG. 3 depicts a schematic view of the biosupercapacitor of the instant disclosure in an electric circuit.
[0016] Mitochondria, enzymes, or enzyme cascades can all be effectively immobilized to create bioelectrodes. Additionally, a means is also provided for electrons to be transferred to and from the electrodes. This can be done either directly from the enzyme to the electrode (“direct electron transfer”) or with the aid of other chemicals or substances that transfer electrons from the enzyme to the electrode (“mediated electron transfer”). These chemical substances are termed “electron transfer mediators” or simply “mediators” throughout this disclosure. An advantage of this approach is that biological materials are renewable, non-hazardous, high capacitance, and non-waste generating (complete oxidation of fuels to CO 2 ).
Definitions
[0017] The following terms shall have, for the purposes of this application, the respective meaning set forth below.
[0018] Electron carrier: An electron carrier is a composition that provides electrons in an enzymatic reaction. Electron carriers include, without limitation, reduced nicotinamide adenine dinucleotide (denoted NADH; oxidized form denoted NAD or NAD+), reduced nicotinamide adenine dinucleotide phosphate (denoted NADPH; oxidized form denoted NADP or NADP+), reduced nicotinamide mononucleotide (NMOSH; oxidized form NMN), reduced flavin adenine dinucleotide (FADH2; oxidized form FAD), reduced flavin mononucleotide (FMNH2; oxidized form FMN), reduced coenzyme A, and the like. Electron carriers include proteins with incorporated electron-donating prosthetic groups, such as coenzyme A, protoporphyrin IX, vitamin B12, and the like. Further electron carriers include glucose (oxidized form: gluconic acid), alcohols (e.g., oxidized form: ethylaldehyde), and the like.
[0019] Electron-receiving composition: An electron-receiving composition receives the electrons conveyed to the cathode by the supercapacitor.
[0020] Electron transfer mediator: An electron transfer mediator is a composition, which facilitates transfer to an electrode of electrons released from an electron carrier. Redox enzyme: A redox enzyme is an enzyme that catalyzes the transfer of electrons from an electron carrier to another composition, or from another composition to the oxidized form of an electron carrier. Examples of appropriate classes of redox enzymes include: oxidases, dehydrogenases, reductases and oxidoreductases. Additionally, other enzymes, with redox catalysis as their secondary property could be used e.g., superoxide dismutase.
[0021] Composition: Composition refers to a molecule, compound, charged species, salt, polymer, or other combination or mixture of chemical entities.
[0022] Metabolon: A metabolon is a supramolecular organization of the Krebs cycle enzymes in mitochondria where the continuous surface pattern electrostatically favors efficient intermediate transport between active sites in the complex, known as substrate channeling.
[0023] Enzyme cascade: An enzyme cascade is a group of sequential enzymes of metabolic pathways.
[0024] Electrocyte: As used herein, an electrocyte is an electrogenic cell.
DETAILED DESCRIPTION OF THE INVENTION
[0025] A biological supercapacitor according to the present disclosure includes at least several practical advantages over those known in the art. It has an increased device energy density when compared with carbon capacitors and low-cost biocatalysts instead of costly or rare metals. Moreover, the biological supercapacitors of the instant disclosure are disposable and biodegradable devices.
[0026] The current invention achieves high energy storage capability using biologically derived or biomimetic components. The citric acid cycle enzymes, which for purposes of this application are known to occur in a specific enzymatic sequence in the mitochondria, may be used individually or in any combination thereof. They may be crosslinked and removed from the organelle prior to immobilization at the anode or cathode, hereinafter referred to as “bioanode” and “biocathode” respectively.
[0027] Enzymes that catalyze oxidation reactions include pyruvate dehydrogenase, isocitrate dehydrogenase, ketoglutarate dehydrogenase, succinate dehydrogenase, and malate dehydrogenase. The other enzymes catalyze additional necessary chemical reactions to rearrange the reactant molecules for the next step of oxidation.
[0028] Reference will now be made in detail to the present embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.
[0029] Referring now to FIG. 1 , an embodiment of a supercapacitor as described herein comprises two electrodes, a biocathode 130 and a bioanode 150 . These bioelectrodes are separated from each other by a barrier 140 . The barrier 140 may be fabricated from an electrically inert material or it may be a separator as described herein. The electrodes and barrier 140 are placed within a capsule 170 . The capsule 170 will eventually be filled with electrolyte fluid 180 . A bioanode chamber is defined by the walls of the capsule 170 which surround the bioanode 150 and by the surface of the barrier 140 that faces the bioanode 150 . A biocathode chamber is defined by the walls of the capsule 170 which surround the biocathode 130 and by the surface of the barrier 140 that faces the bioanode 130 . The biocathode 130 , the barrier 140 , and the bioanode 150 are compressed together by two electrically inert plates 120 a and 120 b, one positioned parallel to each of the electrodes. The plates 120 a and 120 b are adjacent to the side of each electrode that is opposite the side facing barrier 140 . Two housing walls 110 a and 110 b are positioned parallel to each of the plates 120 a and 120 b. These may be constructed of aluminum, carbon fiber, steel, or other material that one of skill in the art would understand to be applicable. In this embodiment, a spring 160 is positioned between the plate 120 a that is adjacent to the bioanode 150 and the housing wall 110 b. The spring 160 is employed to apply pressure to the electrodes thus keeping them in position. Prior to use, the capsule 170 , including the bioanode chamber and the biocathode chamber, will be filled with electrolyte solution 180 .
[0030] Referring now to FIG. 2 , the bioelectrode 210 of FIG. 2 may comprise a metal electrode, such as steel or aluminum, and carbon nanotube layer 220 that is well dispersed in a redox-polymer-enzyme 230 matrix. Enzymes of a bioelectrode catalyze redox reactions. It will be appreciated by those skilled in the art that the bioelectrode may also be fabricated with the enzymes covalently bonded to the matrix, or attached with an immobilizer, such as a linker protein, in which case some enzymes may require a mediator in the electrolyte fuel fluid to transfer the charge to the electrode.
[0031] Referring now to FIG. 3 , a schematic diagram of a biosupercapacitor 310 of the instant disclosure is positioned in a circuit 320 , which provides peak power for all functions of the high power voltage rail 330 and steady state low power voltage rail 340 , and backup power for the unit. The biosupercapacitor will provide power in bursts as needed by the different functions on the high voltage power rail 330 , and is re-charged in between peaks.
[0032] Myriad techniques for immobilizing mitochondria, enzymes, and enzyme cascades exist and may include crosslinking of mitochondria to a carbon electrode in the presence of stabilizing proteins, and/or crosslinking the enzymes to each other for greater efficiency. In some embodiments, the immobilization technique employs non-covalent (van der Waals, hydrophobic-hydrophobic, and ionic) or covalent interactions between unmodified and modified nanotubes. Other embodiments include techniques that employ the adsorption or desorption of intercalation metal oxides or conductive redox polymers. Furthermore, in some embodiments the enzymes to be immobilized are genetically engineered to include artificially added residues or complexes that comprise metal binding sites. These metal binding sites may be allocated to a specific region of on the enzyme, which enables covalent bonding to occur between the enzymes and the immobilization material on the electrode.
[0033] More specifically, the immobilizer may be produced from a naturally, or non-naturally occurring, colloidal material, a micellar or inverted micellar material, polymer, membrane, gel, carbon black, carbon nanotubes, and/or graphene. Furthermore, carbon black, nanotubes, and graphene, may be modified, such as with a manganese dioxide coating or other coatings that act as a catalyst for oxygen reduction reaction and may be either single walled (SWCNTs) or multiwalled (MWCNTs).
[0034] Referring again to FIG. 1 , the bioelectrodes of the instant disclosure comprise a biocathode 130 and a bioanode 150 . As discussed above, these bioelectrodes are separated from each other by a barrier 140 . The barrier defines the interface between a bioanode chamber and a biocathode chamber. In some embodiments, the barrier 140 may comprise a separator. The separator, as defined herein, comprises a material that absorbs or adsorbs electrolyte 180 . Such an electrolyte-absorbing or -adsorbing separator may fill the entire volume between the electrodes. It may be comprised of a membrane, a microporous material, or an ion-conducting material. Exemplary materials for constructing a separator include paper, microporous hydrophilic plastic films, and glass felts. The separator may further comprise an ion-conducting solid, gel, or other material.
[0035] Myriad materials, such as collector grids, expanded metal, meshes and foils, or scintered matrixes may be employed in the electrode assembly. It will further be appreciated that biological supercapacitors may be constructed without separators, for instance with a physical separation between electrodes or electrolyte.
[0036] The electrolyte 180 , as shown in the embodiment of FIG. 1 , may be comprised of organic fuels, such as pyruvate or its metabolites (such as succinate, malate, fumarate, acetyl-CoA, citrate, isocitrate, and ketoglutarate), fatty acids and their metabolites, or amino acids.
[0037] For electron transfer, the electron may be transferred directly to the electrode, or a mediator may be included in the design. In one aspect of the invention, mitochondria, which also contain the electron transport chain, will allow for the transport of electrons generated from oxidation of the fuel in the Kreb's cycle to the outer surface of the mitochondria for communication with the electrode.
[0038] In some embodiments, mediators may be used to conduct or enhance the enzymatic reaction. Appropriate mediators will have good redox potential, reversibility, and other features that increase the lifetime and stability of the device. A common polymeric redox mediator is poly(methylene green) and ferricyanide is a common small molecule mediator. In addition, osmium redox hydrogels, metallacarboranes, and ferrocene-based redox polymers may also be used as mediators. In some embodiments, the mediator comprises a biological enzyme co-factor.
[0039] Further, the inclusion of a mediator in a biological supercapacitor in connection with the double layer capacitance phenomenon, may cause charge transfer (Faradaic) to occur between the electrode/electrolyte interface. This is termed pseudocapacitance. Pseudocapacitance is accompanied by an electron charge-transfer between electrolyte and electrode coming from a de-solvated and adsorbed ion.
[0040] Biological supercapacitors according to the instant disclosure have a variety of uses. They may be used to provide pulse power, drop test and hot swap support, support for “last gasp” transmissions and “graceful shutdown”. In addition, they may be used to enable smaller, cheaper, lighter, and more efficient batteries/power supplies by providing peak power for all functions and backup power for the unit. The battery will only need to deliver average power and the biological supercapacitor will deliver peak power in bursts as needed by the different functions, and is re-charged in between peaks. This also means the DC:DC converter only needs to be sized for average power rather than peak power. Typically the battery would be a Li-ion cell.
[0041] Biocompatible and “micro” energy sources are critical to the development of novel commercial bioelectronics, such as health monitoring devices and medical technologies (rapid analysis of DNA, RNA, metabolites—i.e. biomolecule to biosensors), disease treatment devices (nanoscale delivery vehicles that require biocompatibility to interface with tissues or single cells) and neural and biochemical prosthetics (artificial sensory organs that require tissue integration or wireless networks). Additional uses are for self-powered sensors, and bioelectrocatalytic logic gates, consumer and hand-held electronics, the “Internet of Things”, smart grid infrastructure, other types of energy generating infrastructure (i.e. wind turbines).
EXAMPLE 1
Biosupercapacitor Fabrication
[0042] In general, the biological supercapacitor according to the instant disclosure comprises a biocathode, a bioanode, a barrier which may comprise a separator positioned between the biocathode and the bioanode, and an electrolytic fuel fluid. Both of the electrodes may comprise a carbon element, for example metallic, glassy carbon or other conventional electrode surfaces onto which one or more enzymes may be immobilized.
[0043] In one embodiment, the bioelectrodes comprise buckypaper of various thicknesses (15-250 μm), purity of ˜100% MWNTs, and/or CMN grade-buckypaper of 15-250 μm. The carbon nanotube layer can be well dispersed in a redox-polymer-enzyme matrix, for mediated charge transfer. Enzymes of a bioelectrode catalyze redox reactions. It will be appreciated by those skilled in the art that the bioelectrode may also be fabricated with the enzymes covalently bonded to the matrix, or attached with an immobilizer, like a linker protein, in which case they may require mediators in the electrolyte fuel fluid to transfer the charge. Other embodiments may comprise multi-layers of modified Nafion® NRE-212 PEM, bonded redox enzymes, and mediators like poly(methylene green). It will be appreciated by those skilled in the art that the bioelectrode material may also be fastened to a metal disk or plate, such as steel, aluminum, copper, or other metal. A separator is positioned between the biocathode and the bioanode. In separating the bioanode from the biocathode, two chambers are defined.
[0044] The biological supercapacitor may further comprise an electrically conductive current collector element immobilized with a biological electron donor or acceptor. In some embodiments, the electrically conductive current collector element may comprise of nickel, copper, aluminum, titanium, or combinations thereof. The current collector element may be connected to elements in a circuit, such as: comparator with hysteresis, microgenerators, active balance circuit, boost converter, single or paired (p-channel) metal-oxide-semiconductor field-effect transistors, and the like.
[0045] In one embodiment, the biosupercapacitor may be fabricated by packing and pressing both the bioanode and the biocathode into their respective chambers within a biosupercapacitor cell as is known in the art. Specifically, the cell may resemble a box or container of any shape that will serve to enclose the fuel, the bioanode, and the biocathode, along with a barrier or separator. In one embodiment, the cell comprises PVC. Hardware, including but not limited to bolts and nuts, may be employed to compress the chambers and hold the parts of the apparatus together as described herein as well as ensure that proper seal forms between the biocathode and bioanode chambers. Fuel may then be added to both the bioanode chamber and the biocathode chamber.
[0046] In one embodiment, the electrically conductive current collector element is a nickel mesh. This nickel mesh may be connected to the each of the chambers to serve as the current collector and then subsequently connected to a galvanostat for electrochemical characterization. The potentiostat/galvanostat may be interfaced with a computer for data collection of power density, current density and open circuit potential, as well as the charging and discharging profile output generated by the biosupercapacitor. When the biosupercapacitor is in use to power an electrical device, the electrically conductive current collector element may be connected to key circuit features that will interface an energy harvesting source from the biosupercapacitor to the circuit. These include: maximum power tracking, maintaining the output voltage or current of the energy harvesting source so it delivers the maximum possible power, over-voltage protection to ensure the supercapacitor rated voltage is not exceeded, and active balancing to maintain the supercapacitor cells at the same voltage with a low current circuit.
Bioanode Fabrication
[0047] In one embodiment, fabrication of the bioanode may be achieved by immobilizing lactate oxidase (LOx) on a laser cut buckypaper anode by mixing the enzymes with C8-LPEI (linear polyethylenimine) hydrogel and cross-linker. To prepare electrodes, 1.125 U of LOx (0.3 mg) may be combined with 154 μl of 10 mg/ml C8-LPEI (in deionized water) and mixed thoroughly. Then 8 μl of a 20% v/v solution of EGDGE (ethylene glycol diglycidyl ether) in deionized water may be added and the solution will again be mixed. Finally, 50 μl of the resulting solution may pipetted onto each electrode and allowed to dry for at least one hour. It will be appreciated by those skilled in the art that the bioanode materials may also be further fastened to a metal disk or plate, such as steel, aluminum, copper, or other metal.
Biocathode Fabrication
[0048] In one embodiment, fabrication of the biocathode may be achieved by placing laser-cut buckypaper in a 0.4 mM 1-pyrenemethyl anthracene-2-carboxylate (436 g/mol) solution in methylene chloride for 24 hours. During this time, the pyrene binds to the multi-walled carbon nanotubes (MWCNTs) within the buckypaper through π-π stacking, leaving the anthracene end free to bind to the bilirubin oxidase (BOD) or laccase (LAC) enzyme, thus orienting the enzyme for better direct electron transfer. The modified buckypaper will be removed from the solution and air-dried, and the leads will be dipped in wax for insulation. Then BOD/LAC will be cast onto the electrode in a TBAB-modified Nafion/PBS solution, which may be synthesized as previously described in the art. Specifically, for electrodes, 1.5 mg of BOD may be mixed thoroughly with 75 μl of 150 mM PBS (130 mM NaCl, 10 mM sodium phosphate monobasic, 10 mM sodium phosphate dibasic, pH-adjusted to 7.4). Next, 25 μl of TBAB-modified Nafion may be added and the solution will be mixed again. Finally, 30 μl of solution may be pipetted onto each cathode and allowed to air-dry for at least an hour. It will be appreciated by those skilled in the art that the biocathode material may also be further fastened to a metal disk or plate, such as steel, aluminum, copper, or other metal.
Fuel
[0049] A variety of biomolecules may be used as fuel. The biomolecules typically comprise organic molecules. Examples include, but are not limited to, sugars (including, but not limited to, sucrose, glucose, and fructose), alcohols (including, but not limited to, methanol, ethanol, and glycerol), acids (including, but not limited to, pyruvate and lactate), and fatty acids. In one embodiment, the fuel comprises 200 mM glucose in O 2 saturated phosphate buffer, pH 6.4.
[0050] High energy density is a very important characteristic of the fuel to be used in the biosupercapacitor. However, the usable energy density is usually decreased significantly when the degree of catalytic oxidation of the fuel is considered, as well as the maximum allowable fuel concentration for the fuel cell. Here, we ensure deep oxidation of fuel by using several enzymes that oxidize the fuel in a stepwise fashion.
Equivalents
[0051] The foregoing written specification is sufficient to enable one skilled in the art to practice the invention. Indeed, various modifications of the above-described means for carrying out the invention, which are obvious to those skilled in the field of biochemistry, molecular biology, electrical engineering, mechanical engineering, or materials science or related fields are intended to be within the scope of the following claims. Although the invention has been shown and described with respect to a certain preferred embodiment or embodiments, it is obvious that equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings. In particular regarding the various functions performed by the above described elements (components, assemblies, devices, compositions, etc.), the terms (including a reference to a “means”) used to describe such elements are intended to correspond, unless otherwise indicated, to any element which performs the specified function of the described element (i.e., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiment or embodiments of the invention. In addition, while a particular feature of the invention may have been described above with respect to only one or more of several illustrated embodiments, such feature may be combined with one or more other features of other embodiments, as may be desired and advantageous for any given or particular application. | A biological supercapacitor comprising at least one pair of electrodes that comprise immobilized biological materials that includes enzymes. The enzymes are immobilized to the electrodes and may be isolated enzymes, enzyme cascades comprising multiple enzymes, whole cells, organelles from cells, or parts of organelles from cells. An aspect of the disclosed biological supercapacitor is that a byproduct is water. The disclosed biological supercapacitor combines the energy density of a battery with the power density of a supercapacitor in order to reduce the size and weight of the energy storage devices. Methods of fabrication and of use of the biological supercapacitor are also disclosed. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application of U.S. application Ser. No. 13/064,987, filed Apr. 29, 2011, which was a continuation of U.S. application Ser. No. 12/801,952, filed Jul. 2, 2010, which was a continuation of U.S. application Ser. No. 12/659,980, filed Mar. 26, 2010, which issued as U.S. Pat. No. 7,797,970, which was a divisional of U.S. application Ser. No. 11/806,245, filed May 30, 2007, which issued as U.S. Pat. No. 7,743,633, which in turn claims the benefit of Korean Patent Application Nos. 2006-49501 and 2006-49482, both filed on Jun. 1, 2006, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference.
BACKGROUND
[0002] 1. Field
[0003] The present invention relates generally to a washing machine having at least one balancer, and more particularly to a washing machine having at least one balancer that increases durability by reinforcing strength and that is installed on a rotating tub in a convenient way.
[0004] 2. Description of the Related Art
[0005] In general, washing machines do the laundry by spinning a spin tub containing the laundry by driving the spin tub with a driving motor. In a washing process, the spin tub is spun forward and backward at a low speed. In a dehydrating process, the spin tub is spun in one direction at a high speed.
[0006] When the spin tub is spun at a high speed in the dehydrating process, if the laundry leans to one side without uniform distribution in the spin tub or if the laundry leans to one side by an abrupt acceleration of the spin tub in the early stage of the dehydrating process, the spin tub undergoes a misalignment between the center of gravity and the center of rotation, which thus causes noise and vibration. The repetition of this phenomenon causes parts, such as a spin tub and its rotating shaft, a driving motor, etc., to break or to undergo a reduced life span.
[0007] Particularly, a drum type washing machine has a structure in which the spin tub containing laundry is horizontally disposed, and when the spin tub is spun at a high speed when the laundry is collected on the bottom of the spin tub by gravity in the dehydrating process, the spin tub undergoes a misalignment between the center of gravity and the center of rotation, thus resulting in a high possibility of causing excess noise and vibration.
[0008] Thus, the drum type washing machine is typically provided with at least one balancer for maintaining a dynamic balance of the spin tub. A balancer may also be applied to an upright type washing machine in which the spin tub is vertically installed.
[0009] An example of a washing machine having ball balancers is disclosed in Korean Patent Publication No. 1999-0038279. The ball balancers of a conventional washing machine include racers installed on the top and the bottom of a spin tub in order to maintain a dynamic balance when the spin tub is spun at a high speed, and steel balls and viscous oil are disposed within the racers to freely move in the racers.
[0010] Thus, when the spin tub is spun without maintaining a dynamic balance due to an unbalanced eccentric structure of the spin tub itself and lopsided distribution of the laundry in the spin tub, the steel balls compensate for this imbalance, and thus the spin tub can maintain the dynamic balance.
[0011] However, the ball balancers of the conventional washing machine have a structure in which upper and lower plates formed of plastic by injection molding are fused to each other, and a plurality of steel balls are disposed between the fused plates to make a circular motion, so that the ball balancers are continuously supplied with centrifugal force that is generated when the steel balls make a circular motion, and thus are deformed at walls thereof, which reduces the life span of the balancer.
[0012] Further, the ball balancers of the conventional washing machine do not have a means for guiding the ball balancers to be installed on the spin tub in place, so that it takes time to assemble the balancers to the spin tub.
[0013] In addition, the ball balancers of the conventional washing machine have a structure in which a racer includes upper and lower plates fused to each other, so that fusion scraps generated during fusion fall down both inwardly and outwardly of the racer. The fusion scraps that fall down inwardly of the racer prevent motion of the balls in the racer, and simultaneously result in generating vibration and noise.
SUMMARY
[0014] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a washing machine having at least one balancer that increases durability by reinforcing the strength of the balancer, which is installed on a rotating tub in a rapid and convenient way.
[0015] Another object of the present invention is to provide a washing machine having at least one balancer, in which fusion scraps generated by fusion of the balancer are prevented from falling down inward and outward of the balancer.
[0016] Additional aspects and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the invention.
[0017] In order to accomplish these objects, according to an aspect of the present invention, there is provided a washing machine having a spin tub to hold laundry to be washed and at least one balancer. The balancer includes first and second housings, the first housing having at least one support for reinforcing a strength of the balancer. The first and second housings have an annular shape and are fused together to form a closed internal space.
[0018] Here, the first housing may have the cross section of an approximately “C” shape, and the support protrudes outwardly from at least one of opposite walls of the first housing.
[0019] Further, the spin tub may include at least one annular recess corresponding to the balancer such that the balancer is able to be coupled to the spin tub by being fitted within the recess.
[0020] Further, the support may protrude from the first housing and comes into contact with a wall of the recess, and guides the balancer to be maintained in the recess in place.
[0021] Also, the supports may be continuously formed along and perpendicular to the opposite walls of the first housing.
[0022] Further, the supports may be disposed parallel to the opposite walls of the first housing at regular intervals.
[0023] Meanwhile, the washing machine may be a drum type washing machine. A front member may be attached to a front end of the spin tub and a rear member may be attached to a rear end of the spin tub. The recesses may be provided at the front and rear members of the spin tub, and the balancers may be coupled to opposite ends of the spin tub at the recesses of the front and rear members.
[0024] The foregoing and/or other aspects of the present invention can be achieved by providing a washing machine having at least one balancer. The balancer includes a first housing and a second housing fused to the first housing, and the first and second housings are fused together to form at least one pocket between the first housing and the second housing, the pocket capable of collecting fusion scraps generated during fusion.
[0025] Here, the first housing may include protruding fusion ridges protruding from ends of the first housing, and the second housing may include fusion grooves receiving the fusion ridges of the first housing when the first housing and the second housing are fused together.
[0026] Further, the first housing may further include inner pocket ridges protruding from the first housing and spaced inwardly apart with respect to the fusion ridges of the first housing.
[0027] Further, the second housing may further include outer pocket flanges protruding from the second housing and being situated on outer sides of the fusion grooves when the first housing is fused together with the second housing so the outer pocket flanges are spaced apart from the fusion ridges of the first housing by a predetermined distance, causing an outer pocket to be formed between the fusion ridges and the outer pocket flanges.
[0028] Further, the second housing may include guide ridges protruding from the second housing and protruding toward the first housing to closely contact the inner pocket ridges of the first housing when the first and second housings are fused together.
[0029] Also, the balancer may further include a plurality of balls disposed within an internal space formed by fusing the first and second housings together, the balls performing a balancing function.
[0030] In addition, the washing machine may further include a spin tub disposed horizontally, and the balancers may be installed at front and rear ends of the spin tub.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] The above and other aspects, features and advantages of the present invention will be more apparent from the following detailed description of the embodiments, taken in conjunction with the accompanying drawings, in which
[0032] FIG. 1 is a sectional view illustrating a schematic structure of a washing machine according to the present invention;
[0033] FIG. 2 is a perspective view illustrating balancers according to the present invention, in which the balancers are disassembled from a spin tub;
[0034] FIG. 3 is a perspective view illustrating a balancer according to a first embodiment of the present invention;
[0035] FIG. 4 is an enlarged view illustrating section A of FIG. 1 in order to show the sectional structure of a balancer according to a first embodiment of the present invention;
[0036] FIG. 5 is a perspective view illustrating a balancer according to a second embodiment of the present invention;
[0037] FIG. 6 is an enlarged view illustrating the sectional structure of a balancer according to the second embodiment of the present invention;
[0038] FIG. 7 is a perspective view illustrating a disassembled balancer according to a third embodiment of the present invention;
[0039] FIG. 8 is a perspective view illustrating an assembled balancer according to the third embodiment of the present invention;
[0040] FIG. 9 is a partially enlarged view of FIG. 7 ; and
[0041] FIG. 10 is a sectional view taken line A-A of FIG. 8 .
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0042] Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements throughout. The embodiments are described below to explain the present invention by referring to the figures.
[0043] Hereinafter, exemplary embodiments of the present invention will be described with reference to the attached drawings.
[0044] FIG. 1 is a sectional view illustrating the schematic structure of a washing machine according to the present invention.
[0045] As illustrated in FIG. 1 , a washing machine according to the present invention includes a housing 1 forming an external structure of the washing machine, a water reservoir 2 installed in the housing 1 and containing washing water, a spin tub 10 disposed rotatably in the water reservoir 2 which allows laundry to be placed in and washed therein, and a door 4 hinged to an open front of the housing 1 .
[0046] The water reservoir 2 has a feed pipe 5 and a detergent feeder 6 both disposed above the water reservoir 2 in order to supply washing water and detergent to the water reservoir 2 , and a drain pipe 7 installed therebelow in order to drain the washing water contained in the water reservoir 2 to the outside of the housing 1 when the laundry is completely done.
[0047] The spin tub 10 has a rotating shaft 8 disposed at the rear thereof so as to extend through the rear of the water reservoir 2 , and a driving motor 9 , with which the rotating shaft 8 is coupled, installed on a rear outer side thereof. Therefore, when the driving motor 9 is driven, the rotating shaft 8 is rotated together with the spin tub 10 .
[0048] The spin tub 10 is provided with a plurality of dehydrating holes 10 a at a periphery thereof so as to allow the water contained in the water reservoir 2 to flow into the spin tub 10 together with the detergent to wash the laundry in a washing cycle, and to allow the water to be drained to the outside of the housing 1 through a drain pipe 7 in a dehydrating cycle.
[0049] The spin tub 10 has a plurality of lifters 10 b disposed longitudinally therein. Thereby, as the spin tub 10 rotates at a low speed in the washing cycle, the laundry submerged in the water is raised up from the bottom of the spin tub 10 and then is lowered to the bottom of the spin tub 10 , so that the laundry can be effectively washed.
[0050] Thus, in the washing cycle, the rotating shaft 8 alternately rotates forward and backward by of the driving of the driving motor 9 to spin the spin tub 10 at a low speed, so that the laundry is washed. In the dehydrating cycle, the rotating shaft 8 rotates in one direction to spin the spin tub 10 at a high speed, so that the laundry is dehydrated.
[0051] When spun at a high speed in the dehydrating process, the spin tub 10 itself may undergo misalignment between the center of gravity and the center of rotation, or the laundry may lean to one side without uniform distribution in the spin tub 10 . In this case, the spin tub 10 does not maintain a dynamic balance.
[0052] In order to prevent this dynamic imbalance to allow the spin tub 10 to be spun at a high speed with the center of gravity and the center of rotation thereof matched with each other, the spin tub 10 is provided with balancers 20 or 30 according to a first or a second embodiment of the present invention (wherein only the balancer 20 according to a first embodiment is shown in FIGS. 1-4 ) at front and rear ends thereof. The structure of the balancers 20 and 30 according to the first and second embodiments of the present invention will be described with reference to FIGS. 2 through 6 .
[0053] FIG. 2 is a perspective view illustrating balancers according to the present invention, in which the balancers are disassembled from a spin tub.
[0054] As illustrated in FIG. 2 , the spin tub 10 includes a cylindrical body 11 that has open front and rear parts and is provided with the dehydrating holes 10 a and lifters 10 b , a front member 12 that is coupled to the open front part of the body 11 and is provided with an opening 14 permitting the laundry to be placed within or removed from the body 11 , and a rear member 13 that is coupled to the open rear part of the body 11 and with the rotating shaft 8 (see FIG. 1 ) for spinning the spin tub 10 .
[0055] The front member 12 is provided, at an edge thereof, with an annular recess 15 that has the cross section of an approximately “C” shape and is open to the front of the front member 12 in order to hold any one of the balancers 20 . Similarly, the rear member 13 is provided, at an edge thereof, with an annular recess 15 (not shown) that is open to the rear of the front member 12 in order to hold the other of the balancers 20 .
[0056] The front and rear members 12 and 13 are fitted into and coupled to the front or rear edges of the body 11 in a screwed fashion or in any other fashion that allows the front and rear members 12 and 13 to be maintained to the body 11 of the spin tub 10 .
[0057] The balancers 20 , which are installed in the recesses 15 of the front and rear members 12 and 13 , have an annular shape and are filled therein with a plurality of metal balls 21 performing a balancing function and a viscous fluid (not shown) capable of adjusting a speed of motion of the balls 21 .
[0058] Now, the structure of the balancers 20 and 30 according to the first and second embodiments of the present invention will be described with reference to FIGS. 3 through 6 .
[0059] FIG. 3 is a perspective view illustrating a balancer according to a first embodiment of the present invention, and FIG. 4 is an enlarged view illustrating part A of FIG. 1 in order to show the sectional structure of a balancer according to a first embodiment of the present invention.
[0060] As illustrated in FIGS. 3 and 4 , a balancer 20 according to a first embodiment of the present invention has an annular shape and includes first and second housings 22 and 23 that are fused to define a closed internal space 20 a.
[0061] The first housing 22 has first and second walls 22 a and 22 b facing each other, and a third wall 22 c connecting ends of the first and second walls 22 a and 22 b , and thus has a cross section of an approximately “C” shape. The second housing 23 has opposite edges that protrude toward the first housing 22 and that are coupled to corresponding opposite ends 22 d of the first housing 22 by heat fusion.
[0062] The opposite ends 22 d of the first housing 22 protrude outward from the first and second walls 22 a and 22 b of the first housing 22 , and the edges of the second housing 23 are sized to cover the ends 22 d of the first housing 22 .
[0063] Thus, when the balancer 20 is fitted into the recess 15 of the front member 12 of the spin tub 10 , the first and second walls 22 a and 22 b are spaced apart from a wall of the recess 15 because of the ends and edges of the first and second housings 22 and 23 which protrude outward from the first and second walls 22 a and 22 b . Further, because the first and second walls 22 a and 22 b are relatively thin, the first and second walls 22 a and 22 b are raised outward when centrifugal force is applied thereto by the plurality of balls 21 that move in the internal space 20 a of the balancer 20 in order to perform the balancing function.
[0064] In this manner, the plurality of balls 21 make a circular motion in the balancer 20 , so that the first and second walls 22 a and 22 b are deformed by the centrifugal force applied to the first and second walls 22 a and 22 b of the first housing 22 . In order to prevent this deformation, the second housing 22 is provided with supports 24 according to a first embodiment of the present invention.
[0065] The supports 24 protrude from and perpendicular to the first and second walls 22 a and 22 b of the first housing 22 which are opposite each other, and may be continued along an outer surface of the first housing 22 , thereby having an overall annular shape.
[0066] The supports 24 have a length such that they extend from the first housing 22 to contact the wall of the recess 15 . Hence, the first and second walls 22 a and 22 b are further increased in strength, and additionally function to guide the balancer 20 so as to be maintained in the recess 15 in place.
[0067] Here, when the plurality of balls 21 make a circular motion in the first housing 22 , the centrifugal force acts in the direction moving away from the center of rotation of the spin tub 10 . Hence, the centrifugal force acts on the first wall 22 a to a stronger level when viewed in FIG. 4 . Thus, the supports 24 may be formed only on the first wall 22 a.
[0068] In the balancer 20 according to the first embodiment of the present invention, when the first and second housings 22 and 23 are fused together and fitted into the recess 15 of the spin tub 10 , the supports 24 are maintained in place while positioned along the wall of the recess 15 . Finally, the balancer 20 is coupled and fixed to the front member 12 of the spin tub 10 by screws (not shown) or in any other fashion that allows the balancer 20 to be coupled to the front member 12 .
[0069] Although not illustrated in detail, the balancer 20 is similarly installed on the rear member 13 of the spin tub 10 .
[0070] The ends 22 d of the first housing 22 include fusion ridges 42 a that protrude toward the second housing 23 . The fusion ridges 42 a are inserted within fusion grooves 43 a of the second housing 23 .
[0071] FIGS. 5 and 6 correspond to FIGS. 3 and 4 , and illustrate a balancer 30 according to a second embodiment of the present invention.
[0072] The balancer 30 according to the second embodiment of the present invention has an annular shape and includes first and second housings 32 and 33 that are fused together forming an internal space 30 a therebetween in which a plurality of balls 31 are disposed. The balancer 30 according to the second embodiment of the present invention is similar to that of balancer 20 according to the first embodiment of the present invention, except the structure of supports 34 of balancer 30 is different from that of the structure of the supports 24 of balancer 20 .
[0073] As illustrated in FIGS. 5 and 6 , the supports 34 according to the second embodiment of the present invention protrude parallel to first and second walls 32 a and 32 b of a first housing 32 which are opposite each other, and the supports 34 are disposed at regular intervals along the first and second walls 32 a and 32 b . The first housing 32 further includes a third wall 32 c . Ends 22 d of the first housing 32 extend from an end of the first and second walls 32 a and 32 b.
[0074] Similar to the supports 24 according to the first embodiment, the supports 34 of the second embodiment have a length such that the supports 34 extend from the first housing 32 to contact the wall of the recess 15 . The surfaces of the supports 34 thereby abut portions of the front member 12 . Hence, the first and second walls 32 a and 32 b are further increased in strength, and additionally function to guide the balancer 30 so as to be maintained in the recess 15 in place.
[0075] Next, the construction of a balancer 40 according to a third embodiment of the present invention will be described with reference to FIGS. 7 through 10 .
[0076] FIGS. 7 and 8 are perspective views illustrating disassembled and assembled balancers according to the third embodiment of the present invention, FIG. 9 is a partially enlarged view of FIG. 7 , and FIG. 10 is a sectional view taken along line A-A of FIG. 8 .
[0077] As illustrated in FIGS. 7 and 8 , a balancer 40 includes a first housing 42 having an annular shape and a second housing 43 having an annular shape that is fused to the first housing 42 , thereby forming an annular housing corresponding to the recess 15 (see FIG. 2 ) of the spin tub 10 . The first and second housings 42 and 43 may be, for example, formed of synthetic resin, such as plastic by injection molding.
[0078] As illustrated in FIG. 9 , the first housing 42 has a cross section of an approximately “C” shape, includes fusion ridges 42 a protruding to the second housing 43 at opposite ends thereof which are coupled with the second housing 43 , and inner pocket ridges 42 b protruding to the second housing 43 spaced inwardly apart from the fusion ridges 42 a.
[0079] The second housing 43 , which is coupled to opposite ends of the first housing 42 in order to form a closed internal space 40 a for holding a plurality of balls 41 and a viscous fluid, includes fusion grooves 43 a recessed along edges thereof so as to correspond to the fusion ridges 42 a , outer pocket flanges 43 b and guide ridges 43 c . The outer pocket flanges protrude to the first housing 42 on outer sides of the fusion grooves 43 a so as to be spaced apart from the fusion ridges 42 a of the first housing 42 by a predetermined distance. The guide ridges 43 c protrude to the first housing 42 on inner sides of the fusion grooves 43 a and closely contact the inner pocket ridges 42 b of the first housing 42 .
[0080] The guide ridges 43 c of the second housing 43 move in contact with the inner pocket ridges 42 b of the first housing 42 when the second housing 43 is fitted into the first housing 42 , to thereby guide the fusion ridges 42 a of the first housing 42 to be fitted into the fusion grooves 43 a of the second housing 43 rapidly and precisely.
[0081] Thus, when the fusion ridges 42 a of the first housing 42 are fitted into the fusion grooves 43 a of the second housing 43 in order to fuse the first housing 42 with the second housing 43 , as shown in FIG. 10 , an inner pocket 40 b having a predetermined spacing is formed between the fusion ridges 42 a and inner pocket ridges 42 b , and an outer pocket 40 c having a predetermined spacing is formed between the fusion ridges 42 a and the outer pocket flanges 43 b.
[0082] In this state, when heat is generated between the fusion ridges 42 a of the first housing 42 and the fusion grooves 43 a of the second housing 43 , the fusion ridges 42 a and the fusion grooves 43 a are firmly fused with each other. At fusion, fusion scraps that are generated by heat and fall down inward of the first housing 42 are collected in the inner pocket 40 b , so that the scraps are not introduced into the internal space 40 a of the balancer 40 in which the balls 41 move. Fusion scraps falling down outward of the first housing 42 are collected in the outer pocket 40 c , and thus are prevented from falling down outward of the balancer 40 .
[0083] In the embodiments, the balancers 20 , 30 and 40 have been described to be installed on a drum type washing machine by way of example, but it is apparent that the balancers can be applied to an upright type washing machine having a structure in which a spin tub is vertically installed.
[0084] As described above in detail, the washing machine according to the embodiments of the present invention has a high-strength structure in which at least one balancer is provided with at least one support protruding outward from the wall thereof, so that, although the strong centrifugal force acts on the wall of the balancer due to a plurality of balls making a circular motion in the balancer, the wall of the balancer is not deformed. Thus, the plurality of balls can make a smooth circular motion without causing excess vibration and noise, and thus increasing the durability and life span of the balancer.
[0085] Further, the washing machine according to the embodiments of the present invention has a structure in which the balancer can be rapidly and exactly positioned in the recess of the spin tub by the supports, so that an assembly time of the balance can be reduced.
[0086] In addition, the washing machine according to the present invention has a structure in which fusion scraps generated when the balancer is fused are collected in a plurality of pockets, and thus are prevented from falling down inward and outward of the balancer, so that the internal space of the balancer, in which a plurality of balls are filled and move in a circular motion, has a smooth surface without the addition of fusion scraps. As a result, the balls are able to move more smoothly, and excess noise and vibration are minimized. The balancer may have a clear outer surface to provide a fine appearance without the fusion scraps, so that it can be exactly coupled to the spin tub without obstruction caused by the fusion scraps.
[0087] Although a few embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims and their equivalents. | A drum type washing machine including a housing, a rotating spin tub to hold laundry to be washed and a ball balancer coupled to the spin tub to compensate for a dynamic imbalance during rotation thereof. The ball balancer includes a first plastic member and a second plastic member joined to each other to form a closed internal space in which a plurality of balls and viscous fluid are accommodated, the first plastic member includes a first side wall, a second side wall and a connecting wall to form a three-sided annular-shaped structure having an open side, and the second plastic member is adapted to cover the open side of the first plastic member. A diameter of each of the balls is smaller than a depth of the three-sided annular-shaped structure measured from the connecting wall to a top of the first side wall. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to whipstocks for installation in subterranean well casings and an improved apparatus for effecting the installation of a whipstock in a casing with the arcuate face of a whipstock disposed at a desired angular relationship with respect to the casing.
2. Description of the Prior Art
Obstructions and blockages are often encountered in subterranean well casings which interfere with the production or further drilling of the well. In such cases, it has been the practice to deflect the drilling tool angularly so that it cuts through the casing and then produces a new bore which is directed downwardly and laterally in order to pass around the blockage or obstruction and re-orientate the hole. Whenever it is necessary that such hole or window be cut in the casing wall, it is generally required that the angular position of the window be precisely located, so that the new hole will successfully avoid the blockage or other obstructions and will proceed toward the production formation along a prescribed path.
The angular deflection of the drill bit has in the past been accomplished by the installation of a whipstock which is a guide element having a longitudinally tapered arcuate face so as to deflect the drilling tool angularly toward the inside wall of the casing to permit it to cut a hole or window in the casing. Special packers have heretofore been employed for mounting whipstocks in casings, and a common problem of such prior art packers has been the necessity for installing the packer in a precise angular position within the casing in order to insure that the arcuate face of the whipstock will be precisely positioned at the desired angle. For example, U.S. Pat. No. 4,153,109 issued to Szescila discloses a whipstock mounting system wherein the angular orientation of the arcuate face of the whipstock is determined by the engagement of a key slot provided on the whipstock anchor with a key provided in the central bore of a packer. The packer must, therefore, first be located in the well casing with the key in the precise angular position desired to effect the subsequent precise angular location of the arcuate face of the whipstock. This requirement has resulted in the necessity of employing a tubing string to effect the installation of the packer in the well casing resulting in an expensive and time consuming operation.
SUMMARY OF THE INVENTION
This invention provides an apparatus for effecting the installation and acurate angular orientation of the arcuate tool guiding face of a whipstock in a well conduit, such as casing. A packer designed in accordance with this invention is first lowered into the well casing and expanded therein at the depth where the cutting of a window is required. Such packer is installed by conventional wire line operated equipment, can also be set on tubing or drill pipe and is provided with a key projecting into its angular bore which may occupy any angular orientation relative to the conduit. A conventional well survey is then run to precisely determine the angular location of the packer key and this location is expressed in terms of polar coordinates. A whipstock anchor is provided having a socket portion in which a whipstock is rigidly secured and an elongated shaft portion which is rotatable relative to the socket portion about an axis that is coincident with the casing axis when the shaft portion is installed within the bore of the packer. The shaft portion is provided with a keyway to cooperate with the packer key when installation is effected.
An annular compass card is slipped over the shaft portion of the whipstock anchor and a scribe on such shaft portion indicates the angular location of the keyway. The socket portion of the anchor is rotated relative to the shaft to bring the arcuate tool guiding face of the whipstock into precisely the desired angular orientation relative to the keyway that is necessary to effect the cutting of a window in the casing in the desired direction when the installation is completed. The whipstock socket is then rigidly anchored to the shaft by tightening of set screws and the entire assembly is lowered on drill pipe or other tubular conduit into the casing and into cooperating relationship with the packer, with the keyway of the shaft of the whipstock anchor engaging the key of the packer. An expandable thread dog mechanism is provided on the whipstock anchor to engage the internal threads customarily provided on the packer and to effect the rigid vertical securement of the whipstock and whipstock anchor in the well conduit, at the desired depth, with the arcuate face of the whipstock positioned to face precisely in the direction that the window in the conduit is to be cut.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of an assembled whipstock and packer designed in accordance with this invention.
FIGS. 2a, 2b, 2c, 2d and 2e together constitute an enlarged scale combined side elevational view and longitudinal section of the whipstock and packer shown in FIG. 1, FIGS. 2b, 2c, 2d and 2e being lower continuations of FIGS. 2a, 2b, 2c and 2d, respectively.
FIGS. 3a, 3b and 3c together constitute a longitudinal sectional view of a packer embodying this invention shown with its elements in their well inserting positions and prior to expansion of the elements into engagement with the well casing, FIGS. 3b and 3c being lower continuations of FIGS. 3a and 3b respectively.
FIG. 4 is a sectional view taken on the plane 4--4 of FIG. 2c.
FIG. 5 is an elevational view of an annular compass card employed to orient the whipstock relative to the whipstock anchor shaft.
FIG. 6 is a perspective view showing the utilization of the compass card of FIG. 5 in the orientation procedure.
FIG. 7 is a partial sectional view similar to FIG. 2c, but with the fluid guide sleeve located in its packer inserting position.
FIG. 8 is an enlarged scale, partial sectional view of the anchor teeth portion of the packer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIGS. 1 and 2a, 2b, 2c, 2d and 2e there is shown a whipstock 10 having an arcuate tool guiding face 13, mounted in a whipstock anchor 20 which includes a socket portion 22, a shaft portion 26, and an anchor sub or sleeve 23 and an expandable thread sleeve 30. The sleeve 30 effects the mounting of the whipstock anchor 20 within the interior bore of a packer assembly 40 which has its upper and lower slips 42 and 44 respectively expanded into gripping engagement with the interior wall 1a of the casing 1 and an annular mass of elastomeric material 46 disposed intermediate the upper and lower slips is expanded to sealingly engage the interior wall 1a of the casing 1. At the extreme lower end of the packer assembly 40, a key 48e is provided which cooperates with an axially extending keyway 26a provided in the bottom end of the shaft portion 26 of the whipstock anchor 20. The interengagement of the key 48e with the keyway 26a determines the angular orientation of the arcuate tool guiding face 13 of the whipstock 10.
The primary purpose of this invention is to provide an apparatus for conveniently effecting the mounting of the whipstock 10 rigidly within the casing 1 with its arcuate tool guiding face 13 accurately facing exactly the direction in which it is desired to produce a window in the casing 1 by lowering a drilling tool 2 (FIG. 1) into the well which will be guided by the arcuate face 13 of the whipstock into engagement with the side wall of casing 1 to cut the window 1b.
The detailed structure of each of the aforementioned major components, namely, the whipstock, anchor and packer assemblages will now be described. Referring first to FIGS. 3a, 3b, and 3c, there is shown only the packer assembly 40 with the various movable elements thereof disposed in the position in which the packer assembly 40 is lowered into the well, i.e. the packer elements occupying the positions prior to expansion of the expandable elements to secure engagement of the packer 40 with the well casing 1.
The packer assembly 40 comprises a central sleeve-like body portion 41 which supports on its outer periphery a plurality of annular elements for effecting the expansion of the upper and lower slips 42 and 44 and the elastomeric packing sleeve 46 into firm engagement with the interior wall 1a of the casing 1. The main body sleeve 41 also defines adjacent its upper portions an axially extending length of internal anchor threads 41a.
The only other important element in the interior of the packer assembly is the axially extending, inwardly projecting key 48e previously mentioned which is rigidly mounted, as by welding, in the lowermost portions of an orientation sleeve 48 which is threadably secured by threads 48b to the bottom end of the main packer sleeve 41.
A plurality of relatively movable annular elements are mounted on the outer periphery of the main packer body sleeve 41. At the top of the packer 40, there is first an actuating sleeve 43 which extends upwardly beyond the end of the packer body sleeve 41 by a significant distance. The lower portion of actuating sleeve 43 is provided with an inwardly thickened portion 43a which has its internal bore surface formed with ratchet teeth or wickers 43b which cooperate with similarly formed external teeth on a body ring 41b which is secured to the periphery of the main body sleeve 41 of the packer 40. The purpose of the cooperating ratchet elements 43b and 41b is to readily permit downward movement of the actuating sleeve 43 relative to the main body sleeve 41 but to prevent any upward relative movement.
Immediately below the bottom end of actuating sleeve 43 is located the radial top surface 42a of the upper slip 42. The upper slip 42 is of conventional configuration, having a plurality of serrations or cutting edges 42b formed on its outer periphery and a vertically inclined cam surface 42c formed on its lower end to cooperate with the similarly inclined top surface 50a of an annular camming sleeve or upper cone 50. Additionally, the upper slip 42 is provided with a plurality of axially extending weakening slots (not shown) which permit this element to separate into annular segments when it is displaced outwardly by the cam surface 50a of upper cone 50.
A radial shear pin 50c is provided in radial relationship in the upper cone 50 engaging a suitable groove 41c provided on the external surface of the main body sleeve 41. The shear pin 50c maintains the cam 50 in its indicated position shown in FIG. 3a during the lowering of the packer 40 into the well casing.
The upper cone 50 additionally is provided with a lower cam surface 50b which engages the similarly inclined surface 52d of one of a pair of abutting back-up rings 52a and 52b. Rings 52a and 52b are axially split so as to permit them to be readily expanded outwardly by the action of the cam surface 50b of the upper cone 50 and are interconnected by an annular ridge and slot 52c to move as a unit. The axial splits in the elements 52a and 52b are preferably displaced 180° from each other, permitting both rings to expand into contact with the casing wall 1a.
Immediately below the back-up rings 52a and 52b, the annular mass 46 of elastomeric packing material is mounted. The end portions of the mass 46 are of reduced diameter as indicated at 46a and 46b and are respectively surrounded by rigid metallic cam rings 54 and 55. Upper ring 54 has an inclined surface 54a cooperating with the similarly inclined bottom surface 52e of the back-up ring 52b while the inclined lower surface 55a of cam ring 55 cooperates with the inclined upper surface 56d of a pair of back-up rings 56a and 56b which are identical in construction to the back-up rings 52a and 52b.
Immediately adjacent the lower inclined surface 56e of backup ring 56b is a lower cone 58 having its top surface 58a inclined to cooperate in camming relationship to the bottom surface 56e of the back-up ring 56b. The lower surface of the lower cone 58 is also of inclined configuration and incorporates a plurality of peripherally spaced dove-tailed key slots 58b which respectively receive correspondingly shaped elements 44a of a lower slip 44. Additionally, the lower cone 58 is provided with a shear pin 58c which temporarily engages an annular slot 41g provided in the surface of the main body sleeve 41. The outer periphery of the lower slip 44 is provided with a plurality of axially extending teeth or cutting edges 44b by which a firm engagement with the inside wall of the casing 1 may be secured when the lower slip 44 is expanded outwardly into engagement therewith.
The bottom end of the lower slip 44 is somewhat downwardly inclined but is similarly provided with dove-tailed slots 44c which cooperate with similarly shaped, inclined dove-tailed surfaces 48a provided on the top portion of an orientation sleeve 48. The sleeve 48 has a somewhat enlarged upper annular portion 48c provided with internal threads 48b which are engageable with threads provided on the bottom of the body sleeve 41.
The lower portions of orientation sleeve 48 define a bore 48d for slidably receiving the lower end portions of the whipstock anchor shaft 26. The bottom portion of the orientation sleeve 48 is provided with a radial recess within which the key 48e is rigidly affixed, such as by welding. The radially inward edge 48f of the key 48e engages the key slot 26a provided in the bottom end portion of the shaft 26 to secure such shaft in a fixed angular orientation relative to the packer assembly 40.
As previously mentioned, FIGS. 3a, 3b and 3c show the packer assembly 40 with its various components in the positions occupied during the running of the packer in the well casing. When the packer has been lowered to the desired vertical position in the well casing, the upper and lower slips 42 and 44 and the elastomeric packing element 46 are expanded into rigid sealing engagement with the interior wall 1a of the casing 1. The radial expansion of the elements of the packer assembly to the positions shown in FIGS. 2c, and 2d may be accomplished by any one of several well known packer expansion actuating devices, for example, the apparatus shown in U.S. Pat. No. 3,208,355 to Baker et al, which effects the necessary relative movements of elements of the packer assembly through forces derived by gas pressure developed by the explosion of a contained slow-burning powder charge or pellet. In any event, the setting of the packer is accomplished by concurrently applying a downward force to the top end 43c of the actuating sleeve 43, and an upward force to the internal square threaded portion 41a provided on the packer body portion 41.
The application of such relative forces results in the relative downward movement of the actuating sleeve 43, thus forcing the upper slip 42 outwardly to first split into annular segments and then to grip the casing wall 1a by virtue of its engagement with the conical cam surface 50a of the upper cone 50. The downward component of force on the upper cone 50 produced by such movement effects the severance of the shear pin 50c and the upper cone 50 then produces a downward and outward movement of the back-up rings 52a and 52b. These rings move outwardly toward the inner wall 1a of the casing 1 and at the same time exert a downward force on the cam ring 54 and, hence, on the annular elastomeric packing 46, forcing it outwardly by virtue of the compressive forces exerted thereon. The back up rings 52a and 52b effectively prevent axial displacement of the elastomeric packing 46.
Due to the fact that the packer body sleeve 41 is concurrently moving upwardly, similar actions are occurring at the lower end of the packer assembly to effect the outward expansion of the lower slip 44. The shearing of the shear pin 58c in the lower cone 58, and the upward and outward urging of the lower back-up rings 56a and 56b exert a compressive force on the elastomeric sleeve 46 thru the cam ring 55. As previously mentioned, the inter-engaging ratchet teeth 43b of the sleeve portion 43a and the lock sleeve 41b prevent any reverse relative movement of the actuating sleeve 43 and the packer body sleeve 41. Hence, once the respective expansion of the upper and lower slips 42 and 44 and the packing sleeve 46 into rigid engagement with the inner wall 1a of casing 1 has been accomplished, the packer is locked in such position relative to the casing and fluid flow between the exterior of the packer and the casing is effectively eliminated by the elastomeric packing 46. Any fluid leakage between the exterior of the packer body sleeve 41 and the expandable elements is eliminated by a seal structure 46c provided in the center of the elastomeric sleeve 46.
The packer 40 is, of course, anchored at a depth in the well which is slightly below the location of the window 1b that is desired to be cut in the casing 1 by a cutting tool 2 guided by a whipstock. The next step is to lower a well directional surveying apparatus into the well to determine the exact angular position of the key 48e of the anchored packer. A conventional and known gyroscopic survey apparatus is employed for this service which may actually engage the key 48e and provide an indication of its angular position relative to polar coordinates.
The completion of the survey thus provides the operator with precise knowledge of the angular position of the key 48e with respect to the normal polar coordinates. The operator then proceeds to assemble the whipstock, and the whipstock anchor and to effect the angular adjustment of the whipstock relative to the keyway provided in the bottom end of the whipstock anchor shaft. Such assembly operations are performed, of course, at the earth surface and do not require welding or other special machining operations.
Referring now to FIGS. 2a, 2b, 2c, and 2d, the assembled whipstock 10, whipstock socket 22, whipstock shaft 26 and the anchor sub 23 are illustrated. The whipstock 10 includes a lower anchor section 12 and an upper section 11 which has a partially cylindrical or convex exterior and a concave tapered inner tool guiding face 13. The lower end of the upper section is connected to the lower anchor section by means of a hinge pin 14. The anchor section 12 is threadably secured to the internal threads 22a provided in the socket portion 22 of the whipstock anchor. A plurality of radially disposed set screws 22b effect the securement of the threaded connection.
Immediately below the socket portion 22, the whipstock socket 22 is provided with internal threads 22k that engage the top end of the generally cylindrical guide sleeve 23 which extends a substantial distance into the packer and at its lower end is provided with an axially extending annular recess 23a within which a plurality of chevron-type seals 24 are provided to sealingly engage the internal bore surface 41d of the packer body sleeve 41. The bore 23b of the anchor sleeve 23 receives the anchor shaft portion 26 therein.
The bottom end of the anchor sleeve 23 is threaded at 23c to receive a shaft retaining sleeve or nut 25 which has an internally projecting shoulder 25a engaging an external shoulder 26b on the shaft 26 to hold the shaft in assembly prior to locking it to the socket portion 22 of the anchor assembly 20.
The extreme top portion 26c of the anchor shaft 26 is provided with an eccentric configuration, illustrated in FIG. 4, and a plurality of radially disposed set screws 27 are mounted in the socket portion 22 to engage the eccentric shaft portion 26c and secure it against angular displacement with respect to the whipstock socket, once the socket 22 has been correctly oriented relative to the keyway 26a provided in the bottom end of the anchor shaft.
The guide sleeve 23 is secured in surrounding relationship to the shaft 26 by internal threads 22k provided at the top end portion of sleeve 23 and the lower end of whipstock anchor socket 22. In an internal annular recess 22h provided in the bottom portion of socket 22 an expandable anchor sleeve 30 is mounted. The lower portions of anchor sleeve 30 are axially slotted to provide a plurality of annular segmental locking dogs 31, each of which has teeth portions 31a formed on their peripheries which cooperate with the internal square threads 41a provided on the packer body sleeve 41 (FIG. 8). The threaded dog elements 31 are not shown in detail since they are commonly employed in the art to effect the anchoring of a whipstock or any other form of downhole apparatus to the internal threads of a packer by being axially insertable within such threads and then radially expanded to engage the internal threads in threaded relationship. See, for example, U.S. Pat. No. 2,737,248 to Baker.
The external periphery of the guide sleeve 23 is suitably recessed as indicated at 23b to provide adequate clearance for inward deflection of the locking dogs 31 as the whipstock anchor assembly is inserted within the packer assembly 40. Additionally, the axial splines 23m are formed on the sleeve 23 lying intermediate dogs 31 to key the sleeves 30 and 23 together. Upon full insertion of the whipstock anchor assemblage 20 in the packer 40, the downwardly facing shoulder 23e provided on the sleeve 23 engages an upwardly facing shoulder 41e provided in the internal bore of the packer body sleeve 41. To permit insertion of the anchor sleeve 30, the threaded dog segments 31 slip past the internal threads 41a of the packer by virtue of being inclined surfaces on the bottom edges of the threads 31a. However, once the whipstock anchor assembly 20 reaches its described lowermost position, a slight upward movement of the assembly produced by the drill pipe 16 results in an outward camming of the locking dogs 31 through the engagement of the upwardly facing inclined surface 23f provided on the anchor sleeve 23 with the downwardly facing inclined surface 31b provided on the bottom ends of the cam dogs 31. As a result, the cam dogs 31 are fully threadably engaged with the interior threads 41a of the packer body sleeve 41 and the whipstock anchor 20 is rigidly secured to the packer assembly 40.
Prior to insertion of the whipstock anchor assembly into the packer assembly, it is necessary to angularly orient the arcuate tool guiding face 13 of the whipstock 10 relative to the keyway 26a provided in the bottom of the anchor shaft 26. Referring now to FIGS. 5 and 6, this invention provides a convenient apparatus for accurately effecting such angular orientation. An annular compass card 70 is provided having polar coordinates 71 printed on one face thereof. Such coordinates are, however, in mirror image reversed relationship to the normal direction of polar coordinates, because the annular compass card 70 will be applied to the shaft portion 26 of the whipstock anchor assembly 20 in an upside down relationship.
The annular compass card 70 may be slipped over one end of the shaft 26 and moved until the compass card engages the radial end face 25b of the retaining nut or sleeve 25. In this position, the compass card 70 intersects the vertical scribe line 26h which is angularly aligned with the center of the keyway 26a. The top surface of the compass card 70 is provided with a plurality of radially spaced, sheet like magnetic elements 75 which engage the radial end face 25b and adjustably secure the compass card 70 in position thereon, yet permitting convenient angular adjustment of such compass card relative to the axis of the shaft 26. The polar coordinates 71 on the compass card 70 are on the bottom face of the card and hence readily readable.
The directional well survey that had been previously made has provided an indication of the actual angular orientation of the key 48e in terms of polar coordinates. The desired direction of facing of the tool guiding surface 13 of the whipstock 10, when installed, is also known in terms of polar coordinates. Therefore, the correct angular displacement of the whipstock arcuate face 13 relative to the keyway 26a will be known. It is therefore only necessary to angularly adjust the position of the whipstock anchor socket portion 22 about the axis of the anchor shaft 26 in order to effect the desired orientation of the face 13 of the whipstock 10.
Such location of the working face 13 of the whipstock 10 may be conveniently achieved by securing a flexible line or string to the shear pin 18 by which the whipstock upper section 11 is connected to the drill pipe 16. The string is then pulled downwardly along the whipstock anchor assembly and positioned in a plane that passes through the axis of the whipstock shaft 26 and also corresponds to the facing direction of the tool guiding surface 13 of the whipstock 10. This line or string (not shown) is pulled across the edge of the annular compass card 70 and the compass card will then indicate the degrees of angularly displacement of the tool guiding face 13 of the whipstock relative to the scribed line 26h hence relative to keyway 26a in the bottom of shaft 26. The whipstock anchor portion 22 is angularly shifted about the eccentric top portion 26c of the anchor shaft 26 until the string and compass card indicate that the desired degree of angular displacements of the tool guiding face 13 of the whipstock 10 relative to the keyway 26a of the shaft 26 has been achieved. At this point, a set screw 28, passing radially through the anchor socket portion 22 is tightened against the adjacent portion of the shaft 26 and then the plurality of radially disposed set screws 27 are tightened against the eccentric top portion 26c of shaft 26 to effect the rigid securement of such shaft to the whipstock anchor portion 22 with the desired angular relationship being maintained between the tool guiding face 13 of the whipstock 10 and the keyway 26a of the whipstock shaft 20.
The compass card 70 can then be removed from the shaft 26, and the whipstock 10 and its anchor assembly 20 is ready for insertion in the well by the drill pipe 16.
To facilitate the alignment of the whipstock shaft keyway 26a with the anchor key 48e, a tapered mule shoe configuration 26e may be provided for the bottom end of the shaft 26. This configuration cooperates with the top edge of the key 48e to turn the shaft 26 and the remaining elements of the whipstock anchor assembly 20 with it until the keyslot 26a in the shaft 26 is aligned with the internally projecting key 48e whereupon the key 48e enters the key slot 26a and the whipstock anchor assembly 20 moves into its lowermost position relative to the packer 40.
In most instances, there will be fluid contained within the bore of the packer body sleeve 41 when the whipstock anchor assembly 20 is being lowered therein. Since the chevron type seals 24 carried by the anchor sleeve 23 effectively prevent any upward flow of such fluid, it is necessary to provide a temporary bypass for such fluid to permit the convenient insertion of the whipstock anchor assembly 20 into the packer assembly 40. Such fluid bypass comprises a radial port 25c provided in the retaining sleeve or nut 25, which communicates with an upwardly extending annular space 29 provided between the exterior of the shaft 26 and the interior of the anchor sleeve 23. The annular space 29 in turn communicates with a radial port 22d provided in the whipstock anchor socket portion 22.
Fluid passing out of the radial port 22d is directed to the interior of the casing 1 prior to the final setting of the whipstock anchor assembly 20 in the packer assembly 40 by fluid passages provided in an axially shiftable fluid guide sleeve 72 which is mounted in surrounding relationship to the socket portion 22 and the anchor sleeve 23. The sleeve 72 is provided with an annular passage 72a which, during the well inserting of the anchor assembly 20, is in fluid communication at its top and bottom ends with annular recesses 22f and 22g, respectively, provided in the periphery of the socket portion 22. The recess 22g, in turn, communicates with a radial port 72b provided in the fluid guide sleeve 72 which communicates with the interior of the casing.
A shear pin 73 holds the fluid guide sleeve 72 in the position shown in FIG. 7 until just prior to the final seating of the whipstock anchor assembly 20 in the packer 40. As the final vertical seating position of the whipstock anchor assembly 20 in the packer 40 is approached, an upwardly facing shoulder 41f (FIG. 2c) on the packer body sleeve 41 engages the the bottom surface 72d of the fluid guide sleeve 72 and moves it upwardly, shearing the shear pin 73, and aligning the annular passage 72a exactly with the annular passage 22f provided in the whipstock socket portion 22. Concurrently, O-ring seals 74a and 74b respectively provided in the periphery of the whipstock anchor socket portion 22 are disposed on opposite sides of the aligned annular passages 22f and 72a and the seals effectively block any further fluid flow through the bypass.
From the foregoing description, it will be readily apparent to those skilled in the art that the apparatus of this invention provides a most economic and highly reliable system for effecting the installation of a whipstock anchor in a packer so that the tool guiding face of the whipstock can be disposed in the desired angular configuration. Furthermore, the installation of the whipstock anchor assembly of this invention completely blocks all portions of the well below the whipstock anchor assembly and prevents the entry therein of undesired particulate material produced in the subsequent drilling or production operations conducted through the window cut in the wall of the casing.
It should also be recognized that it is entirely a matter of choice as to whether the key is provided on the packer or on the whipstock anchor shaft. For this reason, the language employed in the claims will interchangeably refer to either the key or the keyslot as a "key element".
Although the invention has been described in terms of a specific embodiment which is set forth in detail, it should be understood that this is by illustration only and that the invention is not necessarily limited thereto, since alternative embodiments and operating techniques will become apparent to those skilled in the art in view of the disclosure. Accordingly, modifications are contemplated which can be made without departing from the spirit of the described invention. | The invention provides an improved method and apparatus for effecting the setting of a whipstock in a desired angularly oriented position in a well conduit solely by the use of a wire line but can be set on tubing or drill pipe, if desired. A packer is provided which can be expanded into sealed engagement with the casing at a desired location. The packer is provided with a key element, either a key or a key slot, and orienting elements by which a conventional well bore survey can provide an accurate indication of the angular alignment of the anchor key element. A whipstock anchor is provided incorporating a socket portion in which the whipstock may be rigidly secured and a shaft portion which is insertable within the bore of the packer and has a key element cooperating with the keyway, or key, provided in the packer. After setting of the packer in the well conduit, a survey is made to provide an accurate indication of the angular position of the packer keyway or key. The whipstock is assembled in the whipstock anchor socket and the socket is rotated relative to the shaft portion so that the arcuate face of the whipstock is positioned at a desired angular displacement from the angular position of the key element in the whipstock shaft. The whipstock shaft is then rigidly secured to the whipstock socket and the complete assembly is lowered into the well on drill pipe, or the like, and secured in the packer. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to a method for improving thermal shock resistance of a member made of ceramics to which thermal shock resistance against rapid heating-cooling cycle in wide temperature range from room temperature to 1500° C. is required, further, relates to a member having thermal shock resistance obtained by said method.
[0002] In the present invention, a member made of ceramics to which thermal shock resistance is required indicates a high temperature structural material to which heat cycle resistance and thermal shock resistance are required, for example, dome for etcher, electrostatic chuck, vacuum chuck, suscepter, handling arm, dummy wafer, wafer heater, window of high temperature reaction furnace, reaction tube of diffusion furnace and wafer boat which composes semiconductor producing equipment, and thermocouple protecting tube, radiant tube for aluminum alloy melting, stoke for low pressure casting, stirring propeller for aluminum alloy melting, sleeve for die cast, piping component, high temperature bearing, shaft, heat sink substrate for power module, heat radiation insulated substrate and turbine blade.
BACKGROUND OF THE INVENTION
[0003] At producing process for semiconductor, an electrostatic chuck is used as a method to fix and maintain a semiconductor wafer in each process such as transportation of semiconductor wafer, pattern formation, formation of thin film of CVD or sputtering, plasma cleaning, etching or dicing. An electrostatic chuck is a member to fix and maintain a semiconductor wafer on an adsorption face of the electrostatic chuck by obtaining electrostatic adsorption force by charging electric voltage to the electrostatic chuck. At a thin film forming process or a plasma cleaning process, since the electrostatic chuck suffers rapid heating and cooling with adsorbing a semiconductor wafer, excellent thermal conductivity and high thermal shock resistance are required to the electrostatic chuck.
[0004] Further, as a member to fix and to hold a semiconductor wafer, a vacuum chuck which uses vacuum adsorption force is also used besides an electrostatic chuck. Also in this case, since rapid heating and cooling is loaded to the vacuum chuck with adsorbing a semiconductor wafer, excellent thermal conductivity and high thermal shock resistance are required to the electrostatic chuck.
[0005] Furthermore, excellent resistance to multiple heat cycle or thermal shock are required for a suscepter which is used at placing a semiconductor wafer at forming process of epitaxial growth film on surface of semiconductor wafer by CVD method or for a dummy wafer which is used at investigation, evaluation or inspection of various treatment condition such as sputtering treatment, CVD treatment, ion implantation processing or thermal diffusion treatment or used for adherence prevention of contamination substance in producing process of semiconductor wafer.
[0006] In JP4-61331A publication (Document 1), among above mentioned structural members, subjects relates to dummy wafer are mentioned. That is, it is recorded that strength against strain caused by formed film thickness can be improved by enlarging thickness of silicon substrate. Further, in JP11-278966A publication (Document 2), it is recorded that by forming very fine and voidless SiC film on a surface of basic material which consists from any of sintered product of SiC, Si 3 N 4 or AlN at least, a member is remarkably excellent in resistance to heat cycle or resistance to thermal shock.
[0007] However, in a case to shorten a temperature elevating time for further shortening of a cleaning time aiming to improve productivity, above mentioned conventional technology has following problem.
[0008] A dummy wafer whose basic material is silicon mentioned in Document 1 has a problem of easily cracking by thermal shock caused by rapid temperature elevation. In the meanwhile, resistance for heat cycle or resistance to thermal shock of a member on which SiC is formed by chemical vapor deposition method mentioned in Document 2 are fairly improved. However, to the requirement for further rapid temperature elevation along with the recent requirement for effectiveness of current semiconductor production process, the member is not reaching the place which guarantees the sufficient reliability. In W. Pfeiffer and T. Frey. “Shot Peening of Ceramics: Damage or Benefit”, Ceramic forum international Cfi/Ber. Dkag79 No. 4, E25 (2002) (Document 3), shot blast condition is recited and relationship between blasting material or blasting pressure and toughening characteristic is discussed. However, in this Document, relationship between shot blast and dislocation density of homogeneously distributed linear dislocation which can be measured by a transmission electron microscope or thermal shock resistance is not referred.
[0009] Concerning above mentioned problems which conventional technology has, the subject of the present invention is can be summarized as follows. That is, provision of a ceramic materials whose thermal shock resistance is improved, wherein said ceramic materials is characterized that being difficult to cause cracks by thermal shock by rapid temperature elevating and cooling, shortening cleaning time remarkably and being possible to improve productivity of silicon wafer thereby, further, provision of a method for improvement of thermal shock resistance of the ceramic materials.
[0010] For the purpose to find out a method to improve thermal shock resistance of a ceramics materials, the inventors of the present invention make a trial of fine blast working at room temperature to a ceramics product to which thermal shock resistance is required, and find out that a dislocation which improves thermal shock resistance can be formed by a specific condition of fine blast working and the subject of the present invention is accomplished. By finding out above mentioned technique, a member which has strong mechanical strength against thermal shock accompanied to rapid temperature elevation can be designed, and by applying said technique to an electronics field, that is, to a producing apparatus of semiconductor, display or a optical communication device, said cleaning time can be remarkably shortened and can improve productivity of silicon wafer and others.
DISCLOSURE OF THE INVENTION
[0011] The 1 st one of the present invention is (1) a method for improving surface thermal shock resistance of a member made of ceramics to which thermal shock resistance is required comprising, forming homogeneously distributed linear dislocation structure on the surface of the member made of ceramics to which thermal shock resistance is required by blasting abrasives composed of fine particles whose average particle size is from 5 μm to 200 μm and whose surface shape is convex, wherein Vickers hardness (HV) of said fine particles is 800 or more and equal to or less than the hardness of the member made of ceramics to which thermal shock resistance is required. Desirably, the 1 st one of the present invention is (2) the method for improving surface thermal shock resistance of a member made of ceramics to which thermal shock resistance is required of (1), wherein plastic working is carried out by blasting pressure; 0.1-0.5 MPa, blasting speed; 20 m/sec-250 m/sec, blasting amount 50 g/min-800 g/min, blasting time; 1 sec/cm 2 -60 sec/cm 2 . More desirably the 1 st one of the present invention is (3) the method for improving surface thermal shock resistance of a member made of ceramics to which thermal shock resistance is required of (1) or (2), wherein the homogeneously distributed linear dislocation on the surface of the member made of ceramics to which thermal shock resistance is required forms a dislocation structure whose dislocation density is 1×10 4 -9×10 13 cm −2 .
[0012] And, the 2 nd one of the present invention is (4) a thermal shock resistance member comprising, a basic material composing a member made of ceramics to which thermal shock resistance is required is at least consists from any of alumina, silicon nitride, SIALON, aluminum nitride or silicon carbide, forming a dislocation structure of dislocation density from 1×10 4 to 9×10 13 cm −2 of homogeneously distributed linear dislocation which is measured by a transmission electron microscope on the surface of the basic material.
[0000] Desirably, the 2 nd one of the present invention is (5) the thermal shock resistance member of (4), wherein the member made of ceramics to which thermal shock resistance is required is a dome for etcher, an electrostatic chuck, a vacuum chuck, a suscepter, a handling arm, a dummy wafer, a heater for wafer heating, window of a high temperature reaction furnace, a reaction tube of diffusion furnace, a wafer boat, a thermocouple protecting tube, a radiant tube for aluminum alloy melting, a stoke for low pressure casting, a stirring propeller for aluminum alloy melting, sleeve for die cast, piping component, a high temperature bearing, a shaft, a heat sink substrate for power module, heat radiation insulated substrate and turbine blade.
EFFECT OF THE INVENTION
[0013] A structure member, which is obtained by forming a structure having said characteristics and by treating, has a structure existing by less than several 10 micron of dislocation density from 1×10 4 to 9×10 13 cm −2 , which is measured by a transmission electron microscope. And by having this structure, characteristics of thermal shock resistance and heat cycle resistance are improved. As a basic material which can form said structure and can improve thermal shock resistance, a basic material made of ceramics whose thermal shock resistance is high is basically desirable. Especially, single crystal alumina (sapphire), high purity alumina, silicon nitride, SIALON, aluminum nitride and silicon carbide are superior.
BRIEF ILLUSTRATION OF DRAWINGS
[0014] FIG. 1 is a conceptual drawing of a device of the present invention which carries out blasting treatment to accomplish plastic working at ordinary temperature. 1 is a cabinet of the device, 2 is a door of the cabinet, 3 is a blasting nozzle, 4 is a work piece to be processed (ceramics to be treated), 5 is X-Y table, 6 is a driving part of the X-Y table and 7 is a recovery equipment of blasting abrasives (blasting material for formation of surface toughening structure).
[0015] FIG. 2 is a transmission electron microscopic picture of a structure forming homogeneously distributed linear dislocation obtained by a method for surface toughening of the present invention, allow mark indicates a treated surface and can be observed that dislocation density of surface side is higher.
[0016] FIG. 3 shows the characteristics of thermal shock temperature difference of alumina specimen of Example 3 by relationship between temperature difference and progress of crack (length). It is obvious that thermal shock resistance is improved in the processed specimen.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] FIG. 1 is a device (Product of SINTOBRATOR, Ltd.; product name is microblaster MBI) to carry out fine blasting working treatment which accomplishes plastic working at ordinary temperature of the present invention. Since a work shown in FIG. 1 is a tabular ceramics product 4 , blasting abrasives for plastic working which are different along with the ceramic product to be treated are blasted from a blasting nozzle 3 toward the ceramic product to be treated which is held by a product holding parts composed of X-Y direction drivable table by adjusting blasting pressure and blasting amount B of blasting abrasives for plastic working. Same effect can be obtained by making the blasting nozzle possible to be driven to X-Y direction. Used blasting abrasives for plastic working can be recovered by a recovery equipment 7 and separated from degraded blasting abrasives, then reused. Blasting abrasives can be blasted with air or can be blasted with liquid same as liquid horning. Blasting speed 20 m/sec-250 m/sec is a condition when blasting abrasives are blasted vertically toward the surface of a specimen. And the lower limit of blasting speed is a limitation from a view point of workability of plastic working (fine blast working) treatment, and the upper limit is to restrict the region in which a problem such as chipping is not caused.
[0018] A. As mentioned above, as a basic material, a ceramics which has excellent thermal shock resistance is desirable. Among the ceramics materials having high thermal shock resistance, single crystal alumina (sapphire), high purity alumina, silicon nitride, SIALON, aluminum nitride and silicon carbide are selected and a test pieces are prepared using these materials and fine blast working treatment is carried out on these test pieces and deformed to have a structure existing by dislocation density from 1×10 4 to 9×10 13 cm −2 measured by a transmission electron microscope by less than several 10 micron.
[0019] B. Technical effect of the present invention is indicated. Actual testing method for thermal shock resistance of polycrystal will be illustrated as follows.
[0000] A square test piece prescribed in JIS test piece size of each ceramics are prepared and surface treatment according to above mentioned item A is carried out. On the square test piece, a test for thermal shock resistance prescribed in thermal shock test (JIS R1615: This standard was abolished on Jan. 20, 2002. At the present, it is correspondent to JIS R1648.) is carried out.
[0020] That is, a test piece, which is heated to the desired temperature, is thrown into water and an existence of the generation of the crack is investigated. This action is repeated by elevating heating temperature until a crack is observed in the test piece by the thermal shock. Thermal stress is caused on the test piece by the difference of cooling rate between surface part and inner part, and when said thermal stress generates stronger tensile stress than tensile strength of the test piece, crack occurs.
[0021] Test conditions of said thermal shock resistance test are, (1) test piece size: 3×4×40 mm, (2) temperature of test piece: 150-1000° C., (3) temperature of water: 20° C.
[0022] Kind of blasting abrasives, blasting pressure, blasting amount and treating time can be experimentally decided in the conditions mentioned in claim 1 and claim 2 . Desirable condition of blasting pressure is 0.1-0.5 MPa.
[0023] The present invention will be illustrated more in detail according to Examples. However, these Examples are intending to make the usefulness of the present invention more clear, and not intending to limit the scope of the present invention.
[0024] Instrument for Measurement;
[0000] (1) Dislocation density and structure: Thin film specimen for TEM observation is prepared by an Focused Ion Beam Apparatus (Hitachi F-2000) and the structural characteristics is observed by a transmission electron microscope (TEM) JEOL-200CX (accelerating voltage: 200 kV), product of JAPAN ELECTRON OPTICS LABORATORY CO., Ltd. Dislocation density can be obtained by measuring the dislocation length per unit volume. Concretely, the dislocation density is measured by following procedure, that is, (1) measure the thickness of a thin film specimen, (2) take a TEM observation picture of the point where dislocation density is measured, (3) measure the length of dislocation contained in the unit volume.
(2) Thermal shock resistance test: JIS R1615
Thermal Shock Resistance Test of Examples 1-10 and Comparative Examples 1-6
[0025] In Table 1-1 and Table 1-2, surface roughness, dislocation density, thermal shock resistance and improved ratio of thermal shock resistance temperature of a structural member obtained by changing blasting abrasives and blasting condition (Example 1-10) are shown in comparison with specimen of Comparative Examples (Comparative Examples 1-6) to which blast working is not carried out.
[0026] As a specimen, high purity alumina (alumina 99.5%) of hardness 1600 HV, high purity alumina (alumina 99.99%) of hardness 1700 HV, silicon nitride, SIALON, aluminum nitride and silicon carbide are used. Thermal shock resistance test is carried out in accordance with JIS R1615.
[0027] Dislocation density mentioned in Table 1-1 and Table 1-2 are measuring results by TEM observation of specimen to which fine blast working is carried out vertically to the surface of specimen from thickness direction.
[0000]
TABLE 1-1
Thermal shock test results (1)
improv-
ed
ratio of
specimen
ther-
bend-
blasting condition
surface
thermal
mal
ing
blasting abrasives
blasting
roughness
disloca-
shock
shock
hard
stren-
hard-
pres-
time
Ra μm
tion
resis-
resis-
ness
gth
size
ness
sure
amt.
speed
sec/
before
after
density/
tance
tance
No.
material
HV
MPa
material
μm
HV
MPa
g/m
m/s
cm 2
process
process
cm 2
temp. ° C.
temp.
Comp.
alumina
1600
360
—
—
—
—
—
—
—
0.130
—
—
200
—
Example 1
(99.5%)
Example 1
alumina
1600
360
mullite
100
1020
0.25
400
50
6
0.130
0.159
2.3 × 10 12
400
2.00
(99.5%)
Comp.
alumina
1700
400
—
—
—
—
—
—
—
0.089
—
—
200
—
Example 2
(99.99%)
Example 2
alumina
1700
400
zircon
200
810
0.15
400
30
12
0.089
0.093
3.7 × 10 8
250
1.25
(99.99%)
Example 3
alumina
1700
400
mullite
100
1020
0.25
400
50
8
0.089
0.096
2.8 × 10 13
400
2.00
(99.99%)
Example 4
alumina
1700
400
zirconia
50
1380
0.25
600
60
4
0.089
0.102
6.1 × 10 12
400
2.00
(99.99%)
Comp.
silicon
1370
1115
—
—
—
—
—
—
—
0.033
—
—
700
—
Example 3
nitride
Example 5
silicon
1370
1115
zircon
200
810
0.15
400
30
10
0.033
0.034
7.1 × 10 8
800
1.14
nitride
[0000]
TABLE 1-2
Thermal shock test results (2)
improv-
ed
ratio of
specimen
ther-
bend-
blasting condition
surface
thermal
mal
ing
blasting abrasives
blasting
roughness
disloca-
shock
shock
hard
stren-
hard-
pres-
time
Ra μm
tion
resis-
resis-
ness
gth
size
ness
sure
amt.
speed
sec/
before
after
density/
tance
tance
No.
material
HV
MPa
material
μm
HV
MPa
g/m
m/s
cm 2
process
process
cm 2
temp. ° C.
temp.
Example 6
silicon
1370
1115
zirconia
50
1380
0.15
600
50
10
0.033
0.035
4.9 × 10 12
950
1.36
nitride
Example 7
silicon
1370
1115
zirconia
50
1380
0.35
600
70
6
0.033
0.040
5.8 × 10 13
950
1.36
nitride
Comp.
SIALON
1630
1050
—
—
—
—
—
—
—
0.113
—
—
650
—
Example 4
Example 8
SIALON
1630
1050
zirconia
50
1380
0.35
600
70
10
0.113
0.149
4.9 × 10 13
950
1.46
Comp.
aluminum
1060
390
—
—
—
—
—
—
—
0.161
—
—
300
—
Example 5
nitride
Example 9
aluminum
1060
390
zircon
200
810
0.15
400
30
4
0.161
0.172
7.7 × 10 11
500
1.66
nitride
Comp.
silicon
2700
610
—
—
—
—
—
—
—
0.247
—
—
400
—
Example 6
carbide
Example 10
silicon
2700
610
alumina
100
1500
0.35
400
60
4
0.247
0.331
8.3 × 10 12
600
1.50
carbide
[0028] From the results recorded in Tables 1-1 and 1-2, compared with thermal shock resistance of non-treated specimen (refer to column of Comparative Examples), thermal shock resistance of a specimen which is treated by a method of this invention is improved along with increase of dislocation density of linear dislocation formed on the surface of specimen after plastic working (fine blast working), and is improved to have durability at temperature difference of 400° C. in a case of alumina, 950° C. in a case of silicon nitride, 950° C. in a case of SIALON, 500° C. in a case of aluminum nitride and 600° C. in a case of silicon carbide.
Heat Cycle Test of Examples 1-10 and Comparative Examples 1-6
[0029] Test pieces of Examples 1-10 and Comparative Examples 1-6 which are prepared for previous thermal shock test are used for thermal shock test by heat cycle;
[0030] 10 pieces each of said test pieces are set into an infrared heating furnace and the temperature is elevated from ordinary temperature to 1200° C. by 10 minutes and maintained for 15 minutes, then cooled down to ordinary temperature. This cycle is repeated for 50 cycles and occurrence of crack on each specimen is observed. Results are shown in Tables 2-1 and 2-2. Numerical values mentioned in heat cycle resistance indicate numbers of specimen on which any crack is observed.
[0000]
TABLE 2-1
Heat cycle test results (1)
specimen
bend-
blasting condition
surface
heat cycle
ing
blasting abrasives
blasting
roughness
disloca-
resistance
hard
stren-
hard-
pres-
time
Ra μm
tion
(numbers of test
ness
gth
size
ness
sure
amt.
speed
sec/
before
after
density/
pieces in which
No.
material
HV
MPa
material
μm
HV
MPa
g/m
m/s
cm 2
process
process
cm 2
crack is observed)
Comp.
alumina
1600
360
—
—
—
—
—
—
—
0.130
—
—
10
Example 1
(99.5%)
Example 1
alumina
1600
360
mullite
100
1020
0.25
400
50
6
0.130
0.159
2.3 × 10 12
0
(99.5%)
Comp.
alumina
1700
400
—
—
—
—
—
—
—
0.089
—
—
10
Example 2
(99.99%)
Example 2
alumina
1700
400
zircon
200
810
0.15
400
30
12
0.089
0.093
3.7 × 10 8
7
(99.99%)
Example 3
alumina
1700
400
mullite
100
1020
0.25
400
50
8
0.089
0.096
2.8 × 10 13
0
(99.99%)
Example 4
alumina
1700
400
zirconia
50
1380
0.25
600
60
4
0.089
0.102
6.1 × 10 12
0
(99.99%)
Comp.
silicon
1370
1115
—
—
—
—
—
—
—
0.033
—
—
2
Example 3
nitride
Example 5
silicon
1370
1115
zircon
200
810
0.15
400
30
10
0.033
0.034
7.1 × 10 8
1
nitride
[0000]
TABLE 2-2
Heat cycle test results (2)
specimen
bend-
blasting condition
surface
heat cycle
ing
blasting abrasives
blasting
roughness
disloca-
resistance
hard
stren-
hard-
pres-
time
Ra μm
tion
(numbers of test
ness
gth
size
ness
sure
amt.
speed
sec/
before
after
density/
pieces in which
No.
material
HV
MPa
material
μm
HV
MPa
g/m
m/s
cm 2
process
process
cm 2
crack is observed)
Example 6
silicon
1370
1115
zirconia
50
1380
0.15
600
50
10
0.033
0.035
4.9 × 10 12
0
nitride
Example 7
silicon
1370
1115
zirconia
50
1380
0.35
600
70
6
0.033
0.040
5.8 × 10 13
0
nitride
Comp.
SIALON
1630
1050
—
—
—
—
—
—
—
0.113
—
—
2
Example 4
Example 8
SIALON
1630
1050
zirconia
50
1380
0.35
600
70
10
0.113
0.149
4.9 × 10 13
0
Comp.
aluminum
1060
390
—
—
—
—
—
—
—
—
—
6
Example 5
nitride
Example 9
aluminum
1060
390
zircon
200
810
0.15
400
30
4
0.161
0.172
7.7 × 10 11
0
nitride
Comp.
silicon
2700
610
—
—
—
—
—
—
—
—
—
4
Example 6
carbide
Example 10
silicon
2700
610
alumina
100
1500
0.35
400
60
4
0.247
0.331
8.3 × 10 12
0
carbide
[0031] As clearly understood from Tables 2-1 and 2-2, regarding a specimen which is treated by a method of this invention, dislocation density of linear dislocation formed on the surface of specimen increases after plastic working (fine blast working) and on a test piece to which heat cycle test is carried out any crack becomes not to be observed. On the contrary, crack is observed on a non-treated test piece by a method of this invention. As mentioned above, it becomes clear that the heat cycle characteristic is remarkably improved and effectiveness of the present invention can be confirmed.
Measurement of Relationship Between Thermal Shock Temperature Difference and Length of Crack of Example 1 and Comparative Example
[0032] Experiment Using Thermal Shock Resistance Test Piece of Single Crystal Alumina;
[0033] Fine blast working treatment is carry out on an single crystal alumina test piece (shape 10×10×1 t mm) by conditions indicated in Table 1 and a specimen for thermal shock test is prepared. In Table 2, TEM picture of linear dislocation formed on the surface of single crystal alumina test piece obtained by fine blast working. Indentations by Vickers Hardness tester is marked on prepared thermal shock test piece and heated and maintained at 300° C., 500° C. and 700° C. for 10 minutes then thrown in water (20° C.) and left for 5 minutes. After that, length of crack of indentations of said test piece is measured, and appearance of crack of test pieces to which dislocation is introduced and not introduced are observed. Results are shown in FIG. 3 . Compared with non-treated test piece, progress of crack can not be observed even in 700° C. and excellent effect is recognized.
[0000]
TABLE 3
Preparation condition of thermal shock test piece (single crystal alumina)
surface
specimen
blasting abrasives
blasting condition
roughness
bending
hard-
blasting
Ra μm
dislocation
hardness
strength
size
ness
pressure
amt.
speed
time
before
after
density/
No.
material
HV
MPa
material
μm
HV
MPa
g/min
m/s
sec/cm 2
process
process
cm 2
Comparative
single
1630
—
—
—
—
—
—
—
—
—
—
—
Example 1
crystal
alumina
Example 1
single
1630
—
mullite
100
1020
0.45
80
85
12
0.016
0.059
1.6 × 10 12
crystal
alumina
INDUSTRIAL APPLICABILITY
[0034] The present invention can be used in a process in which cycles of rapid heating and rapid cooling is included. For example, the present invention can be applied to improve thermal shock resistance of a dome for etcher, an electrostatic chuck, a vacuum chuck, a susceptor, a handling arm, a dummy wafer, a heater for wafer heating, window of a high temperature reaction furnace, a reaction tube of diffusion furnace, a wafer boat, a thermocouple protecting tube, a radiant tube for aluminum alloy melting, a stoke for low pressure casting, a stirring propeller for aluminum alloy melting, sleeve for die cast, piping component, a high temperature bearing, a shaft, a heat sink substrate for power module, a heat radiation insulated substrate and a turbine blade. | A method for improving surface thermal shock resistance of a member made of ceramics to which thermal shock resistance is required comprising, forming homogeneously distributed linear dislocation structure on the surface of the member made of ceramics to which thermal shock resistance is required by blasting abrasives composed of fine particles whose average particle size is from 5 μm to 200 μm and whose surface shape is convex, wherein Vickers hardness (HV) of said fine particles is 800 or more and equal to or less than the hardness of the member made of ceramics to which thermal shock resistance is required. | 2 |
FIELD
This disclosure relates to the field of hinges. More particularly, this disclosure relates to a cam hinge having a spring with adjustable tension to provide an adjustable closing force.
BACKGROUND
Cam hinges or lift hinges are commonly used in indoor applications where there is a need to lift the door to overcome thresholds or the like obstacles at floor level, or when the floor below the door is inclined or sloped. Conventional cam springs desire improvement in many regards.
What is desired is a cam hinge that is configured to have spring-assisted closing as a feature. Also desired is a cam hinge with spring assisted closing, with adjustability of the spring tension so as to permit adjustment of the closure speed.
The present disclosure advantageously provides a cam hinge having spring assisted closing, with adjustability of the spring tension to provide adjustable closing speed.
SUMMARY
The above and other needs are met by a self-closing and adjustable closing force cam hinge.
In one aspect, the hinge includes a stationary hinge portion having a hinge body; a pivoting hinge portion having a hinge body; and a hinge pin having a head and passing through the hinge body of the stationary hinge portion and the hinge body of the pivoting hinge portion. The pivoting hinge portion pivots about the hinge pin relative to the stationary hinge portion and cooperates with the stationary hinge portion to enable the pivoting hinge portion to lift as the pivoting hinge portion is rotated from a closed position to an open position and to lower as the pivoting hinge portion is rotated from the open position to the closed position.
A compression spring is located on the hinge so that the hinge pin passes through the compression spring and the head of the hinge pin is retracted from the compression spring to compress the compression spring so that the compression spring applies a closing force to the hinge when the hinge is in the open position. A spring adjuster includes an adjustably positionable body that is adjustably positionable relative to the head of the hinge pin.
Adjustment of the position of the adjustably positionable body raises or lowers the head of the hinge pin such that raising of the hinge pin increases compression of the compression spring to increase the closing force applied by the compression spring and lowering of the hinge decreases compression of the compression spring to decrease the closing force applied by the compression spring.
In another aspect, a self closing and adjustable closing force hinge includes a hinge openable and closeable between an open position and a closed position. The hinge has a compression spring located on the hinge so that a hinge pin passes through the compression spring and a head of the hinge pin is retracted in a direction away from the compression spring to compress the compression spring. The compression spring applies a closing force to the hinge when the hinge is in an open position.
A spring adjuster is located on the hinge and includes an adjustably positionable body that is adjustably positionable relative to the head of the hinge pin. Adjustment of the position of the adjustably positionable body raises or lowers the head of the hinge pin. Raising of the hinge pin increases compression of the compression spring to increase the closing force applied by the compression spring and lowering of the hinge decreases compression of the compression spring to decrease the closing force applied by the compression spring.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages of the disclosure are apparent by reference to the detailed description when considered in conjunction with the figures, which are not to scale so as to more clearly show the details, wherein like reference numbers indicate like elements throughout the several views, and wherein:
FIG. 1 is a side view of a cam hinge according to the disclosure with the hinge in a position corresponding to a gate supported by the hinge being in a fully closed position.
FIG. 2 is a perspective view of a cam hinge according to the disclosure with the hinge in a position corresponding to a gate supported by the hinge being in a fully open position.
FIG. 3 is a cross-sectional view of hinge body portions of the hinge of FIG. 1 with a spring adjustment system thereof adjusted to slightly tension a spring component thereof to provide a relatively light closing force.
FIG. 4 is a cross-sectional view of hinge body portions of the hinge of FIG. 1 with a spring adjustment system thereof adjusted to increase tension of the spring component thereof to provide a stronger closing force.
FIG. 5 is a close-up view of an upper portion of the cam hinge of FIG. 1 showing a spring adjustment components of the cam hinge cooperating with one another to slightly tension the spring component to provide a relatively light closing force.
FIG. 6 is a close-up view of an upper portion of the cam hinge of FIG. 1 showing a spring adjustment components of the cam hinge cooperating with one another to tension the spring component to provide a relatively strong closing force.
FIG. 7 is an exploded perspective view of portions of the cam hinge of FIG. 1 .
FIG. 8 shows a stationary hinge portion of the cam hinge of FIG. 1 .
FIG. 9 shows a pivoting hinge portion of the cam hinge of FIG. 1 .
FIG. 10 shows a stationary hinge portion of the cam hinge of FIG. 1 .
DETAILED DESCRIPTION
With reference to the drawings, the disclosure relates to a bi-directional cam hinge 10 configured to have spring assisted closing, with adjustability of the spring tension to provide adjustable closing speed. The hinge 10 is particularly suitable for use as a hinge for attaching a fence gate to a fence post, and particularly for a vinyl fence and gate. The hinge 10 is configured to function in either direction so that a gate can be opened either with clockwise or counter-clockwise rotation of the hinge 10 . However, but it will be understood that it could be configured to function for only one direction of rotation.
The hinge 10 includes a hinge pin 12 , a lower stationary hinge portion 14 , and an upper pivoting hinge portion 16 . The hinge 10 includes a compression spring 18 for spring assisted closing of the hinge 10 .
The hinge pin 12 is an elongate, preferably metal, pin having a shaft 20 with an enlarged head 22 at one end and a distal end 24 at the opposite end. The compression spring 18 is installed on the pin 12 adjacent the distal end 24 of the pin 12 . The distal end 24 may be tapered and includes a circumferential groove 26 for interfacing with a fastener, such as a retaining ring 28 , for retaining the compression spring 18 . As shown, a washer may be located between the end of the spring 18 and the retaining ring 28 .
The lower stationary hinge portion 14 includes an elongate generally planar base 30 for mounting the lower stationary hinge portion 14 adjacent to a fence post P or the like as by use of screws passed through apertures 32 . A hinge body 34 extends outwardly from the base 30 , and includes a central vertical bore 36 that extends through the hinge body 34 and is open at each end. A lower end 36 a of the bore 36 has an enlarged diameter for receiving the compression spring 18 . An upper end 38 of the hinge body 34 is configured to receive a cam insert 40 .
The cam insert 40 is configured to sit on and nest with the upper end 38 of the hinge body and provide an exterior cam surface 42 with a through bore 44 aligned with the bore 36 . The cam insert 40 may include a key or projection 46 received by a corresponding lock or notch 48 on the hinge body 34 to secure the cam insert 40 to the hinge body 34 and inhibit relative movement thereof. In this regard, the cam insert 40 is configured as a separate piece to simplify manufacturing and reduce manufacturing costs. However, it will be understood that the hinge body 34 may be formed of one piece construction to include the cam surface 42 .
The upper pivoting hinge portion 16 includes an elongate generally planar base 60 for mounting the upper pivoting hinge portion 16 adjacent to a fence gate G or the like as by use of screws passed through apertures 62 . A hinge body 64 extends outwardly from the base 60 , and includes a central vertical bore 66 that extends through the hinge body 64 and is open at each end. An upper end 66 a of the bore 66 has an enlarged diameter for receiving the head 22 of the hinge pin 12 . A lower end 68 of the hinge body 64 is rounded and otherwise configured to include a cam surface configured to cooperate with the cam surface 42 of the hinge body 34 to enable cam or lift hinge operation of the hinge 10 .
A guide 70 is located on the lower end 68 of the hinge body 64 . The guide 70 may be provided, for example, as by a pin or the like extending through an aperture 72 located adjacent the lower end 68 of the hinge body 64 . The guide 70 directly contacts the cam surface 42 to follow the contour thereof. For example, the cam surface 42 is a generally rounded and rising sloped surface, and the lower end 68 of the hinge body 64 is generally rounded and oppositely sloped so as to provide clearance as the hinge rotates as guided by the guide 70 traveling along the cam surface.
When the gate G is closed, the lower end 68 is at its lowest position. As the gate G is opened, either clockwise or counter clockwise, the guide 72 , and hence the lower end 68 , follows the contour of the cam surface 42 and the hinge body 64 rotates and rises relative to the hinge body 34 . As the gate is closed, this is reversed. The compression spring 18 provides a downward pull on the hinge body 64 via the head 22 of the hinge pin 12 bearing on the hinge body 64 to provide a closing force.
The guide 70 also functions to enable the gate G to resist the force of the compression spring 18 and remain in a fully open position, the hinge body 64 . The guide 70 cooperates with a notch 74 defined across an upper portion of the cam surface 42 so as to reside in the notch 74 . This enables the gate G to resist the force of the compression spring 18 and remain in a fully open position. To close the gate G, the user supplies a closing force that unseats the guide 70 from the notch 74 .
To enable adjustment of the closing force supplied by the compression spring 12 , the vertical position of the head 22 of the hinge pin 12 is adjusted by use of a set screw 80 threadably received by a threaded bore 82 of the hinge body 64 at a location proximate the head 22 of the hinge pin 12 .
With reference to FIGS. 3 and 5 , the hinge 10 is shown with the compression spring 18 set to a minimum closing force. As will be seen, the set screw 80 is retracted substantially from the bore 82 so as to not engage the head 22 of the hinge pin 12 . Thus, the head 22 is able to fully seat into the upper end 66 a of the bore 66 . This position of the pin 12 renders the compression spring 18 in a minimally compressed orientation to provide the weakest closing force.
Turning now to FIGS. 4 and 6 , the hinge 10 is shown with the compression spring 18 set to a maximum closing force. As will be seen, the set screw 80 is fully inserted into the bore 82 as by clockwise rotation of the set screw 80 into the bore 82 so as to position the set screw 80 fully span and engage the underside of the head 22 of the hinge pin 12 . This relative positioning of the screw 80 and the head 22 serves to raise the pin 12 . The lower end of the compression spring 18 is engaged by the retaining ring 28 fixed on the distal end 24 of the pin 12 so that raising of the pin 12 compresses the compression spring 18 in the lower end 36 a of the bore 36 of the hinge body 34 . This position of the pin 12 renders the compression spring 18 in a maximum compressed orientation so as to provide the strongest closing force.
The set screw 80 may be adjusted between the fully inserted and the retracted positions to enable incremental adjustment of the position of the head 22 of the pin 12 and hence incremental adjustment of the closing force of the spring 12 . That is, the lower surface of the head 22 of the pin 12 and the set screw 80 cooperate so that as the distal end of the set screw 80 initially contacts the head 22 , the head 22 is raised. As the set screw 80 is further screwed into the bore 80 it continues to span the lower side of the head 22 causing incremental rising of the head 22 , with maximum rising of the head 22 achieved when the set screw 80 fully spans the underside of the head 22 .
As will be appreciated, the described hinge 10 advantageously provides a cam hinge having spring assisted closing, with adjustability of the spring tension to provide adjustable closing speed.
The hinge 10 is particularly suitable for use as a hinge for attaching a fence gate to a fence post, and particularly for a vinyl fence and gate. In this regard, the components for the hinge 10 described above are generally formed of sturdy metal suitable for use as a hinge. However, to facilitate mounting to a vinyl post and a vinyl gate, the hinge 10 may further include mounting pads 90 and 92 configured to connect to and abut the bases 30 and 60 , respectively. The pads 90 and 92 are desirably formed of a vinyl material so that the bases 30 and 60 do not mar or dig into the pot or gate to which they are installed. Also, screw receivers 94 and 96 are located on the opposite surface of the post or gate from the bases 30 and 60 , respectively, for receiving the mounting screws or other fasteners. The screw receivers 94 and 96 are desirably formed of metal.
The foregoing description of preferred embodiments for this disclosure has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiments are chosen and described in an effort to provide the best illustrations of the principles of the disclosure and its practical application, and to thereby enable one of ordinary skill in the art to utilize the disclosure in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the disclosure as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled. | A self closing and adjustable closing force cam hinge includes a compression spring located on the hinge so that a hinge pin passes through the compression spring and the head of the hinge pin is retracted in a direction away from the compression spring to compress the compression spring. Compression of the spring applies a closing force to the hinge when the hinge is in the open position. The hinge also includes a spring adjuster having an adjustably positionable body that is adjustably positionable relative to the head of the hinge pin. Adjustment of the position of the adjustably positionable body raises or lowers the head of the hinge pin such that raising of the hinge pin increases compression of the compression spring to increase the closing force applied by the compression spring and lowering of the hinge decreases compression of the compression spring to decrease the closing force applied by the compression spring. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. patent application Ser. No. 09/756,891, entitled, “Compressed Gas-Powered Gun Simulating The Recoil of a Conventional Firearm,” filed Jan. 9, 2001.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This application relates to compressed gas powered guns. More specifically, the invention relates to training guns duplicating various characteristics of guns firing gunpowder propelled projectiles.
[0004] 2. Description of the Related Art
[0005] Guns firing projectiles propelled by compressed air or gas are commonly used for recreational target shooting or as training devices for teaching the skills necessary to properly shoot guns firing gunpowder propelled projectiles. Ammunition for air guns is significantly less expensive than gunpowder propelled ammunition. A typical gas powered projectile has significantly lower velocity and energy than a gunpowder propelled projectile, making it much easier to locate a safe place to shoot an air gun, and much less expensive to construct a suitable backstop. Additionally, the low velocity and energy of air powered projectiles makes air guns significantly less useful as weapons than guns firing gunpowder propelled projectiles. Lack of usefulness as a weapon is an important factor in making air guns available in regions where national or local governments regulate firing gunpowder propelled projectiles (firearms).
[0006] To be an effective training tool, an air gun must duplicate the characteristics of a firearm as closely as possible. These characteristics include size, weight, grip configuration, trigger reach, type of sights, level of accuracy, method of reloading, method of operation, location of controls, operation of controls, weight of trigger pull, length of trigger pull, and recoil. The usefulness of a gas powered gun as a training tool is limited to the extent that any of the above listed characteristics cannot be accurately duplicated.
[0007] Presently available air guns increasingly tend to have an exterior configuration resembling that of a gun firing a powder propelled projectile. Presently available air guns may be used in a semi-automatic (one shot per pull of the trigger) or very rarely full automatic (more than one shot per pull of the trigger) mode of fire, although the cyclic rate of full automatic fire typically does not duplicate the cyclic rate of a full automatic firearm firing a projectile powered by gunpowder. The vast majority of presently available airguns which are advertised as being semiautomatic are actually nothing more than double-action revolver mechanisms disguised within an outer housing that simply looks like a semiautomatic gun. However, because they are true double-action mechanisms, the weight of trigger pull is much heavier than the weight of trigger pull of the present invention, which has a true single-action trigger. Presently available air guns have also been designed to simulate the trigger pull and reloading of guns firing gunpowder propelled projectiles.
[0008] Presently available air guns do not duplicate the recoil of a gun firing a powder propelled projectile. The inability to get a trainee accustomed to the recoil generated by conventional firearms is one of the greatest disadvantages in the use of air guns as training tools. Additionally, although presently available air guns can be made extremely accurate, variations in gas pressure can cause differences in shot placement from shot to shot, or from the beginning of a gas cartridge to the end. Further, duplication of the cyclic rate of a conventional firearm within an air gun would enable a trainee to learn how to properly depress the trigger to fire short bursts of approximately three shots in full automatic mode of fire using an air gun. Because recoil is significantly more difficult to control during full automatic fire than during semi-automatic fire, an air gun simulating both recoil and the cyclic rate of a conventional firearm would be particularly useful as a training tool.
[0009] Accordingly, there is a need for an air powered gun duplicating the recoil of a conventional firearm. Additionally, there is a need for an air powered gun maintaining a consistent compressed gas pressure behind the projectile from shot to shot, thereby maintaining a constant velocity, energy, and point of impact for each projectile. Further, there is a need for an air gun duplicating the full automatic cyclic rate of a conventional full automatic firearm. There is also a need to combine these characteristics into an air gun that is not particularly useful as a weapon, thereby facilitating safe use by inexperienced trainees, making training facilities easier and more economical to construct, lowering the cost of ammunition and training, reducing noise levels, and broadening the legality of ownership.
SUMMARY OF THE INVENTION
[0010] The preferred embodiment of the invention is an air or gas powered gun providing a recoil similar to that of a gun firing a powder propelled projectile. The compressed gas powered gun includes an improved magazine and magazine indexing system, contributing to the accuracy of the gun. The compressed gas powered gun preferably also duplicates many other features of a conventional firearm, for example, the sights, the positioning of the controls, and method of operation. One preferred embodiment simulates the characteristics of an AR-15 or M-16 rifle, although the invention can easily be applied to simulate the characteristics of other conventional firearms.
[0011] The operation of a compressed gas powered gun of the present invention is controlled by the combination of a trigger assembly, bolt, buffer assembly and valve. Preferred embodiments will be capable of semi-automatic fire, full automatic fire at a low cyclic rate, and full automatic fire at a high cyclic rate. One of the two full automatic cyclic rates preferably approximately duplicates the cyclic rate of a conventional automatic rifle, for example, an M-16 rifle.
[0012] The trigger assembly includes a trigger having a finger-engaging portion and a selector-engaging portion, a selector switch, a trigger bar, a sear trip, and a sear. The selector switch will preferably by cylindrical, having three bearing surfaces corresponding to safe, semi-automatic fire, and full automatic fire at a low cyclic rate, and a channel corresponding to full automatic fire at a high cyclic rate. These surfaces and channel of the selector bear against the selector engaging portion of the trigger, permitting little or no trigger movements if safe is selected, and increasing trigger movement for semi-automatic fire, low cyclic rate full automatic fire, and high cyclic rate full automatic fire, respectively. The sear is mounted on a sliding pivot, and is spring-biased towards a rearward position. The sear has a forward end for engaging the sear trip, and a rear end for engaging the bolt. The bolt preferably contains a floating mass, and reciprocates between a forward position and a rearward position. Although the bolt is spring-biased towards its forward position, the bolt will typically be held in its rearward position by the sear except during firing.
[0013] The valve assembly includes a reciprocating housing containing a stationary forward valve poppet, a sliding rear valve poppet, and a spring between the front and rear valve poppets. The spring pushes the rear valve poppet rearward, causing the rear poppet to bear against the housing, thereby closing the rear valve and pushing the housing rearward. Pushing the housing rearward causes the housing to bear against the front valve poppet, thereby closing the front valve.
[0014] Before the trigger is pulled, the trigger is in its forwardmost position, the bolt is held to the rear by its engagement with the sear, and the sear, although spring-biased rearward, is pushed towards its forwardmost position by the bolt. Pulling the trigger causes the trigger bar to move rearward, pivoting the sear trip upward. The upward movement of the sear trip pushes upward on the forward end of the sear, causing the rearward end of the sear to move down. The bolt is then free to travel forward, where the bolt strikes the rear valve, thereby moving the rear valve relative to the housing and opening the rear valve. Air pressure between the O-ring on the bolt face and the O-ring on the rear of the valve housing causes the housing to move forward, thereby opening the forward valve. Opening the forward valve dispenses pressurized gas to a position directly behind the projectile, causing the projectile to exit the barrel. Opening the rear valve supplies air pressure to the bolt face, thereby causing the bolt to return to its rearward position. If semi-automatic fire is selected, the limited movement of the sear trip, combined with the rearward spring-bias on the sear, causes the sear to move backwards on its pivot to a position where the sear trip can no longer apply upward pressure to the forward portion of the sear. The rear portion of the sear therefore pivots upward. The bolt will be propelled rearward to a point slightly behind the position wherein it engages the sear. As the bolt returns forward, the sear, which is no longer held in place by the sear trip, will engage the bolt, preventing further forward movement. From this position of the components, the trigger must be released before it can be pulled to fire another shot.
[0015] If full automatic fire at a slow cyclic rate is selected, the trigger may be pulled slightly farther to the rear before it engages the selector, thereby causing the sear trip to pivot slightly higher. Whereas the upper bearing surface of the sear trip pushes the sear up to initially release the bolt, here, the lower end bearing surface of the sear trip pushes the sear up sufficiently so that, when the bolt catches the sear, there is only about {fraction (1/32)} nd inch of engagement between the sear and bolt. The floating mass bolt is thereby momentarily held in its rearward position by the sear, which cams forward off the sear trip as the forward motion of the bolt pushes the sear from its rearward position to its forward position.
[0016] If full automatic fire at a high cyclic rate is selected, the trigger is allowed to travel to its maximum rearward position. The sear trip is thereby pivoted upward to its maximum extent, causing the lower end bearing surface of the sear trip to push the sear completely out of the way of the bolt. Therefore, as soon as the spring behind the bolt driver overcomes the rearward momentum of the bolt, the bolt will simply return forward and again actuate the valve.
[0017] A compressed gas powered gun of the present invention preferably includes a magazine and magazine indexing assembly configured to facilitate precise alignment of the firing chambers with the barrel. A preferred embodiment of the magazine is a cylinder. The term “cylinder” as used herein does not necessarily mean a perfect geometrical cylinder, but is used to denote a generally cylindrical magazine wherein a plurality of firing chambers are located around its circumference, as known to those skilled in the art of revolvers. A preferred cylinder will have six chambers, although this number may vary. The exterior surface of the cylinder will preferably include a plurality of flutes, with the flutes located between the chambers, and with an equal number of chambers and flutes. One preferred embodiment of the cylinder aligns the chamber with the barrel in the three o'clock position when viewed from the rear or the nine o'clock position when viewed from the front. A spring-biased bearing preferably engages the flutes, thereby precisely aligning the cylinder with the barrel. A preferred bearing will have a larger radius than the radius of the flutes, thereby maximizing the precision with which the chamber and barrel may be aligned. This arrangement permits the barrel and chamber to be aligned with such precision that a forcing cone is not needed at the breach of the barrel.
[0018] Indexing of the cylinder is controlled by the forward and backward movements of the bolt. A spring-biased pawl mounted on a pawl carrier is located directly behind the cylinder. The pawl carrier reciprocates between a left most position and a right most position, with the left most position corresponding to the engagement of the pawl with one chamber of the cylinder, and the right most position corresponding to engagement of the pawl with another chamber of the cylinder. An operating rod extends forward from the bolt, overlapping the pawl carrier. The bottom surface of the operating rod includes an angled slot, dimensioned and configured to guide an upwardly projecting pin on the pawl carrier. With the bolt in its rear most position, the pawl carrier pin is located in the forwardmost portion of the operating rod's angled slot. The pawl carrier and pawl are therefore in their right side position. The pawl is spring-biased forward to engage the chamber in the one o'clock position when viewed from the rear, or the eleven o'clock position when viewed from the front. As the operating rod moves forward due to forward travel of the bolt, the pawl carrier is moved from its right side position to its left side position. The left side of the pawl includes a ramped surface which permits the pawl to be pushed rearward by the cylinder wall, against the bias of the spring, allowing the pawl to move from the top right side chamber to the top left side chamber. When the bolt returns to its rearward position, the pawl and pawl carrier are moved from their left side position to their right side position. The right side of the pawl is parallel to the inside of the cylinder wall, so that movement of the pawl from left to right will cause the cylinder to index in a clockwise direction when viewed from the rear, or a counterclockwise direction when viewed from the front. The bearing will be biased out of the current flute, and will bear against the next flute at the completion of indexing, thereby properly aligning the next firing chamber with the barrel.
[0019] Another preferred embodiment includes a tubular magazine in addition to the cylinder. The tubular magazine is aligned with one chamber of the cylinder whenever another chamber of the cylinder is aligned with the barrel. The tubular magazine includes a spring-biases follower for pushing projectiles rearward into the cylinder. Whenever the cylinder is indexed, another projectile will thereby be pushed into an empty chamber of the cylinder as that chamber is aligned with the tubular magazine.
[0020] If no tubular magazine is present, or if use of only the cylinder is desired, a preferred method of reloading the compressed gas powered gun is to remove the cylinder, place a single pellet into each chamber, and then replace the cylinder. If the tubular magazine is used, a preferred method of loading the compressed gas powered gun includes retracting the follower using a finger tab secured to the follower and extending outside the gun, opening a loading gate, and pouring projectiles into the tubular magazine. Preferred projectiles for use of a tubular magazine include spherical pellets. Preferred projectiles for use with the cylinder alone include spherical pellets or conventional air gun pellets.
[0021] A compressed gas powered gun of the present invention uses a recoiled buffer system for biasing the bolt forward, and for providing a recoil for the shooter. A preferred buffer system includes a floating mass bolt driver, and an air resistance bolt driver, with a spring disposed therebetween. This assembly is located in a tube within the air gun's shoulder stock, which is preferably a cylindrical tube. The buffer assembly may be oriented so that either the air resistance bolt driver or the floating mass bolt driver is positioned directly behind the bolt, with the other bolt driver placed at the rear of the stock. The forward bolt driver will thereby abut the rear of the bolt, pushing the bolt forward.
[0022] If the air resistance bolt driver is positioned directly behind the bolt, light recoil results. The air resistance bolt driver has less mass than the floating mass bolt driver, resulting in less mass reciprocating back and forth. Additionally, the air resistance bolt driver will trap air behind it as it reciprocates, thereby slowing travel of the reciprocating mass. Conversely, positioning the floating mass bolt driver behind the bolt results in heavier recoil, due to the increased reciprocating mass and the lack of the ability of the floating mass bolt driver to trap air. The shooter may therefore select the desired level of recoil to correspond with the recoil of the conventional firearm the shooter wishes to simulate.
[0023] It is therefore an aspect of the present invention to provide a compressed gas powered gun simulating the recoil of a conventional firearm.
[0024] It is another aspect of the present invention to provide a compressed gas powered gun wherein the level of recoil provided to the shooter may be selected by the shooter.
[0025] It is further aspect of the present invention to provide a compressed gas powered gun capable of simulating the operation of a conventional firearm.
[0026] It is another aspect of the present invention to provide a compressed gas powered gun capable of both semi-automatic and full automatic operation.
[0027] It is a further aspect of the present invention to provide a compressed gas powered gun wherein different cyclic rates of full automatic fire may be utilized.
[0028] It is another aspect of the present invention to provide a compressed gas powered gun utilizing a magazine and magazine indexing system providing precise alignment of the firing chambers with the barrel.
[0029] It is a further aspect of the present invention to provide a compressed gas powered gun capable of utilizing multiple types of projectiles.
[0030] It is another aspect of the present invention to provide a compressed gas powered gun for providing training that accurately simulates shooting a conventional firearm.
[0031] It is a further aspect of the present invention to provide a compressed gas powered gun that may be legally owned and utilized in locations where conventional firearms are heavily restricted.
[0032] Theses and other aspects of the present invention will become apparent through the following description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] [0033]FIG. 1 is a side view of a compressed gas powered gun according to the present invention.
[0034] [0034]FIG. 2 is a side view of a four-position selector switch according to the present invention.
[0035] [0035]FIG. 3 is a side view of a four-position selector switch according to the present invention, rotated 90° from the position of FIG. 2.
[0036] [0036]FIG. 4 is a side cross-sectional view of a trigger assembly, valve assembly and bolt of a gas powered gun according to the preset invention, showing the position of the components before the trigger is pulled.
[0037] [0037]FIG. 5 is a side cross-sectional view of a trigger assembly, valve assembly, and bolt of a gas powered gun according to the present invention, showing the position of the components at the moment of firing.
[0038] [0038]FIG. 6 is a side cross-sectional view of a trigger assembly, valve assembly, and bolt of a gas powered gun according to the present invention, showing the position of the parts after firing and with the trigger still depressed during semi-automatic fire.
[0039] [0039]FIG. 7 is a side cross-sectional view of a trigger assembly, valve assembly, a bolt of a gas powered gun according to the present invention, showing the position of the components after the bolt has returned and with the trigger still pulled during full automatic fire at a slow cyclic rate.
[0040] [0040]FIG. 8 is a side cross-sectional view of a trigger assembly, valve assembly and bolt of a gas powered gun according to the present invention, showing the position of the components with the bolt retracted and trigger depressed during full automatic fire at a high cyclic rate.
[0041] [0041]FIG. 9 is a top cross-sectional view of one preferred embodiment of a magazine assembly for a gas powered gun according to the present invention, showing the location of the components when the bolt is in the forward position.
[0042] [0042]FIG. 10 is a top cross-sectional view of a magazine assembly of FIG. 9 for a gas powered gun according to the present invention, showing the position of the components when the bolt is in the rearward position.
[0043] [0043]FIG. 11 is a top cross-sectional view of another preferred embodiment of a magazine assembly, with the operating rod deleted for clarity, illustrating the position of the components with the bolt in the forward position.
[0044] [0044]FIG. 12 is a front cross-sectional view of a magazine assembly for a gas-powered gun according to the present invention.
[0045] [0045]FIG. 13 is a top cross-sectional view of a magazine assembly of FIG. 1, showing the position of the components with the bolt in the rearward position.
[0046] [0046]FIG. 14 is a top cross-sectional view of the magazine assembly of FIG. 11, showing the position of the components with the bolt in the forward position.
[0047] [0047]FIG. 15 is a front cross-sectional view of an additional alternative embodiment of a magazine for a gas-powered gun of the present invention.
[0048] [0048]FIG. 16 is a bottom view of an operating rod for a gas-powered gun according to the present invention.
[0049] [0049]FIG. 17 is a side partially cut away view of a bolt, operating rod, and front portion of a bolt driver for a gas powered gun according to the present invention.
[0050] [0050]FIG. 18 is a side view of a bolt and bolt driver for a gas powered gun according to the present invention.
[0051] [0051]FIG. 19 is a side view of an air resistance bolt driver and floating mass bolt driver for a gas-powered gun according to the present invention.
[0052] [0052]FIG. 20 is a side cut away view of a buffer assembly for a gas powered gun according to the present invention, showing the components configured for low recoil.
[0053] [0053]FIG. 21 is a side cut away view of a buffer assembly for a gas-powered gun according to the present invention, showing the components configure for high recoil.
[0054] [0054]FIG. 22 is a side cross-sectional view of a trigger assembly, valve assembly and bolt for a compressed gas gun of the present invention, showing an alternative preferred valve assembly.
[0055] [0055]FIG. 23 is an exploded view of a captive assembly of a forward valve poppet, rear valve poppet, and spring for a gas powered gun according to the present invention.
[0056] Like reference numbers denote like elements throughout the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0057] The preferred embodiments of the present invention is a compressed gas powered gun that simulates the recoil of a conventional firearm discharging a powder propelled projectile. Referring to FIG. 1, a preferred embodiment of the compressed gas powered gun 10 is illustrated. The illustrated embodiments of the compressed gas powered gun simulates an AR-15 or M-16 rifle. The rifle 10 includes an action portion 12 , a barrel 14 , and a stock portion 16 . The stock portion 16 includes a shoulder stock 18 and a pistol grip 20 . The action portion 12 includes an upper receiver portion 22 , to which the barrel 14 is secured, and a lower receiver portion 24 , to which the shoulder stock 18 and pistol grip 20 are secured. A trigger 26 is located just ahead of the pistol grip 20 within the lower receiver portion 24 . The lower receiver portion 24 also includes at least one compressed gas container 28 , and may include a pressure gauge 30 . The upper receiver portion 22 includes a sight mounting rail 32 on its top surface, upon which the electronic dot sight 34 is illustrated. Any conventional sight may be substituted for the electronic dot sight 34 , including telescopic sights, or standard post front, aperture rear iron sights.
[0058] Referring to FIGS. 2 - 8 , 17 - 18 , and 22 , the trigger assembly 36 , bolts 38 , and valve assembly 40 are illustrated. The trigger 26 is pivotally secured within the lower receiver portion 24 at pivot 42 , and is biased towards its forward position by the trigger return spring 44 . The trigger 26 includes a finger-engaging portion 48 , and a selector-engaging portion 50 . The selector-engaging portion 50 is dimensioned and configured to abut a selector 46 when the trigger 26 is pulled rearward. The selector 46 is best illustrated in FIGS. 2 - 3 . The selector 46 includes an actuator 52 for permitting the shooter to rotate the selector 46 as explained below, and a trigger-engaging portion 54 . The trigger-engaging portion 54 includes a first surface 56 , corresponding to safe. A second surface 58 of the trigger-engaging portion 54 corresponds to semi-automatic fire. A third surface 60 of the trigger-engaging portion 54 corresponds to full automatic fire at a slow cyclic rate. This surface 60 is different from selectors used in firearms in that it is cut to a different geometry to be used as a cam stop for the trigger as opposed to a surface that controls disconnectors. It is therefore sufficiently different that it cannot be used in a firearm. Lastly, the trigger-engaging portion 54 defines a channel 62 , corresponding to full automatic fire at a high cyclic rate. Referring back to FIGS. 4 - 8 , the trigger 26 is pivotally secured to one end of a trigger bar 64 , with the other end of the trigger bar 64 secured to a sear trip 66 . The sear trip 66 includes a sear-engaging end 68 , having an upper radius surface 70 and a lower radius surface 72 . The sear 74 is pivotally secured within the lower housing 24 by the sliding pivot 76 . The sear 74 includes a front end 78 , dimensioned and configured to engage the sear trip 66 , and a back end 80 , dimensioned and configured to mate with a notch 82 defined within the bolt 38 . A spring 75 biases the sear rearward, and the front end 78 downward. The bolt 38 contains floating mass 39 , and includes a bolt key 83 , dimensioned and configured to secure an operating rod (described below). A spring-biased bolt driver is located directly behind the bolt 38 , as will also be explained below. The forward portion of the bolt preferably includes an O-ring 84 around its circumference.
[0059] The valve assembly 40 includes a housing 86 , a forward valve 88 , a rear valve 90 , and a spring 92 between the forward valve 88 and rear valve 90 . The front valve 88 is stationary. The housing 86 reciprocates between a forward position and a rearward position, with the inward flange 94 bearing against the front O-ring 96 to close the front valve 88 when the housing 86 is in its rearward position, and with the forward position of the housing 86 corresponding to the front valve being opened. The rear valve 90 reciprocates within the housing 86 , with the rearward position of the valve 90 bringing the O-ring 98 against the housing's rear flange 100 , thereby closing the rear valve. When the rear valve 90 moves forward relative to the housing 86 , the rear valve 90 is opened. Compressed gas is supplied to the valve assembly 40 through the hose 102 , connected between the valve 40 and the compressed gas channels 104 within the lower receiver 24 . The compressed gas container 28 is secured to the compressed gas channels 104 , thereby supplying compressed gas through the channels 104 , hose 102 to the valve assembly 40 . The rear end of the housing 86 also includes an O-ring 106 .
[0060] Referring to FIGS. 9 - 14 and 16 - 17 , a preferred embodiment of a magazine assembly 108 is illustrated. A preferred magazine is a cylinder 110 , located immediately in front of the valve assembly 40 , and directly behind the barrel 14 . A cylinder is defined herein as a rotary magazine similar to that used in a revolver wherein a plurality of firing chambers are arranged around the circumference, and is not necessarily a perfect geometrical cylinder. Cylinder 110 rotates about a central axis (not shown, and well known in the art) and has a plurality of chambers 112 , parallel to the central axis, and bored around the circumference. A preferred and suggested number of firing chambers 112 is six, although a different number may easily be used. The firing chambers 112 are each dimensioned and configured to receive one projectile, with the projectile positioned so that compressed air from the valve 88 will be positioned behind the projectile. The cylinder 110 also includes a plurality of flutes 114 around its circumference, with the flutes 114 located between the chambers 112 , and equal in number to the number of chambers 112 . A spring-biased bearing 116 preferably engages the flutes 114 to precisely align a chamber 112 of the cylinder 110 with the barrel 14 . The bearing 116 preferably has a radius larger than the radius of the flutes 114 , thereby facilitating more precise alignment.
[0061] Indexing of the cylinder 110 is controlled by movement of the bolt 38 . The bolt key 83 secures an operating rod 118 to the bolt 30 , so that as the bolt 38 reciprocates, the operating rod 118 will reciprocate with the bolt 38 . The operating rod 118 , shown in phantom for maximum clarity, defines an angled slot 120 along its bottom surface. A pawl assembly 122 is located directly behind the cylinder 110 . The pawl assembly 122 includes a pawl carrier 124 , having a spring-biased pawl 126 . The pawl carrier 124 includes a pin 128 , dimensioned and configured to fit within the angled slot 120 of the operating rod 118 . The pawl 126 includes a reloading tab 130 , and a cylinder-engaging end 132 having a pusher surface 134 and ramp surface 136 . The cylinder-engaging end 132 is biased into one of chambers 112 by the spring 138 . The magazine assembly 108 may also include a magazine tube 140 , aligned with one of the chambers 112 of the cylinder 110 . The magazine tube 140 is dimensioned and configured to contain a plurality of spherical projectiles. The magazine tube 140 includes a spring-biased follower 142 , and has a loading gate 144 at its forward end. In one preferred embodiment, the chamber 112 in the three o'clock position when viewed from the rear is aligned with the barrel 14 , and the chamber in the eleven o'clock position when viewed from the rear is aligned with the magazine tube 140 . Additionally, in one preferred embodiment, the pawl 126 acts on the chambers in the eleven o'clock and one o'clock positions when viewed from the rear, as will be explained below.
[0062] An alternative embodiment of a magazine assembly 108 is illustrated in FIG. 15. The cylinder 110 has been replaced by an elongated bar 146 , having a plurality of chambers 148 , indexing holes 150 , and flutes 152 along its bottom surface. At least one spring-biased bearing 116 engages a flute 152 to align the chambers 148 with the barrel 14 . A pair of slots 154 , 154 permit the rod 146 to be inserted into the rifle 10 by accommodating the pawl 126 . As will be seen below, indexing of the magazine 146 is very similar to the indexing of the cylinder 110 .
[0063] Referring to FIGS. 18 - 21 , the buffer system 158 is illustrated. A preferred buffer system 158 includes an air piston bolt driver 160 , a floating mass bolt driver 162 having a floating mass 164 therein, and a spring 166 disposed therebetween. The air piston bolt driver may preferably be made of two pieces, a forward portion 168 and rear portion 170 . The buffer system 158 is located directly behind the bolt 38 , and is housed within a buffer tube 172 within the shoulder stock 18 . Depending on the length of the buffer tube 172 , the forward portion 168 of the air resistance bolt driver may either be attached or removed from the rear portion 170 of the air piston bolt driver 158 .
[0064] Referring to FIGS. 22 and 23, an improved valve assembly 174 is illustrated. As before, this valve includes a housing 176 , a forward valve 178 , a rear valve 180 , and a spring therebetween 182 . The valve assembly 174 is a captive assembly, permitting easy disassembly and reassembly. The front valve 178 and rear valve 180 include mating male and female components 184 , 186 forming a telescoping spring guide. As before, moving the valve housing 176 forward with respect to the front valve 178 opens the front valve, and moving the rear valve 180 forward with respect to the housing 176 open the rear valve 180 . The spring 182 biases the rear valve 180 and housing 176 rearward, closing both valves.
[0065] To use the rifle 10 , a gas cartridge 28 is first secured to the compressed gas channel 104 . At least one gas cartridge 28 must be used, and more than one may be used. If desired, a pressure gauge 30 may also be connected to the compressed gas channels 104 . The gas selected may be either compressed air, or any compressed gas commonly used for air guns. One example is carbon dioxide. Next, projectiles are loaded into the magazine. If a rotary magazine or cylinder 110 is used, any projectile suitable for use in an air gun may be used, including spherical projectiles, conventional pellets, darts, etc. The cylinder 110 is loaded by first depressing the bearing 116 so that it does not block removal of the cylinder 110 , and then pushing forward on the reloading tab 130 , thereby retracting the pawls end 132 from the chamber. The cylinder 110 is now free to exit the rifle 10 . The projectiles are pushed into place through the front portion of the chambers, and secured with friction. After loading all six chambers, the cylinder 110 may be inserted back into place within the rifle 10 , after which the shooter re-engages the bearing 116 with the magazine flute 114 . If a tubular magazine is used, preferred projectiles include spherical projectiles. These may be loaded by first retracting the follower 142 using a finger tab secured to the follower (not shown and well known in the art), opening the loading gate 144 , and pouring spherical projectiles into the magazine tube. Releasing the follower 102 will push the first spherical projectile into the chamber 112 aligned with the tubular magazine 140 .
[0066] Compressed air will be supplied from the compressed air container 28 , through the compressed air channels 104 and hose 102 to the center portion of the valve assembly 40 between the forward valve 88 and rear valve 90 . Before firing, the trigger mechanism 36 , valve assembly 40 and bolt 38 are in the positions illustrated in FIG. 4. The bolts 38 , although biased forward by pressure from the spring 166 , is held in its rear position by the rear end 80 of the sear 74 engaging the notch 82 . Pressure from the spring 75 holds the sear 74 in this position, forward pressure from the bolt 38 against the sear 74 pushes the sear towards its forwardmost position on the sliding pivots 76 . The trigger spring 44 holds the trigger 26 in its forwardmost position. The selector 46 may be rotated to the appropriate position, corresponding to safe, semi-automatic, or full automatic at a low or high cyclic rate. FIG. 5 depicts the location of the parts when the trigger is pulled in semi-automatic mode. Trigger 26 has been pulled rearward until the selector-engaging portion 50 engages the surface 58 of the selector 46 . The trigger bar 64 moves rearward, thereby pivoting the end 68 of the sear's trip 66 upward so that the radiused surface 70 pushes the sear's forward end 78 upward, thereby pivoting the sear's back end 80 downward, releasing the bolt 38 to travel forward. During the forward travel of the bolt 38 , the operating rod 118 moves from the rearward position depicted in FIGS. 10 and 13 to the forward position depicted in FIGS. 9 and 14. The pawl carrier 124 is thereby moved from its right side position of FIGS. 10 and 13 to its left side position of FIGS. 9 and 14. The pawl's end 132 is pushed out of the chamber 112 in the one o'clock position when viewed from the rear (FIGS. 10 and 13) to the eleven o'clock position of FIGS. 9 and 14, without rotating the cylinder 110 . When the bolt 38 reaches its forwardmost position, air pressure between the bolt 38 and valve housing 86 , enhanced by the O-rings 84 and 106 , causes the valve housing 86 to move forward, thereby opening the forward valve 88 . This releases compressed air to a position immediately behind the projectile in the chamber 112 aligned with the barrel 14 , thereby discharging the projectile. At the same time, the bolt 38 strikes the rear valve 90 , thereby moving the rear valve 90 forward to open the rear valve 90 , thereby releasing compressed air to the bolt 38 . The bolt 38 is thereby pushed to its rearward position as the pressure from the compressed air overcomes the bias of the spring 166 . At the same time, the operating rod 118 is pulled from its forward position of FIGS. 9 and 14 to its rearward position of FIGS. 10 and 13. The pawl carrier 24 is thereby moved from its left most position to its right most position. As the pawl carrier 124 moves, the surface 134 of the pawl 126 engages the wall of a cylinder 112 , thereby pushing the cylinder 110 so that the next chamber 112 is aligned with the barrel 14 . The bearing 116 is briefly biased out of the flute 114 , engaging the next flute 114 once the appropriate 112 chamber is aligned with the barrel 14 . The above portion of the firing sequence, although based on semi-automatic fire, is identical for full automatic fire. The subsequent portion of the firing sequence changes depending on whether semi-automatic or full automatic fire is selected, and the rate of full automatic fire selected.
[0067] [0067]FIG. 6 depicts the location of the components after firing a shot in semi-automatic mode, with the trigger still depressed. The spring 75 has pulled the sear 74 to the rear, where the end 78 slips off the radiused surface 70 , permitting the sear to rotate so that the rear end 80 rotates upward. The bolt 38 is retracted to a position slightly behind the point where the notch 82 engages the sear 74 . As the bolt 38 returns forward under pressure from spring 166 , the notch 82 and sear 74 engage each other, thereby arresting forward travel of the bolt 38 . At this point, releasing the trigger 26 is necessary to fire another shot.
[0068] [0068]FIG. 7 depicts the position of the parts when the rifle 10 is discharged in full automatic mode at a slow rate of fire. In this mode of operation, the selector 46 is rotated so that the surface 60 engages the selector-engaging portion 50 of the trigger 26 . The trigger 26 is thereby permitted to move back farther than in semi-automatic mode. As before, gas pressure forces the bolt 38 back to a position slightly behind the point wherein it engages the sear 74 . The sear trip 66 is thereby rotated slightly higher, so that the lower radius 72 pushes upward on the front end 78 of the sear 74 . The sear is pulled towards its rear most position on the sliding pivot 76 by the spring 75 , and is thereby also pulled so that the rear end 80 of the sear 74 is rotated upward. As the bolt 38 returns forward under pressure from spring 166 , about {fraction (1/32)} nd inch of the rear end 80 of the sear 74 catches the notch 82 of the bolt 38 . The floating mass 39 , which at this point will be located in the rear portion of the bolts 38 , has slowed the bolt 38 sufficiently so that it will momentarily catch on the sear 74 . When the bolt 38 engages the sear 74 , forward pressure applied to the sear 74 by the bolt 38 will cause the sear 74 to cam off the radiused surface 70 as it moves towards its forwardmost position on the sliding pivot 76 , rotating the sear 74 out of the path of the bolt 38 . The bolt 38 is then free to travel forward to discharge another shot.
[0069] [0069]FIG. 8 depicts the location of the parts if full automatic fire is selected. The selector 46 is rotated so that the selector-engaging portion 50 of the trigger 26 corresponds to the channel 62 within the selector 46 , permitting the trigger 26 to travel to its maximum rearward position. The sear trip 66 is thereby rotated to its maximum upward position, thereby rotating the sear 74 completely out of the way of the bolt 38 . When the bolt 38 travels rearward sufficiently for the spring 166 to overcome the air pressure from the valve 90 , there is nothing to impede the forward motion of the bolt. This results in a maximum cyclic rate.
[0070] A typical cyclic rate for full automatic fire with the low cyclic rate is approximately 600 rounds per minute. A typical cyclic rate for a full automatic fire at a high cyclic rate is approximately 900 rounds per minute, approximately simulating the cyclic rate of an M-16 rifle.
[0071] Upon reading the above description, it becomes obvious that a magazine 146 may be substituted for the cylinder 110 without changing the basic operation of the rifle 10 . As the bolt 38 travels forward, the pawl carrier 124 will move from right to left as before, indexing the pawl 126 from one indexing chamber 150 to the next indexing chamber 150 . As the bolt 38 travels rearward, the pawl carrier 124 will move from left to right as before, causing the pawl 126 to index the magazine 146 so that the next firing chamber 148 is aligned with the barrel 14 . As before, the bearings 116 will fit within the corresponding flutes 152 to align the chambers 148 precisely with the barrel 14 .
[0072] The airgun 10 has two accuracy-enhancing features. The combination of the bearing 116 and smaller radius flutes 114 ensures that the chamber 112 of the cylinder 110 aligns with the barrel 14 so precisely that a forcing cone at the breech end of the barrel is not required. This provides a totally straight path for the projectile throughout the chamber 112 and barrel 14 . Additionally, as compressed gas pressure from the container 28 decreases, the bolt 38 will push the valve 90 further inward as it strikes the valve 90 , thereby increasing the gas flow within the valve assembly 40 . This ensures that each projectile will have a substantially consistent velocity. Therefore, the projectile will have a substantially consistent energy and trajectory.
[0073] While a specific embodiment of the invention has been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalence thereof. | A compressed gas powered gun provides recoil simulating the recoil of a gun firing gunpowder propelled projectiles. The valve assembly provides both consistent shot to shot pressure, and rearward gas pressure for generating recoil. Preferred embodiments of the compressed gas powered gun may include means for adjusting the amount of recoil provided. A trigger mechanism permitting semiautomatic operation, or full automatic operation at a user selectable cyclic rate, is provided. The air gun provides consistent gas pressure behind the projectile from shot to shot. A magazine and magazine indexing system for loading projectiles into the firing chamber in a manner contributing to the accuracy of the air gun is also provided. | 5 |
This application is a continuation-in-part of application Ser. No. 09/978,693 filed on Oct. 18, 2001, now abandoned the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an automatic transmission of a vehicle. More particularly, the present invention relates to a 2-3 up-shifting shift control device of an automatic transmission of a vehicle, and a method thereof.
2. Description of the Related Art
Generally, in an automatic transmission used for a vehicle, a shift control system performs control to realize automatic shifting into different speeds and shift ranges according to various factors including throttle valve opening, vehicle speed and load, and several other engine and driving conditions sensed through a plurality of sensors. That is, based on such factors, the shift control device controls a plurality of solenoid valves of a hydraulic control device such that hydraulic flow in the hydraulic control device is controlled, resulting in shifting of the transmission into the various speeds and shift ranges.
In more detail, when the driver manipulates a shift lever to a particular shift range, a manual valve of the hydraulic control device undergoes port conversion as a result of the manual valve being indexed with the shift lever. By this operation, hydraulic pressure supplied from a hydraulic pump selectively engages a plurality of friction elements of a gearshift mechanism according to the duty control of the solenoid valves, thereby realizing shifting into the desired shift range.
In such an automatic transmission, shift quality is determined by how smoothly the friction elements are engaged and disengaged. Namely, when changing shift ranges, the timing between the engagement of a specific set of friction elements and the disengagement of another specific set of friction elements determines the shift quality of the automatic transmission. Accordingly, there have been ongoing efforts to develop improved shift control methods that enhance shift quality by better controlling the timing of friction elements to engaged and disengaged states.
In the automatic transmission described above, shift control is performed for up-shifting from the first forward speed to the fourth forward speed in turn, down-shifting from the fourth forward speed to the first forward speed in turn and down-skip shifting 4-2 or 3-1, according to the driving condition of a vehicle.
The 2-3 up-shifting shift control of the prior art performs shifting from the 2 driving range into the 3 driving range according to driving speed (output shaft rpm). In such a 2-3up-shifting shift of the prior art, a combination of only two intermediate solenoid valves is applied during the entire shift in order to ensure hydraulic control and shift quality maintenance during the shifting.
Accordingly, the degrees of freedom of hydraulic control are minimal when applying the combination of just two intermediate solenoid valves in 2-3 up-shifting, and the hydraulic control and shift quality maintenance is difficult to ensure without taking into account throttle valve opening. In addition, shift shock from interlocking frequently occurs.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a 2-3 up-shifting shift control device of an automatic transmission of a vehicle and a method thereof to reduce shift shock in shifting from a 2 driving range to a 3 driving range, and to improve the endurance of an automatic transmission.
To achieve the above object, the present invention provides a 2-3 up-shifting shift control device of an automatic transmission, comprising a vehicle speed sensor sensing a vehicle speed, a shift lever position sensor sensing a shift lever position of the vehicle, a throttle position sensor sensing a throttle valve opening of the vehicle, a shift control unit outputting a 2-3 up-shifting drive control signal corresponding to the sensed throttle valve opening when the shift lever position is changed from a 2 driving range to a 3 driving range and the vehicle is driving, and a shift drive unit performing a predetermined 2-3 up-shifting drive control operation by controlling hydraulic pressures in response to the control signal received from the shift control unit.
To achieve the above objective, the present invention provides a shift control method of an automatic transmission comprising the steps of sensing the vehicle speed, sensing the shift lever position of the vehicle, sensing the throttle valve opening of the vehicle, determining a shift control condition corresponding to the sensed throttle valve opening when the shift lever position is changed from the 2 driving range to the 3 driving range and the vehicle is driving, and performing the 2-3 up-shifting control operation according to the determined shift control conditions.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a block diagram of a 2-3 up-shifting shift control device of an automatic transmission according to a preferred embodiment of the present invention; and
FIG. 2 is a flowchart showing an operation of a 2-3 up-shifting shift control method of an automatic transmission according to a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of the present invention will hereinafter be described in detail with reference to the accompanying drawings. While this invention is described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the sprit and scope of the appended claims.
FIG. 1 is a block diagram of a 2-3 up-shifting shift control device of an automatic transmission according to a preferred embodiment of the present invention.
As shown in FIG. 1, a 2-3 up-shifting shift control device of an automatic transmission according to the present invention comprises a vehicle speed sensor 10 sensing the vehicle speed, a shift lever position sensor 20 sensing the shift lever position of the vehicle, a throttle position sensor 30 sensing the throttle valve opening (TVO) of the vehicle, a shift control unit 40 outputting a 2-3 up-shifting drive control signal on condition of the shift control based on the sensed throttle valve opening when the shift lever position is changed from a 2 driving range to a 3 driving range and the vehicle is driving, and a shift drive unit 50 performing the predetermined shift control operation by controlling the hydraulic pressure when it receives a 2-3 up-shifting drive control signal from the shift control unit 40 .
The shift drive unit 50 comprises a first intermediate solenoid valve 52 and a second intermediate solenoid valve 54 controlling a flow of hydraulic pressure when being controlled to do so by the 2-3 up-shifting drive control signal (duty control signal) received from the shift control unit 40 , and a third intermediate solenoid valve 56 being controlled to an on/off state to control a flow of hydraulic pressure according to the on/off signal received from the shift control unit 40 .
Byte values of a 2-3 up-shifting shift control logic code (2, 1, 3, 6, 3, 5, 2, 0, 5, 3, 6, 8, 4, 0, 5, 1) for a preferred embodiment of the present invention will hereinafter be described in detail.
Most importantly, the value 2 of the first byte is a value to check the selection condition of the intermediate solenoid valve combination according to the shift control condition corresponding to the throttle valve opening. The selection condition of the intermediate solenoid valve combination is divided into a first condition and a second condition, where the first condition is set as the condition corresponding to a case when the throttle valve opening (TVO) is less than a predetermined throttle valve opening value, and the second condition is set as the condition corresponding to a case when the throttle valve opening (TVO) is not less than the predetermined throttle valve opening (TVO) value.
The value 1 of second byte is a value for checking the interrupt condition. The interrupt condition concerns turbine speed and throttle valve opening, allowing interruption when a turbine revolution speed is greater than a determined turbine revolution speed, for example 992 rpm (revolutions per minute) and a throttle valve opening is below a determined throttle valve opening value, for example 2.7%.
The value 3 of the third byte is a value for representing output of combinations of three intermediate solenoid valves, and for controlling performance of the fourth byte to the ninth byte under the first condition.
The values of the fourth to the ninth bytes are values for representing the output and maintaining time of first, second, and third combinations of the first, the second and the third intermediate solenoid valves 52 , 54 and 56 under the first condition.
The values 6 and 3 of the fourth and the fifth bytes respectively represent a first code for the first intermediate solenoid valve combination under the first condition and maintaining time for the first intermediate solenoid valve combination under the first condition. The values 5 and 2 of the sixth and the seventh bytes respectively represent a second code for the second intermediate solenoid valve combination under the first condition and maintaining time for the second intermediate solenoid valve combination under the first condition. The values 0 and 5 of the eighth and the ninth bytes respectively represent a third code for the third intermediate solenoid valve combination under the first condition and maintaining time for the third intermediate solenoid valve combination under the first condition.
During 2-3 up-shifting control under the first condition, the shift control unit 40 outputs consecutive signals corresponding to the first, second, and third combination.
The first, second, and third combination of solenoid valves under the first condition can be obviously set corresponding to an automatic transmission by a person skilled in the art, and the codes for the first, second, and third combination may be set arbitrarily by the same.
The value 3 of the tenth byte is a value for representing output of combinations of three intermediate solenoid valves, and for controlling performance of the eleventh byte to the sixteenth byte under the second condition.
The values of the eleventh to the sixteenth bytes are value for representing the output and maintaining time of first, second, and third combinations of the first, the second and the third intermediate solenoid valve 52 , 54 and 56 under the second condition.
The values 6 and 8 of the eleventh and the twelfth bytes respectively represent a first code for the first intermediate solenoid valve combination under the second condition and maintaining time for the first intermediate solenoid valve combination under the second condition. The values 4 and 0 of the thirteenth and the fourteenth bytes respectively represent a second code for the second intermediate solenoid valve combination under the second condition and maintaining time for the second intermediate solenoid valve combination under the second condition. The values 5 and 1 of the fifteenth and sixteenth bytes respectively represent a third code for the third intermediate solenoid valve combination under the second condition and maintaining time for the third intermediate solenoid valve combination under the second condition.
During 2-3 up-shifting control under the first condition, the shift control unit 40 outputs consecutive signals corresponding to the first, second, and third combination.
The first, second, and third combination of solenoid valves under the first condition can be obviously set corresponding to an automatic transmission by a person skilled in the art, and the codes for the first, second, and third combination may be set arbitrarily by the same.
The present invention performs 2-3 up-shifting shift control by using combinations of the three intermediate solenoid valves 52 , 54 , 56 and by dividing the region of the throttle valve opening into a low opening region (the first condition) and a high opening region (the second condition).
As shown above, three intermediate combinations of the valves 52 , 54 , and 56 are employed for each of the first and the second conditions.
FIG. 2 is a flowchart showing an operation of a 2-3 up-shifting shift control method of an automatic transmission according to a preferred embodiment of the present invention. Referring to FIG. 1 and FIG. 2, the method will be described in detail.
The shift control unit 40 senses the vehicle speed by way of the vehicle speed sensor at step 102 of FIG. 2, and when the vehicle is found to be driving it proceeds to step 104 , wherein the shift lever position is sensed. When the shift lever is determined to have moved from a 2 driving range to a 3 driving range in step 106 , the throttle valve opening is sensed in step 108 , and if the throttle valve opening value is not less than the predetermined throttle valve opening value in step 110 , the shift control unit 40 supplies the 2-3 up-shifting shift drive control signal corresponding to the second condition to the shift drive unit 50 , which performs 2-3 up-shifting shift control.
Also, the shift control unit 40 proceeds to step 114 when the sensed shift lever at step 106 described above is not moved from the 2 driving range to the 3 driving range, and it performs whichever other shift control operation that is appropriate at this step. Moreover, the shift control unit 40 proceeds to step 116 when the sensed throttle valve opening value at step 110 described above is less than the predetermined throttle valve opening value, and outputs the 2-3 up-shifting shift drive control signal corresponding to the first condition to the shift drive unit 50 , which then performs the 2-3 up-shifting shift control operation corresponding to the first condition.
As described above, the 2-3 up-shifting shift control device and method of the present invention comprises one more degree of freedom of control of the intermediate solenoid valves in 2-3 up-shifting compared with the prior art, through dividing the region of throttle valve opening during shifting into a low opening region and a high opening region. This results in smoother shifting under multiple conditions during 2-3 up-shifting, thereby reducing shift shock and increasing automatic transmission endurance.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | In order to reduce shift shock in shifting from a 2 driving range to a 3 driving range and improve the endurance of an automatic transmission, a 2-3 up-shifting shift control device of an automatic transmission of the present invention is provided, comprising a vehicle speed sensor, a shift lever position sensor, a throttle position sensor, a shift control unit, and a shift drive unit performing a predetermined 2-3 upshifting drive control operation by controlling hydraulic pressures in response to the sensors. | 5 |
This application is a 371 of PCT/GB00/00183 and claims priority from Great Britain Application No. 9912429.9, filed May 27, 1999, Great Britain Application No. 9901744.4, filed Jan. 27, 1999, and Great Britain Application No. 9901743.6, filed Jan. 27, 1999.
BACKGROUND OF THE INVENTION
The present invention relates to a class of substituted triazolo-pyridazine derivatives and to their use in therapy. More particularly, this invention is concerned with substituted 1,2,4-triazolo[4,3-b]pyridazine derivatives which are ligands for GABA A receptors and are therefore useful in the therapy of deleterious mental states.
Receptors for the major inhibitory neurotransmitter, gamma-aminobutyric acid (GABA), are divided into two main classes: (1) GABA A receptors, which are members of the ligand-gated ion channel superfamily; and (2) GABA B receptors, which may be members of the G-protein linked receptor superfamily. Since the first cDNAs encoding individual GABA A receptor subunits were cloned the number of known members of the mammalian family has grown to include at least six α subunits, four β subunits, three γ subunits, one δ subunit, one ε subunit and two ρ subunits.
Although knowledge of the diversity of the GABA A receptor gene family represents a huge step forward in our understanding of this ligand-gated ion channel, insight into the extent of subtype diversity is still at an early stage. It has been indicated that an α subunit, a β subunit and a γ subunit constitute the minimum requirement for forming a fully functional GABA A receptor expressed by transiently transfecting cDNAs into cells. As indicated above, δ, ε and ρ subunits also exist, but are present only to a minor extent in GABA A receptor populations.
Studies of receptor size and visualisation by electron microscopy conclude that, like other members of the ligand-gated ion channel family, the native GABA A receptor exists in pentameric form. The selection of at least one α, one β and one γ subunit from a repertoire of seventeen allows for the possible existence of more than 10,000 pentameric subunit combinations. Moreover, this calculation overlooks the additional permutations that would be possible if the arrangement of subunits around the ion channel had no constraints (i.e. there could be 120 possible variants for a receptor composed of five different subunits).
Receptor subtype assemblies which do exist include, amongst many others, α1β2γ2, α2β2/3γ2, α3βγ2/3, α2βγ1, α5β3γ2/3, α6βγ2, α6βδ and α4βδ. Subtype assemblies containing an al subunit are present in most areas of the brain and are thought to account for over 40% of GABA A receptors in the rat. Subtype assemblies containing α2 and α3 subunits respectively are thought to account for about 25% and 17% of GABA A receptors in the rat. Subtype assemblies containing an α5 subunit are expressed predominantly in the hippocampus and cortex and are thought to represent about 4% of GABA A receptors in the rat.
A characteristic property of all known GABA A receptors is the presence of a number of modulatory sites, one of which is the benzodiazepine (BZ) binding site. The BZ binding site is the most explored of the GABA A receptor modulatory sites, and is the site through which anxiolytic drugs such as diazepam and temazepam exert their effect. Before the cloning of the GABA A receptor gene family, the benzodiazepine binding site was historically subdivided into two subtypes, BZ1 and BZ2, on the basis of radioligand binding studies. The BZ1 subtype has been shown to be pharmacologically equivalent to a GABA A receptor comprising the α1 subunit in combination with a β subunit and γ2. This is the most abundant GABA A receptor subtype, and is believed to represent almost half of all GABA A receptors in the brain.
Two other major populations are the α2βγ2 and α3βγ2/3 subtypes. Together these constitute approximately a further 35% of the total GABA A receptor repertoire. Pharmacologically this combination appears to be equivalent to the BZ2 subtype as defined previously by radioligand binding, although the BZ2 subtype may also include certain α5-containing subtype assemblies. The physiological role of these subtypes has hitherto been unclear because no sufficiently selective agonists or antagonists were known.
It is now believed that agents acting as BZ agonists at α1βγ2, α2βγ2 or α3βγ2 subunits will possess desirable anxiolytic properties. Compounds which are modulators of the benzodiazepine binding site of the GABA A receptor by acting as BZ agonists are referred to hereinafter as “GABA A receptor agonists”. The α1-selective GABA A receptor agonists alpidem and zolpidem are clinically prescribed as hypnotic agents, suggesting that at least some of the sedation associated with known anxiolytic drugs which act at the BZ1 binding site is mediated through GABA A receptors containing the al subunit. Accordingly, it is considered that GABA A receptor agonists which interact more favourably with the α2 and/or α3 subunit than with al will be effective in the treatment of anxiety with a reduced propensity to cause sedation. Also, agents which are antagonists or inverse agonists at α1 might be employed to reverse sedation or hypnosis caused by al agonists.
The compounds of the present invention, being selective ligands for GABA A receptors, are therefore of use in the treatment and/or prevention of a variety of disorders of the central nervous system. Such disorders include anxiety disorders, such as panic disorder with or without agoraphobia, agoraphobia without history of panic disorder, animal and other phobias including social phobias, obsessive-compulsive disorder, stress disorders including post-traumatic and acute stress disorder, and generalized or substance-induced anxiety disorder; neuroses; convulsions; migraine; depressive or bipolar disorders, for example single-episode or recurrent major depressive disorder, dysthymic disorder, bipolar I and bipolar II manic disorders, and cyclothymic disorder; psychotic disorders including schizophrenia; neurodegeneration arising from cerebral ischemia; attention deficit hyperactivity disorder; and disorders of circadian rhythm, e.g. in subjects suffering from the effects of jet lag or shift work.
Further disorders for which selective ligands for GABA A receptors may be of benefit include pain and nociception; emesis, including acute, delayed and anticipatory emesis, in particular emesis induced by chemotherapy or radiation, as well as post-operative nausea and vomiting; eating disorders including anorexia nervosa and bulimia nervosa; premenstrual syndrome; muscle spasm or spasticity, e.g. in paraplegic patients; and hearing loss. Selective ligands for GABA A receptors may also be effective as pre-medication prior to anaesthesia or minor procedures such as endoscopy, including gastric endoscopy.
WO 98/04559 describes a class of substituted and 7,8-ring fused 1,2,4-triazolo[4,3-b]pyridazine derivatives which are stated to be selective ligands for GABA A receptors beneficial in the treatment and/or prevention of neurological disorders including anxiety and convulsions.
SUMMARY OF THE INVENTION
The present invention provides a class of triazolo-pyridazine derivatives which possess desirable binding properties at various GABA A receptor subtypes. The compounds in accordance with the present invention have good affinity as ligands for the α2 and/or α3 subunit of the human GABA A receptor. The compounds of this invention interact more favourably with the α2 and/or α3 subunit than with the α1 subunit. Indeed, the compounds of the invention exhibit functional selectivity in terms of a selective efficacy for the α2 and/or α3 subunit relative to the α1 subunit.
The compounds of the present invention are GABA A receptor subtype ligands having a binding affinity (K i ) for the α2 and/or α3 subunit, as measured in the assay described hereinbelow, of less than 1 nM. Furthermore, the compounds in accordance with this invention exhibit functional selectivity in terms of a selective efficacy for the α2 and/or α3 subunit relative to the α1 subunit. Moreover, the compounds according to the present invention possess interesting pharmacokinetic properties, notably in terms of improved oral bioavailability.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a compound of formula I, or a pharmaceutically acceptable salt thereof:
wherein
Y represents hydrogen and Z represents fluoro, or Y represents fluoro and Z represents hydrogen or fluoro; and
R 1 represents methyl or ethyl.
The compounds in accordance with the present invention are encompassed within the generic scope of WO 98/04559. There is, however, no specific disclosure therein of compounds corresponding to those of formula I as defined above.
For use in medicine, the salts of the compounds of formula I above will be pharmaceutically acceptable salts. Other salts may, however, be useful in the preparation of the compounds of formula I or of their pharmaceutically acceptable salts. Suitable pharmaceutically acceptable salts of the compounds of formula I include acid addition salts which may, for example, be formed by mixing a solution of the compound of formula I with a solution of a pharmaceutically acceptable acid such as hydrochloric acid, sulphuric acid, methanesulphonic acid, fumaric acid, maleic acid, succinic acid, acetic acid, benzoic acid, oxalic acid, citric acid, tartaric acid, carbonic acid or phosphoric acid.
The present invention also provides a compound of formula I as depicted above, or a pharmaceutically acceptable salt thereof, wherein Y and Z both represent fluoro; and R 1 represents methyl or ethyl.
A particular sub-class of the compounds in accordance with the invention is represented by the compounds of formula IA, and pharmaceutically acceptable salts thereof:
wherein Y, Z and R 1 are as defined above.
Specific sub-classes of the compounds in accordance with the invention are represented by the compounds of formula IIA, IIB, and IIC, and pharmaceutically acceptable salts thereof.
wherein R 1 is as defined above.
In one embodiment of the compounds according to the invention, the moiety R 1 represents methyl.
In another embodiment of the compounds according to the invention, the moiety R 1 represents ethyl.
Specific compounds within the scope of the present invention include:
3-(2,5-difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-methyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine;
3-(2,5-difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine;
3-(2,6-difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine;
7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine;
7-(1,1-dimethylethyl)-6-(2-methyl-2H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine;
7-(1,1-dimethylethyl)-6-(1-methyl-1H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine;
and pharmaceutically acceptable salts thereof.
Also provided by the present invention is a method for the treatment and/or prevention of anxiety which comprises administering to a patient in need of such treatment an effective amount of a compound of formula I as defined above or a pharmaceutically acceptable salt thereof.
Further provided by the present invention is a method for the treatment and/or prevention of convulsions (e.g. in a patient suffering from epilepsy or a related disorder) which comprises administering to a patient in need of such treatment an effective amount of a compound of formula I as defined above or a pharmaceutically acceptable salt thereof.
The binding affinity (K i ) of the compounds according to the present invention for the α3 subunit of the human GABA A receptor is conveniently as measured in the assay described hereinbelow. The α3 subunit binding affinity (K i ) of the compounds of the invention is less than 1 nM.
The compounds according to the present invention elicit a selective potentiation of the GABA EC 20 response in stably transfected recombinant cell lines expressing the α3 subunit of the human GABA A receptor relative to the potentiation of the GABA EC 20 response elicited in stably transfected recombinant cell lines expressing the α1 subunit of the human GABA A receptor.
The potentiation of the GABA EC 20 response in stably transfected cell lines expressing the α3 and α1 subunits of the human GABA A receptor can conveniently be measured by procedures analogous to the protocol described in Wafford et al., Mol. Pharmacol., 1996, 50, 670-678. The procedure will suitably be carried out utilising cultures of stably transfected eukaryotic cells, typically of stably transfected mouse Ltk − fibroblast cells.
The compounds according to the present invention exhibit anxiolytic activity, as may be demonstrated by a positive response in the elevated plus maze and conditioned suppression of drinking tests (cf. Dawson et al., Psychopharmacology, 1995, 121,109-117). Moreover, the compounds of the invention are substantially non-sedating, as may be confirmed by an appropriate result obtained from the response sensitivity (chain-pulling) test (cf. Bayley et al., J. Psychopharmacol., 1996, 10, 206-213).
The compounds according to the present invention may also exhibit anticonvulsant activity. This can be demonstrated by the ability to block pentylenetetrazole-induced seizures in rats and mice, following a protocol analogous to that described by Bristow et al. in J. Pharmacol. Exp. Ther., 1996, 279, 492-501.
Since they elicit behavioural effects, the compounds of the invention plainly are brain-penetrant; in other words, these compounds are capable of crossing the so-called “blood-brain barrier”. Advantageously, the compounds of the invention are capable of exerting their beneficial therapeutic action following administration by the oral route.
The invention also provides pharmaceutical compositions comprising one or more compounds of this invention in association with a pharmaceutically acceptable carrier. Preferably these compositions are in unit dosage forms such as tablets, pills, capsules, powders, granules, sterile parenteral solutions or suspensions, metered aerosol or liquid sprays, drops, ampoules, auto-injector devices or suppositories; for oral, parenteral, intranasal, sublingual or rectal administration, or for administration by inhalation or insufflation. For preparing solid compositions such as tablets, the principal active ingredient is mixed with a pharmaceutical carrier, e.g. conventional tableting ingredients such as corn starch, lactose, sucrose, sorbitol, talc, stearic acid, magnesium stearate, dicalcium phosphate or gums, and other pharmaceutical diluents, e.g. water, to form a solid preformulation composition containing a homogeneous mixture of a compound of the present invention, or a pharmaceutically acceptable salt thereof. When referring to these preformulation compositions as homogeneous, it is meant that the active ingredient is dispersed evenly throughout the composition so that the composition may be readily subdivided into equally effective unit dosage forms such as tablets, pills and capsules. This solid preformulation composition is then subdivided into unit dosage forms of the type described above containing from 0.1 to about 500 mg of the active ingredient of the present invention. Typical unit dosage forms contain from 1 to 100 mg, for example 1, 2, 5, 10, 25, 50 or 100 mg, of the active ingredient. The tablets or pills of the novel composition can be coated or otherwise compounded to provide a dosage form affording the advantage of prolonged action. For example, the tablet or pill can comprise an inner dosage and an outer dosage component, the latter being in the form of an envelope over the former. The two components can be separated by an enteric layer which serves to resist disintegration in the stomach and permits the inner component to pass intact into the duodenum or to be delayed in release. A variety of materials can be used for such enteric layers or coatings, such materials including a number of polymeric acids and mixtures of polymeric acids with such materials as shellac, cetyl alcohol and cellulose acetate.
The liquid forms in which the novel compositions of the present invention may be incorporated for administration orally or by injection include aqueous solutions, suitably flavoured syrups, aqueous or oil suspensions, and flavoured emulsions with edible oils such as cottonseed oil, sesame oil, coconut oil or peanut oil, as well as elixirs and similar pharmaceutical vehicles. Suitable dispersing or suspending agents for aqueous suspensions include synthetic and natural gums such as tragacanth, acacia, alginate, dextran, sodium carboxymethylcellulose, methylcellulose, polyvinyl-pyrrolidone or gelatin.
In the treatment of anxiety, a suitable dosage level is about 0.01 to 250 mg/kg per day, preferably about 0.05 to 100 mg/kg per day, and especially about 0.05 to 5 mg/kg per day. The compounds may be administered on a regimen of 1 to 4 times per day.
The compounds of formula I as defined above may be prepared by a process which comprises reacting a compound of formula III with a compound of formula IV:
wherein Y, Z and R 1 are as defined above, and L 1 represents a suitable leaving group.
The leaving group L 1 is typically a halogen atom, especially chloro.
The reaction between compounds III and IV is conveniently effected by stirring the reactants in a suitable solvent, in the presence of a base. Typically, the solvent is N,N-dimethylformamide, and the base is a strong base such as sodium hydride. In one preferred embodiment, the solvent is dimethylsulfoxide, and the base is caesium carbonate. In another preferred embodiment, the solvent is 1-methyl-2-pyrrolidinone, and the base is sodium hydroxide, in which case the reaction is advantageously performed at a temperature in the region of 0° C.
The intermediates of formula III above may be prepared by reacting a compound of formula V with a substantially equimolar amount of a hydrazine derivative of formula VI:
wherein Y, Z and L 1 are as defined above, and L 2 represents a suitable leaving group; followed, if necessary, by separation of the resulting mixture of isomers by conventional means.
The leaving group L 2 is typically a halogen atom, especially chloro. In the intermediates of formula V, the leaving groups L 1 and L 2 may be the same or different, but are suitably the same, preferably both chloro.
The reaction between compounds V and VI is conveniently effected by heating the reactants in the presence of a proton source such as triethylamine hydrochloride, typically at reflux in an inert solvent such as xylene or 1,4-dioxane.
Alternatively, the intermediates of formula III above may be prepared by reacting a hydrazine derivative of formula VII with an aldehyde derivative of formula VIII:
wherein Y, Z and L 1 are as defined above; followed by cyclization of the intermediate Schiff's base thereby obtained.
The reaction between compounds VII and VIII is conveniently effected under acidic conditions, for example in the presence of a mineral acid such as hydrochloric acid. Cyclization of the resulting Schiff's base intermediate may then conveniently be carried out by treatment with iron(III) chloride in a suitable solvent, e.g. an alcoholic solvent such as ethanol, at an elevated temperature, typically at a temperature in the region of 80° C.
The intermediates of formula VII above may be prepared by reacting the appropriate compound of formula V as defined above with hydrazine hydrate, typically in isobutyl alcohol at an elevated temperature, e.g. a temperature in the region of 90° C., or in 1,4-dioxane or ethanol at the reflux temperature of the solvent; followed, if necessary, by separation of the resulting mixture of isomers by conventional means.
In an alternative approach, the intermediates of formula III above may be prepared by reacting the hydrazine derivative of formula VII as defined above with a compound of formula IX:
wherein Y and Z are as defined above, and Q represents a reactive carboxylate moiety; followed, if necessary, by cyclization of the hydrazide derivative of formula X thereby obtained:
wherein Y, Z and L 1 are as defined above.
Suitable values for the reactive carboxylate moiety Q include esters, for example C 1-4 alkyl esters; acid anhydrides, for example mixed anhydrides with C 1-4 alkanoic acids; acid halides, for example acid chlorides; and acylimidazoles. Suitably, Q represents an acid chloride moiety.
The reaction between compounds VII and IX is conveniently effected by heating in a solvent such as 1-methyl-2-pyrrolidinone to a temperature typically in the region of 160° C.
Alternatively, the reaction between compounds VII and IX may be effected under basic conditions, e.g. in the presence of triethylamine, suitably in an inert solvent such as diethyl ether, and typically at a temperature in the region of 0° C. Cyclization of the resulting compound of formula X may then conveniently be carried out by treatment with 1,2-dibromo-1,1,2,2-tetrachloroethane and triphenylphosphine, in the presence of a base such as triethylamine, suitably in an inert solvent such as acetonitrile, and typically at a temperature in the region of 0° C.
The reaction between compound V and hydrazine hydrate or compound VI will, as indicated above, possibly give rise to a mixture of isomeric products depending upon whether the hydrazine nitrogen atom displaces the leaving group L 1 or L 2 . Thus, in addition to the required product of formula III, the isomeric compound wherein the hydrazine moiety displaces the leaving group L 1 will possibly be obtained to some extent; and likewise for compound VII. For this reason it might be necessary to separate the resulting mixture of isomers by conventional methods such as chromatography.
In another procedure, the compounds of formula I as defined above may be prepared by a process which comprises reacting a compound of formula XI (or its 1,2,4-triazolo[4,3-b]pyridazin-6-one tautomer) with a compound of formula XII:
wherein Y, Z and R 1 are as defined above, and L 3 represents a suitable leaving group.
The leaving group L 3 is suitably a halogen atom, typically chloro or bromo.
The reaction between compounds XI and XII is conveniently effected by stirring the reactants in a suitable solvent, typically N,N-dimethylformamide, in the presence of a strong base such as sodium hydride.
The intermediate of formula XI above may conveniently be prepared by reacting a compound of formula III as defined above with an alkali metal hydroxide, e.g. sodium hydroxide. The reaction is conveniently effected in an inert solvent such as aqueous 1,4-dioxane, ideally at the reflux temperature of the solvent.
In a further procedure, the compounds of formula I as defined above may be prepared by a process which comprises reacting trimethylacetic acid with a compound of formula XIII:
wherein Y, Z and R 1 are as defined above; in the presence of silver nitrate and ammonium persulphate.
The reaction is conveniently carried out in a suitable solvent, for example water or aqueous acetonitrile, optionally under acidic conditions, e.g. using trifluoroacetic acid or sulphuric acid, typically at an elevated temperature.
The intermediates of formula XIII correspond to the compounds of formula I as defined above wherein the tert-butyl substituent at the 7-position is absent, and they may therefore be prepared by methods analogous to those described above for preparing the corresponding compounds of formula I.
In a still further procedure, the compounds of formula I as defined above may be prepared by a process which comprises reacting a compound of formula XIV with a compound of formula XV:
wherein Y, Z and R 1 are as defined above, M represents —B(OH) 2 or —Sn(Alk) 3 in which Alk represents a C 1-6 alkyl group, typically n-butyl, and L 4 represents a suitable leaving group; in the presence of a transition metal catalyst.
The leaving group L 4 is suitably a halogen atom, e.g. bromo.
A suitable transition metal catalyst of use in the reaction between compounds XIV and XV comprises dichlorobis(triphenylphosphine)palladium(II) or tetrakis(triphenylphosphine)palladium(0).
The reaction between compounds XIV and XV is conveniently effected in an inert solvent such as N,N-dimethylformamide, typically at an elevated temperature.
The intermediates of formula XIV may be prepared by reacting a compound of formula IV as defined above with a compound of formula XVI:
wherein L 1 and L 4 are as defined above; under conditions analogous to those described above for the reaction between compounds III and IV.
Where R 1 is methyl, the relevant intermediate of formula IV above may be prepared by the procedures described in EP-A-0421210, or by methods analogous thereto. Where R 1 is ethyl, the relevant intermediate of formula IV may conveniently be prepared by the method described in the accompanying Examples.
The intermediates of formula V above may be prepared by reacting trimethylacetic acid with a compound of formula XVII:
wherein L 1 and L 2 are as defined above; in the presence of silver nitrate and ammonium persulphate; under conditions analogous to those described above for the reaction between trimethylacetic acid and compound XIII.
Where they are not commercially available, the starting materials of formula VI, VIII, IX, XII, XV, XVI and XVII may be prepared by methods analogous to those described in the accompanying Examples, or by standard methods well known from the art.
During any of the above synthetic sequences it may be necessary and/or desirable to protect sensitive or reactive groups on any of the molecules concerned. This may be achieved by means of conventional protecting groups, such as those described in Protective Groups in Organic Chemistry, ed. J. F. W. McOmie, Plenum Press, 1973; and T. W. Greene & P. G. M. Wuts, Protective Groups in Organic Synthesis, John Wiley & Sons, 1991. The protecting groups may be removed at a convenient subsequent stage using methods known from the art.
The following Examples illustrate the preparation of compounds according to the invention.
The compounds in accordance with this invention potently inhibit the binding of [ 3 H]-flumazenil to the benzodiazepine binding site of human GABA A receptors containing the α2 or α3 subunit stably expressed in Ltk − cells.
Reagents
Phosphate buffered saline (PBS).
Assay buffer: 10 mM KH 2 PO 4 , 100 mM KCl, pH 7.4 at room temperature.
[ 3 H]-Flumazenil (18 nM for α1β3γ2 cells; 18 nM for α2β3γ2 cells; 10 nM for α3β3γ2 cells) in assay buffer.
Flunitrazepam 100 μM in assay buffer.
Cells resuspended in assay buffer (1 tray to 10 ml).
Harvesting Cells
Supernatant is removed from cells. PBS (approximately 20 ml) is added. The cells are scraped and placed in a 50 ml centrifuge tube. The procedure is repeated with a further 10 ml of PBS to ensure that most of the cells are removed. The cells are pelleted by centrifuging for 20 min at 3000 rpm in a benchtop centrifuge, and then frozen if desired. The pellets are resuspended in 10 ml of buffer per tray (25 cm×25 cm) of cells.
Assay
Can be carried out in deep 96-well plates or in tubes. Each tube contains:
300 μl of assay buffer.
50 μl of [ 3 H]-flumazenil (final concentration for α1β3γ2: 1.8 nM; for α2β3γ2: 1.8 nM; for α3β3γ2: 1.0 nM).
50 μl of buffer or solvent carrier (e.g. 10% DMSO) if compounds are dissolved in 10% DMSO (total); test compound or flunitrazepam (to determine non-specific binding), 10 μM final concentration.
100 μl of cells.
Assays are incubated for 1 hour at 40° C., then filtered using either a Tomtec or Brandel cell harvester onto GF/B filters followed by 3×3 ml washes with ice cold assay buffer. Filters are dried and counted by liquid scintillation counting. Expected values for total binding are 3000-4000 dpm for total counts and less than 200 dpm for non-specific binding if using liquid scintillation counting, or 1500-2000 dpm for total counts and less than 200 dpm for non-specific binding if counting with meltilex solid scintillant. Binding parameters are determined by non-linear least squares regression analysis, from which the inhibition constant K i can be calculated for each test compound.
The compounds of the accompanying Examples were tested in the above assay, and all were found to possess a K i value for displacement of [ 3 H]-flumazenil from the α2 and/or α3 subunit of the human GABA A receptor of less than 1 nM.
EXAMPLE 1
3-(2,5-Difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-methyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine
a) 3,6-Dichloro-4-(1,1-dimethylethyl)pyridazine
Concentrated sulfuric acid (53.6 ml, 1.0 mol) was added carefully to a stirred suspension of 3,6-dichloropyridazine (50.0 g, 0.34 mol) in water (1.25 l). This mixture was then heated to 70° C. (internal temperature) before the addition of trimethylacetic acid (47.5 ml, 0.41 mol). A solution of silver nitrate (11.4 g, 0.07 mol) in water (20 ml) was then added over approximately one minute. This caused the reaction mixture to become milky in appearance. A solution of ammonium persulphate (230 g, 1.0 mol) in water (0.63 l) was then added over 20-30 minutes. The internal temperature rose to approximately 85° C. During the addition the product formed as a sticky precipitate. Upon complete addition the reaction was stirred for an additional 10 minutes, then allowed to cool to room temperature. The mixture was then poured onto ice and basified with concentrated aqueous ammonia, with the addition of more ice as required to keep the temperature below 10° C. The aqueous was extracted with dichloromethane (3×300 ml). The combined extracts were dried (MgSO 4 ), filtered and evaporated to give 55.8 g of crude product as an oil. This was purified by silica gel chromatography using 0-15% ethyl acetate in hexane as eluent to give 37.31 g (53%) of the desired compound. Data for the title compound: 1 H NMR (360 MHz, d 6 -DMSO) δ1.50 (9H, s), 7.48 (1H, s); MS (ES + ) m/e 205 [MH] + , 207 [MH] + .
b) 3-Chloro-4-(1,1-dimethylethyl)-6-hydrazinylpyridazine
To a solution of 3,6-dichloro-4-(1,1-dimethylethyl)pyridazine (2.0 g, 9.76 mmol) in ethanol (30 ml) was added hydrazine hydrate (0.34 ml, 10.9 mmol) dropwise. The reaction mixture was heated at reflux for 18 h under an atmosphere of nitrogen. The solvent was removed under high vacuum to leave a residue to which was added 5N hydrochloric acid (50 ml). The solution obtained was washed with dichloromethane (20 ml) and the aqueous layer was poured on to a mixture of ice and aqueous ammonia. The resultant solid was collected by filtration and dried under vacuum to yield the title compound (1.2 g). Data for the title compound: 1 H NMR (360 MHz, DMSO) δ1.39 (3H, t, J=7.3 Hz), 4.35 (2H), 7.07 (1H, s), 8.07 (1H, s); MS (ES + ) m/e 201, 203 [MH] + .
c) 6-Chloro-3-(2,5-difluorophenyl)-7-(1,1-dimethylethyl)-1,2,4-triazolo[4,3-b]pyridazine
To a slurry of 3-chloro-4-(1,1-dimethylethyl)-6-hydrazinylpyridazine (1.3 g, 6.5 mmol) in 0.1N hydrochloric acid (60 ml) was added 2,5-difluorobenzaldehyde (0.70 ml, 6.5 mmol) and the reaction mixture was stirred at room temperature for 30 minutes and then heated to 60° C. for 40 minutes. The reaction mixture was allowed to cool and the resultant solid was collected by filtration, dried and dissolved in ethanol (60 ml). To this solution was added iron(III) chloride hexahydrate (5.4 g, 32.5 mmol) in ethanol (15 ml) dropwise over 10 minutes at 80° C. The reaction mixture was stirred at 80° C. for 2 h, allowed to cool and the solvent removed by evaporation under vacuum. The residue was dissolved in dichloromethane (100 ml) and washed with water (3×100 ml), brine, dried (MgSO 4 ), filtered and concentrated under vacuum to yield the title compound (0.75 g). Data for the title compound: 1 H NMR (250 MHz, CDCl 3 ) δ1.57 (9H, s), 7.22-7.29 (2H, m), 7.65-7.71 (1H, m), 8.19 (1H, s); MS (ES + ) m/e 323 [MH] + .
d) 3-(2,5-Difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-methyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine
To a solution of (2-methyl-2H-1,2,4-triazol-3-yl)methanol (0.069 g, 0.4 mmol) and 6-chloro-3-(2,5-difluorophenyl)-7-(1,1-dimethylethyl)-1,2,4-triazolo[4,3-b]pyridazine (0.10 g, 0.31 mmol) in DMF (10 ml) was added sodium hydride (0.015 g of a 60% dispersion in oil, 1.2 mol eq.) and the reaction mixture was stirred at room temperature for 40 minutes. After this time the reaction mixture was diluted with water (80 ml) and the solid that precipitated was collected by filtration and washed several times with water in the sinter funnel. The solid was recrystallised from ethyl acetate/hexane to give pure title compound (0.088 g, 65%). Data for the title compound: 1 H NMR (360 MHz, CDCl 3 ) δ1.41 (9H, s), 3.89 (3H, s), 5.54 (2H, s), 7.23-7.26 (2H, m), 7.64 (1H, m), 7.91 (1H, s), 8.00 (1H, s); MS (ES + ) m/e 400 [MH] + . Anal. Found C, 57.36; H, 4.61; N, 24.60%. C 19 H 19 F 2 N 7 O requires C, 57.14; H, 4.79; N, 24.55%.
EXAMPLE 2
3-(2,5-Difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine
a) (2-Ethyl-2H-1,2,4-triazol-3-yl)methanol
To a solution of 1,2,4-triazole (10 g, 0.145 mol) in DMF (150 ml) at room temperature was added sodium hydride (6.4 g of a 60% disp. in oil, 0.16 mol) in portions over 15 min. When the addition was complete, the reaction mixture was allowed to cool to room temperature, then cooled in an ice-bath and iodoethane (14 ml, 0.174 mol) was added dropwise over 10 mins. The reaction mixture was allowed to warm to room temperature and after stirring for 3 h the solvents were removed under high vacuum to leave a residue which was partitioned between water (300 ml) and ethyl acetate (3×300 ml). The combined organic layers were washed with saturated brine and dried (MgSO 4 ), filtered and concentrated under vacuum to leave an oily residue which was purified by distillation (120° C. @˜20 mmHg) to give 1-ethyltriazole contaminated with ˜15% DMF (2.4 g). The crude product (2.4 g, 0.025 mol) was dissolved in dry THF (35 ml), cooled to −40° C. and n-butyllithium (16.2 ml of a 1.6 molar solution in hexane, 0.026 mol) was added slowly over 20 mins keeping the temperature constant. DMF (2.03 ml, 0.026 mol) was then added and after 15 mins the reaction mixture was allowed to warm slowly to room temperature over 2 h. To the reaction mixture was added methanol (20 ml) followed by sodium borohydride (1 g, 0.026 mol) and the solution was allowed to stir for 14 h. The solvents were removed under vacuum and the residue was partitioned between brine (50 ml) and dichloromethane (6×50 ml). The combined organic layers were dried (MgSO 4 ), filtered and concentrated under vacuum to leave a residue which was purified by silica gel chromatography using 0-5% methanol in dichloromethane as eluent to give the title compound as an off-white solid (0.5 g, 3%). Data for the title compound: 1 H NMR (250 MHz, CDCl 3 ) δ1.48 (3H, t, J=7.3 Hz), 4.25 (2H, q, J=7.3 Hz), 4.75 (2H, s), 5.14 (1H, br s), 7.78 (1H, s).
b) 3-(2,5-Difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine
This compound was prepared using the procedures described in Example 1 Steps a), b), c) and d) with (2-ethyl-2H-1,2,4-triazol-3-yl)methanol used instead of (2-methyl-2H-1,2,4-triazol-3-yl)methanol in Step c). Data for the title compound: 1 H NMR (360 MHz, CDCl 3 ) δ1.40 (9H, s), 1.47 (3H, t, J=7.3 Hz), 4.20 (2H, q, J=14.6 & 7.3 Hz), 5.54 (2H, s), 7.23-7.27 (2H, m), 7.65 (1H, m), 7.94 (1H, s), 8.00 (1H, s); MS (ES + ) m/e 414 [MH] + . Anal. Found C, 58.17; H, 5.01; N, 23.79%. C 20 H 21 F 2 N 7 O requires C, 58.10; H, 5.12; N, 23.72%.
EXAMPLE 3
3-(2,6-Difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine
a) 6-Chloro-3-(2,6-difluorophenyl)-7-(1,1-dimethylethyl)-1,2,4-triazolo[4.3-b]pyridazine
A mixture of 3,6-dichloro-4-(1,1-dimethylethyl)pyridazine (2 g, 9.75 mmol), 2,6-difluorobenzoic acid hydrazide (2.52 g, 14.6 mmol) (WO 95/24403) and triethylamine hydrochloride (2.01 g, 14.6 mmol) in 1,4-dioxane (10 ml) was stirred and heated at reflux for 3.5 days. Upon cooling, the volatiles were removed in vacuo and the residue was triturated with dichloromethane. Any undissolved solid was removed by filtration. The residue was purified by chromatography on silica gel eluting with 0%→25% ethyl acetate in dichloromethane to give the required product (0.42 g). Data for the title compound: 1 H NMR (250 MHz, CDCl 3 ) δ1.57 (9H, s), 7.09-7.16 (2H, m), 7.51-7.63 (1H, m), 8.19 (1H, s); MS (ES 30 ) m/e 323 (MH + .
b) 3-(2,6-Difluorophenyl)-7-(1,1-dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-1,2,4-triazolo[4,3-b]pyridazine
This compound was prepared from 6-chloro-3-(2,6-difluorophenyl)-7-(1,1-dimethylethyl)-1,2,4-triazolo[4,3-b]pyridazine and (2-ethyl-2H-1,2,4-triazol-3-yl)methanol following the procedure (sodium hydride, DMF) described in WO 98/04559. Data for the title compound: m.p. 182° C.; 1 H NMR (400 MHz, CDCl 3 ) δ1.39-1.45 (12H, m), 4.10-4.16 (2H, m), 5.46 (2H, s), 7.09-7.15 (2H, m), 7.52-7.59 (1H, m), 7.92 (1H, s), 8.00 (1H, s); MS (ES 30 ) m/e 414 [MH] + ; Anal. Found: C, 58.19; H, 5.05; N, 23.80%. C 20 H 21 F 2 N 7 O requires: C, 58.10; H, 5.12; N, 23.72%.
EXAMPLE 4
7-(1,1-Dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine
a) 6-Chloro-7-(1,1-dimethylethyl)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine
2,3,6-Trifluorobenzoyl chloride (4.0 g) was added dropwise to a cooled (15° C.) solution of 3-chloro-4-(1,1-dimethylethyl)-6-hydrazinylpyridazine (4 g) in dry 1-methyl-2-pyrrolidinone (50 ml). After the addition the reaction mixture was heated at 160° C. for 24 h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate (200 ml), and washed twice with water (200 ml). The organic phase was separated, dried (sodium sulfate), and evaporated at reduced pressure. The residue was crystallised from dichloromethane on dilution with diethyl ether to afford the title compound (5.3 g) as a colourless solid: 1 H NMR (400 MHz, DMSO-d 6 ) δ1.52 (9H, s), 7.50 (1H, m), 7.92 (1H, m), 8.45 (1H, s); MS (ES 30 ) m/z 341/343 [MH] + .
b) (2-Ethyl-2H-1,2,4-triazol-3-yl)methanol: alternative procedure
1,2,4-Triazole (100.0 g, 1.45 mol) in anhydrous THF (950 ml) was cooled to 0° C. and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (220 g, 1.45 mol) was added in one portion. The reaction mixture was stirred for 30 min until complete dissolution was observed. Whilst maintaining the ice/water cooling bath, iodoethane (317 g, 2.03 mol) was added dropwise over a 15 min period resulting in an internal temperature rise to 30° C. The reaction was stirred at room temperature for 16 h, after which the DBU hydroiodide was removed by filtration. The filtrate was cooled to −75° C. under an atmosphere of dry nitrogen. Hexyllithium (458 ml of 33% solution in hexanes) was added dropwise over 25 min keeping the internal temperature below −55° C. The reaction mixture was aged for 30 min (back to −75° C.) and then dry N,N-dimethylformamide (108 ml, 1.39 mol) was added dropwise over 10 min maintaining internal temperature below −60° C. The reaction mixture was aged at −70° C. for 90 min, then allowed to warm to 0° C. over 30 min. Ethanol (340 ml) was added over 10 min. Sodium borohydride (26.3 g, 0.695 mol) was then added portionwise maintaining the internal temperature below 6° C. After the addition the reaction mixture was allowed to warm to room temperature and stirred for 1 h. 2M H 2 SO 4 (200 ml) was then added slowly with caution and the mixture stirred at room temperature for 20 h. The reaction mixture was concentrated to 675 ml and sodium sulfate (135 g) was added in one portion. The reaction mixture was warmed to 35° C. and stirred for 15 min. The solution was extracted with warm (45° C.) isobutyl alcohol (2×675 ml). The combined organic fractions were concentrated under reduced pressure to a volume of approximately 450 ml at which point the product crystallised. Heptane (1,125 l) was added and the slurry concentrated under reduced pressure to remove most of the isobutyl alcohol. Heptane was added to give a final slurry volume of 680 ml. After cooling to 0° C., filtration gave the title compound (137 g, 74% from 1,2,4-triazole). 1 H NMR as for Example 2 Step a).
c) 7-(1,1-Dimethylethyl)-6-(2-ethyl-2H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine
To the product of Step a) (2.60 g) and the foregoing product (1.0 g) in dry dimethylsulfoxide (10 ml) was added caesium carbonate (3.05 g), and the mixture stirred at 50° C. under an atmosphere of dry nitrogen for 24 hours. On cooling to room temperature, the mixture was partitioned between ethyl acetate and water. The organic phase was separated, washed with water, evaporated at reduced pressure, and the residue chromatographed on silica gel (eluent 2.5% methanol-dichloromethane). The product was crystallised from ethyl acetate/diethyl ether/isohexane, to afford the title compound as a colourless solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ1.26 (3H, t, J=7.1 Hz), 1.38 (9H, s), 4.10 (2H, q, J=7.1 Hz), 5.53 (2H, s), 7.46 (1H, m), 7.88 (1H, m), 7.94 (1H, s), 8.18 (1H, s); MS (ES + ) m/z 432 [MH] + .
EXAMPLE 5
7-(1,1-Dimethylethyl)-6-(2-methyl-2H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine
To the product of Example 4 Step a) (2.67 g) and (2-methyl-2H-1,2,4-triazol-3-yl)methanol (prepared as described in EP-A-421210) (0.93 g) in dry dimethylsulfoxide (10 ml) was added caesium carbonate (3.14 g), and the mixture stirred at 50° C. under an atmosphere of dry nitrogen for 24 hours. On cooling to room temperature, the mixture was partitioned between ethyl acetate and water. The organic phase was separated, washed with water, evaporated at reduced pressure, and the residue chromatographed on silica gel (eluent 2.5% methanol-dichloromethane). The product was crystallised from ethyl acetate/diethyl ether/isohexane, to afford the title compound as a colourless solid. 1 H NMR (500 MHz, DMSO- 6 ) δ1.39 (9H, s), 3.74 (3H, s), 5.50 (2H, s), 7.46 (1H, m), 7.88 (1H, m), 7.90 (1H, s), 8.17 (1H, s); MS (ES + ) m/z 418 [MH] + .
EXAMPLE 6
7-(1,1-Dimethylethyl)-6-(1-methyl-1H-1,2,4-triazol-3-ylmethoxy)-3-(2,3,6-trifluorophenyl)-1,2,4-triazolo[4,3-b]pyridazine
To the product of Example 4 Step a) (0.559 g) and (1-methyl-1H-1,2,4-triazol-3-yl)methanol (prepared as described in EP-A-421210) (0.20 g) in dry dimethylsulfoxide (2 ml) was added caesium carbonate (0.67 g), and the mixture stirred at 60° C. under an atmosphere of dry nitrogen for 48 hours. On cooling to room temperature, the mixture was partitioned between ethyl acetate and water. The organic phase was separated, washed with water, evaporated at reduced pressure, and the residue chromatographed on silica gel (eluent 2% methanol-dichloromethane). The product was crystallised from ethyl acetate/diethyl ether, to afford the title compound as a colourless solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ1.39 (9H, s), 3.85 (3H, s), 5.30 (2H, s), 7.46 (1H, m), 7.86 (1H, m), 8.14 (1H, s) 8.46 (1H, s); MS (ES + ) m/z 418 [MH] + . | 1,2,4-triazolo[4,3-b]pyridazine derivatives, possessing a difluoro-or tri-fluoro-substituted phenyl ring at the 3-position, a triazolyl moiety at the 6-position, and a tert-butyl group at the 7-position, are selective ligands for GABA A receptors, in particular having high affinity for the α2 and/or α3 subunit thereof, and are useful in the treatment of anxiety and convulsions. | 2 |
This application is a continuation of application Ser. No. 06/934,403, filed Nov. 24, 1986 now abandoned.
FIELD OF THE INVENTION
The present invention relates to educational kits for classroom teaching in general, and relates, in particular, to educational kits for use in teaching the principles of botany and genetics to elementary or secondary school students.
BACKGROUND OF THE INVENTION
In the teaching of biology to primary and secondary school students it is essential if students are to have a good feel and understanding of the science that they have an opportunity to work with and utilize living materials. Most biology courses lack convenient living materials to use in their course work and, in addition, most biology courses use animal subjects predominately. At an elementary and secondary school level, it is generally considered impractical to teach general or advance courses in botany, genetics, science education, or applied plant sciences because of the difficulty in finding suitable living plant material that would permit students to explore plant growth development, physiology, reproduction, genetics, evolution and ecology. Such studies are normally difficult to perform in an educational setting because the life cycle of most plants is of sufficiently long duration that multiple generations cannot conveniently be grown during any time period convenient to an educational schedule.
Traditionally one of the difficulties in performing research or breeding development in plant species is the long time periods necessary to perform breeding projects in plant species. Since genetic experiments typically require many generations of individuals with appropriately selected cross-breeding among individuals with particular traits, many years of work are necessary if only one, or a relatively few generations, of plants complete their life cycle during any given year. Accordingly, it was perceived as useful to generate plants which would have a shorter life cycle, so that more generations of plants could be grown up and selectively cross-bred in a shorter period of time.
A series of short life cycle plants, referred to as rapid-cycling plants, has been developed for plants in the family Cruciferae. Plants of this family are familiarly referred to as Crucifers because of the four petalled flowers, which are deemed to resemble a cross or crucifix. The Crucifer family is so large that it is broken into sub-groups, referred to as tribes. One of the tribes of Crucifer plants is the Brassicae tribe. The genus Brassica includes a variety of plants of commercial utility, such as mustard, brussel sprouts, cabbage, kale, cauliflower, broccoli, and rape. A related genus is Raphanus which is represented in commercial crop species by the radish. Rapid cycling sub-populations have been generated in populations of the genus Brassica as well as the genus Raphanus. The cytogenetic interrelationships among six Brassica species and Raphanus are illustrated graphically by the following chart, in which cytoplasmic genome is designated by capital letters and nuclear genome is designated by lower case letters, and where a indicates 10, b indicates 8 and c and r indicate 9 chromosomes. ##STR1##
A rapid cycling population of plants has been developed for each of these species (not for Raphanobrassica). Each of the populations grows rapidly and flowers in a time period of between sixteen and thirty days. Plants of these rapid-cycling populations average, depending on the species, between sixteen and thirty days to flower, between thirty-six and sixty days for an entire plant life cycle and between eighteen and one hundred and seven seeds produced from each plant. This allows for these population of plants to be cycled over six and ten successive generations per year.
Stocks of rapid cycling Brassica plants are maintained by the Crucifer Genetics Cooperative, 1630 Linden Drive, University of Wisconsin, Madison, Wis. 53706. The Cooperative publishes a Resource Book describing the manipulation and handling of fast cycling Crucifer stock and also maintains seed reserves of the stocks. Seeds are readily available to anyone interested in Brassica botany or genetics by application for membership to the cooperative, which is open to all. Stocks of the plants are thus readily available and obtainable and maintained indefinitely by the Cooperative.
SUMMARY OF THE INVENTION
The present invention is summarized in that an educational kit for the classroom study of plants comprises a compact plant growth environment including a physical container for receiving plants therein and a continuous watering system capable of providing liquid to plants in the container; and a quantity of seeds of fast-cycling Brassica plants, the seeds having been bred to develop into plants having a characteristic average optimal growing cycle of less than sixty (60) days and having a phenotype of educational interest.
It is an object of the present invention to provide a compact and easy to use educational kit for classroom study at elementary or secondary school level to study plant growth and plant genetics.
It is another object of the present invention to provide such an educational kit which allows for a variety of experiments to be performed with the same plant populations or with seeds of plants of varying genetic makeup in the rapid cycling background, with the same apparatus.
It is another object of the present invention to provide such an educational kit in which experiments can be accomplished in a relatively short period of time so that multiple generation experiments can be accomplished in the time period required by academic scheduling.
Other objects, advantages and features of the present invention will become apparent from the following specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plant elevation view of a plant growth environment suitable for use in the present invention.
FIG. 2 is a perspective view of a four-unit plant container for the environment of FIG. 1.
FIG. 3 is a perspective view of a minipot such as is used in FIGS. 2 and 3.
FIG. 4 is a perspective view illustrating the making of a bee stick.
DETAILED DESCRIPTION OF THE INVENTION
The educational kit of the present invention is constructed to utilize fast growing and flowering plants from the Brassicae tribe. A series of such plants have been developed and their seeds are deposited with and available from the Crucifer Genetics Cooperative at the University of Wisconsin, Madison, Wis. These populations of Brassica species were methodically selected and bred from commonly available Brassica plant populations. Over 2,000 seed samples were obtained from the U.S. Department of Agriculture National Plant Germplasm System and were planted out. It was noted that a few of the plants in each species of Brassica flowered in a significantly shorter time than the mean of plants for each of those species. The fastest flowering plants from each species were cross-pollinated with each other to develop populations intended to be fast-cycling, so that they could be tailored strictly for experimental uses under laboratory conditions. To do so, generations of the fast flowering plants from each Brassica species were grown in high plant densities in 28 by 55 centimeter plastic multi-pots of 96 pots per tray. An artificial soil was used consisting of a one-to-one mixture of peat moss and vermiculite, and the plants were watered with a balanced nutrient solution. The plants were grown at room temperature and continuously illuminated with very high output fluorescent lamps with 250 micromoles per second per square meter of irradiance. Diverse populations were derived by interpollinating diverse early flowering types within each species. From the offspring thus produced individuals were selected for successive generations based on minimum time from sowing to flowering, rapid seed maturation, absence of seed dormancy, small plant size, and high female fertility. Plant populations of 288 plants or more were grown in each cycle of the reproduction and the 10% of each population that flowered the earliest was selected and mass pollinated for the next generation. This process was continued over generations until the average days to flowering became stabilized and when 50% of the population flowered within a 2 to 3 day period, at which point selection on the population was discontinued. The population within each species was then increased by mass pollination and designated as a rapid cycling base population. A rapid cycling base population for each of the six Brassica species and for the one Raphanus species indicated in FIG. 1 above was developed. Those rapid cycling population have been given numbers generated from the Crucifer Genetics Cooperative (CrGC 1 through 7). The characteristics are summarized in the following chart.
TABLE 2__________________________________________________________________________ Mean Mean Length MeanCrGC Days (cm) to Seeds Days Cyclesstock to first per for pernumberSpecies Genome flower flower plant cycle year__________________________________________________________________________1. B. Aaa 16 11.9 78 36 10campestris2. B. Bbb 20 27.1 69 40 9nigra3. B. Ccc 30 22.6 18 60 6oleracea4. B. ABaabb 19 29.6 107 39 9juncea5. B. ACaacc 25 35.3 76 55 6napus6. B. BCbbcc 26 41.7 67 56 6carinata7. R. Rrr 19sativus__________________________________________________________________________
Stocks of rapid-cycling base populations CrGc 1 through CrGC 7 are on deposit with and are maintained by the Crucifer Genetics Cooperative, 1630 Linden Drive, University of Wisconsin, Madison, Wis. 53706 and are readily available to the public.
These rapid cycling populations are homogeneous with respect to plant morphology and flowering time although they contain substantial genetic variation as revealed by isozyme variations among individuals. The individuals also demonstrate a wide variety of plant-to-plant disease susceptibility. It is believed that the base populations possess a significant reservoir of diverse genes useful to plant breeders themselves. Thus significant genetic variation occurs within the plant population which can be useful for experimental and pedagogical purposes.
As may be seen by the foregoing discussion, such rapid-cycling base populations can be readily generated from commonly available plant genetic stocks. While the readily available stocks from the Crucifer Genetics Cooperative are convenient to use, other similar rapid-cycling base populations can be readily created by following a similar breeding program.
Individual plants and sub-populations can be readily selected from these rapid-cycling plant populations on the basis of easily observable traits of educational interest. For example, plants can be selected from the general base population on the basis of response to a plant growth factor. Then, plants of the sub-population can be planted out in two groups, and plants in one of the groups can be exposed to the growth factor so that students can observe the change in growth pattern of the two groups of plants based on the effect. Some plant growth factors would have a positive effect on the treated plants. Examples of this type of growth factor include plant growth regulators or hormones, nutrients or symbionts. Other plant growth factors would adversely affect the treated plants. Such factors would include antibiotics, herbicides, parasites, pathogens, pests and competitive plants (i.e. weeds). To use the rapid-cycling base population plants in an educational kit illustrating the effect of such growth factors, the kit would not only include a supply of the growth factor, but the sub-population of plants would preferably be selected to be made up of plants highly responsive to the growth factors, positively or negatively, so that the classroom illustration of the effect would be as striking as possible.
Another sub-population of plants which would be preferred for selection for use in the present invention would be sub-populations having variant alleles of an easily observable phenotypic trait. Such traits exist with and without the base populations but can easily be transferred into any selected sub-population from other germplasm. For example, stocks exist in the Crucifer Genetics Cooperative of plants of the species of each of the rapid cycling base populations which have one specific easily observable phenotypic difference, petal color of the flowers. It is readily possible, particularly given the fast cycling time of the plants, to breed two subpopulations of a rapid cycling population differing only by petal color. Given seeds of each of these two sub-populations, students could make appropriate cross-breedings to demonstrate the rules of Mendelian population genetic inheritance. Inbred plant lines could be generated from such sub-populations which could then be bred to be either heterozygous or homozygous for the particular phenotypic trait sought so that individual plant-by-plant genetic experiments could be conducted as opposed to whole population studies of inheritance laws. A kit using such plants would normally include an allelic pairing of genes. It would be possible also to demonstrate the difference between nuclear and cytoplasmic genetic inheritance.
In order to effectively use the rapid cycling base population plants within the present invention, it is necessary to have a compact plant growth environment suitable for use in a relatively easy manner in a classroom at elementary or secondary school level. The plant growth environment must include a physical support system suitable for containing plants therein. A suitable plant growth environment is schematically illustrated in FIG. 1. As viewed in FIG. 1, the plant environment includes a plurality of individual plant containers, in the form of plant minipots, 12 bundled in groups of four. The plant containers 12, which are also illustrated in FIG. 2, are formed as a minipot having a rigid exterior supporting shape and an interior cavity extending vertically through it, into which a soil mixture can be placed. The minipots 12 also include on their bottom, as can be viewed in FIG. 2, a porous bottom pad 14 formed of absorbent material. As can be viewed in FIG. 1, the plant minipots 12 sit upon a common porous wicking pad 16. The wicking pad 16 is supported on a platform 18, but extends off of both sides thereof. The ends of the wicking pads, extending off of the platform 18, are contained within the water reservoirs 20 located on either side of the platform 18. Alternatively, one large reservoir 20 could extend completely underneath and out adjacent both sides of the platform 18. Located a short distance above the plants themselves is a bank of fluorescent lights, indicated at 22. The lights 22 are preferably cool white flourescent tubes mounted parallel, separated two and one-half to three inches apart, and maintained 2 to 3 inches above the tallest plant.
Shown in FIG. 2 is a more detailed illustration of a typical four unit assembly of plant containers 12. Four of the plant minipot containers 12 are joined in the common unit, e.g. by a rubber band 24 placed around the exterior thereof. In between the minipots 12 a pair of vertical plastic separators 26 have been placed extending vertically upward between the individual plant pots 12. The plant separators 26 have notched edges so that a plurality of horizontal strings 28 can be extended therebetween the notches to provide a trellis onto which the plants may climb. Alternatively, plants may be tied to small bamboo sticks inserted in the soil. A pot label 30 is provided to label the plants in the minipot grouping.
Individual plants when potted into the mini-pots illustrated in FIGS. 1 to 3, and if they are to be husbanded for optimal growth, should be cultivated in a rich soil mixture. The soil mixture which has been found optimal for the base populations of rapid-cycling plants has been found to contain one part compost top soil, one part sphagnum peat moss finely screened, one part perlite, and one part vermiculite, to which is added a very small amount of trace elements which are sold commercially in a wide variety of formulations, such as Esmigran. The soil mixture may be pasteurized to eliminate microbes detrimental to plant growth. The completed soil mixture may be supplied with the kit and is preferably supplied in the minipots 12 themselves so that they are ready for student use.
Also included with the supplies for the growth of the fast cycling Brassica plants would be the clear plastic support separators 26. Suitable pre-cut squares of cheese cloth may also be provided for germination, as well as a watering pipette for initial watering and chemical treatments. Rapidly dissolving tablets or capsules containing an anti-microbial agent, such as copper sulfate may be included for addition to the reservoir water for control of algae in the reservoir and in the wicking pad 16.
For any given experiment to be formed for educational purposes with the fast cycling populations, one or more of a number of experimental supplies would be necessary. Among the necessary supplies could be rubbing alcohol, which would be useful for sterilizations. Tweezers would be included, which are useful for thinning plants during the growth cycle. In addition, for all experiments requiring cross-pollinations it would be necessary to incorporate a pollination tool, such as a bee stick. A bee stick is a toothpick with the thorax of a honey bee glued on one end so as to make use of the pollen gathering character of the hairy thorax of a bee. The fabrication and use of bee sticks is described in detail in Williams, "Bee-Sticks, an Aid in Pollinating Cruciferae," Horticulture, 15(6), p. 802-803, Dec. 1980. The bee sticks could be supplied preassembled or could be supplied in parts to be assembled by the students from bee cadavers, toothpicks and glue. The making of a bee stick is also illustrated in FIG. 4. The thorax 32 of a honey bee is dissected from the head and abdomen and is then glued to one end of a toothpick 34. The bee stick thus formed can be hand manipulated by the toothpick 34 so that the bee thorax 32 may be used for the pollination. It would be necessary to have appropriate measuring devices and marking and labeling devices, such as pot labels 30, to keep track of the individual plants.
The husbandry of fast-cycling Brassica plants in the apparatus of FIGS. 1-3 is relatively straightforward. Soil mixture is filled into each minipot 12 together with a small amount of N-P-K pellets. Three or four fast-cycling seeds are then sown in the soil and are covered with a layer of vermiculite. Water is then introduced by pipette into the minipot until it runs out the bottom pad 14. The porous wicking mat 16 is then saturated with water and the minipots 12 are placed on it. The reservoirs 20 are then filled with water. The lights 22 are then placed on and the plants illuminated twenty-four hours a day. If plants of B. campestris, i.e. CrGC-1, are used, the cotyledons emerge in two to three days. The plants are thinned with tweezers to one plant per pot. The plants flower in fourteen to sixteen days from seed moistening. The plant separators 16 separate the plants for pollination. Using bee sticks, pollen can be collected from designated male parents for placement on female parents. Twenty days after pollination, water is removed for three to four days. The siliques are cut and air dried in paper bags for five to seven days. The dried siliques can be rolled between the hands over a collecting pan to collect seed for the next generation.
Appropriate instructions, both general as to Brassica cultivation, and specific to the plants and experiment to be performed with each kit would be included describing this process in detail.
Within the basic kit as described heretofore, there would be added to it various materials appropriate for any given experiment. For example, for an experiment related to a specific trait or the demonstration of Mendelian inheritance, the specific seed stocks would need to be selected for their individual observable phenotypes as related to a particular experiment. For an educational effort directed to ecological pollution, potential chemical pollutants having an adverse effect upon plant growth could be supplied with the kit so that they could be applied to the plants without danger to the students so as to demonstrate the negative effect on plant growth as a result. Plant nutrients or hormonal plant growth regulators could be supplied to demonstrate their effect on plant growth. Antibiotics or herbicides could be supplied in small doses to demonstrate their adverse effect on plant growth as could parasites, pests or pathogens. Competitiveness could be determined by growing stocks together in the same pot or by including weed seeds selected to provide competition to the Brassica populations with the kit. Other biological symbionts could be provided to demonstrate their effects, either adverse or positive, on the growing plant populations.
The educational kit of the present invention in actual use would also include appropriate documentation. The documentation would include detailed teacher and student instructions on the husbandry of the Brassica plants as well as instructions on how to perform the demonstration or experiment of the particular kit. In addition, the documentation would preferably include general botanical information on the history and uses of Brassica and other relevant background information to enrich student and teacher learning.
It is understood that the present invention is not limited to the particular embodiments illustrated herein but embraces all such modified forms thereof as come within the scope of the following claims. | An educational kit for the classroom study of plants including a compact plant growth environment and a seed of fast-cycling Brassica plants. The fast-cycling plants grow in compact areas and have generation cycle times of sixty days or less making them convenient for classroom study. Various experiments on plant growth, physiology and genetics can be performed with the kits. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of copending application Ser. No. 777,928, filed Mar. 15, 1977, abandoned, which, in turn, is a continuation-in-part of application Ser. No. 753,619, filed Dec. 22, 1976, and now abandoned, which, in turn, is a continuation-in-part of application Ser. No. 687,332, filed May 17, 1976 and now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to certain novel benzo[c]quinolines and more particularly to 1,9-dihydroxyoctahydrobenzo[c]quinolines, 1-hydroxyhexahydrobenzo[c]quinoline-9(8H)-ones and 1-hydroxy-tetrahydrobenzo[c]quinolines and derivatives thereof useful as CNS agents, especially as analgesics and tranquilizers, as hypotensives in mammals, including man, as agents for the treatment of glaucoma and as diuretics; and to intermediates therefor.
An acceptable alternative nomenclature for the herein described compounds of formulae I-IV is based upon replacement of the root "benzo[c]quinoline" with "phenanthridine". Thus, d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3(5-phenyl-2-pentyloxy)benzo[c]quinoline becomes d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)phenanthridine.
DESCRIPTION OF THE PRIOR ART
Despite the current availability of a number of analgesic agents, the search for new and improved agents continues, thus pointing to the lack of an agent useful for the control of broad levels of pain and accompanied by a minimum of side-effects. The most commonly used agent, aspirin, is of no practical value for the control of severe pain and is known to exhibit various undesirable side-effects. Other, more potent analgesic agents such as d-propoxyphene, codeine, and morphine, possess addictive liability. The need for improved and potent analgesic agents is, therefore, evident.
The analgesic properties of 9-nor-9β-hydroxyhexahydrocannabinol and of other cannabinoid structures, such as Δ 8 -tetrahydrocannabinol (Δ 8 -THC) and its primary metabolite, 11-hydroxy-Δ 8 -THC, have been reported by Wilson and May, Absts. Papers, Am. Chem. Soc., 168 Meet., MEDI 11 (1974), J. Med. Chem. 17, 475-476 (1974), and J. Med. Chem., 18, 700-703 (1975).
U.S. Pat. Nos. 3,507,885 and 3,636,058, issued Apr. 21, 1970 and Jan. 18, 1972, respectively, describe various 1-hydroxy-3-alkyl-6H-dibenzo[b,d]pyrans having at the 9-position substituents such as: oxo, hydrocarbyl and hydroxy or chloro, hydrocarbylidene, and intermediates therefor.
U.S. Pat. No. 3,649,650, issued Mar. 14, 1972, discloses a series of tetrahydro-6,6,9-trialkyl-6H-dibenzo[b,d]pyran derivatives having at the 1-position an ω-dialkylaminoalkoxy group active as psychotherapeutic agents.
German Specification No. 2,451,934, published May 7, 1975, describes 1,9-dihydroxyhexahydrodibenzo[b,d]pyrans and certain 1-acyl derivatives thereof having at the 3-position an alkyl or alkylene group, as hypotensive, psychotropic, sedative and analgesic agents. The precursor hexahydro-9H-dibenzo[b,d]pyran-9-ones used in their preparation, and which are reported to have the same utility as the corresponding 9-hydroxy compounds, are described in German Specification No. 2,451,932, published May 7, 1975.
U.S. Pat. No. 3,856,821, issued Dec. 24, 1974, describes a series of 3-alkoxy substituted dibenzo[b,d]pyrans having antiarthritic, antiinflammatory and central nervous system activity.
Bergel et al., J. Chem. Soc., 286-287 (1943) investigated the replacement of the pentyl group at the 3-position of 7,8,9,10-tetrahydro-3-pentyl-6,6,9-trimethyl-6H-dibenzo[b,d]pyran-1-ol by alkoxy (butoxy, pentyloxy, hexyloxy and octyloxy) and found that it led to biological inactivity. The hexyloxy derivative was reported to exhibit feeble hashish activity at 10 to 20 mg./kg. The remaining ethers showed no activity in doses up to 20 mg./kg.
In a more recent study, Loev et al., J. Med. Chem., 16, 1200-1206 (1973) report a comparison of 7,8,9,10-tetrahydro-3-substituted-6,6,9-trimethyl-6H-dibenzo[b,d]pyran-1-ols in which the 3-substituent is --OCH(CH 3 )C 5 H 11 ; --CH 2 CH(CH 3 )C 5 H 11 ; or --CH(CH 3 )C 5 H 11 . The ether side chain containing compound was 50% less active in central nervous system activity than the corresponding compound in which the alkyl side chain is directly attached to the aromatic ring, rather than through an intervening oxygen atom; and 5 times as active as the compound in which oxygen is replaced by methylene.
Hoops et al., J. Org. Chem., 33, 2995-2996 (1968) describe the preparation of the 5-aza analog of Δ 61 (10a) -tetrahydrocannabinol referred to therein as 7,8,9,10-tetrahydro-1-hydroxy-5,6,6,9-tetramethyl-3-n-pentylphenanthridine, but report no utility for the compound. Beil, in "Psychomimetric Drugs", edited by Efron, Raven Press, New York, 1970, page 336, reports the compound was "completely inert in animal pharmacology."
Hardman et al., Proc. West. Pharmacol. Soc., 14, 14-20 (1971) reports some pharmacological activity for 7,8,9,10-tetrahydro-1-hydroxy-6,6,9-trimethyl-3-n-pentyl phenanthridine, a 5-aza Δ 6a (10)a -tetrahydrocannabinol.
Mechoulam and Edery in "Marijuana", edited by Mechoulam, Academic Press, New York, 1973, page 127, observe that major structural changes in the tetrahydrocannabinol molecule seem to result in steep reductions in analgesic activity.
Paton, in Annular Review of Pharmacology, 15, 192 (1975) presents generalizations on structure-action relationships among cannabinoids. The presence of the gem dimethyl group in the pyran ring is critical for cannabinoid activity and substitution of N for O in the pyran ring removes activity.
SUMMARY OF THE INVENTION
It has now been found that certain benzo[c]quinolines; namely, 1,9-dihydroxyoctahydro-6H-benzo[c]quinolines (I), 1-hydroxyhexahydro-6H-benzo[c]quinoline-9(8H)-ones (II) and 1-hydroxy-tetrahydroquinolines (IV) are effective as CNS agents, especially an analgesics and tranquilizers, as hypotensives, which are non-narcotic and free of addiction liability, as agents for the treatment of glaucoma and as diuretics. Also included in this invention are various derivatives of said compounds which are useful as dosage forms and intermediates therefor. The above-named compounds and their derivatives have the formulae I, II and IV. Compounds of formulae III and IV are precursors to compounds of formulae II and I. ##STR4## wherein
R is selected from the group consisting of hydroxy, alkanoyloxy having from one to five carbon atoms and hydroxymethyl;
R 1 is selected from the group consisting of hydrogen, benzyl, benzoyl, alkanoyl having from one to five carbon atoms and --CO--(CH 2 ) p --NR 2 R 3 wherein p is 0 or an integer from 1 to 4; each of R 2 and R 3 when taken individually is selected from the group consisting of hydrogen and alkyl having from one to four carbon atoms; R 2 and R 3 when taken together with the nitrogen to which they are attached form a 5- or 6-membered heterocyclic ring selected from the group consisting of piperidino, pyrrolo, pyrrolidino, morpholino and N-alkylpiperazino having from one to four carbon atoms in the alkyl group;
R 4 is selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms and --(CH 2 ) z --C 6 H 5 wherein z is an integer from 1 to 4;
R 5 is selected from the group consisting of hydrogen, methyl and ethyl;
R 6 is selected from the group consisting of hydrogen, --(CH 2 ) y -carbalkoxy having from one to four carbon atoms in the alkoxy group and y is 0 or an integer from 1 to 4; carbobenzyloxy, formyl, alkanoyl having from two to five carbon atoms, alkyl having from one to six carbon atoms; --(CH 2 ) x --C 6 H 5 wherein x is an integer from 1 to 4; and --CO(CH 2 ) x-1 --C 6 H 5 ;
R 0 is selected from the group consisting of oxo, methylene and alkylenedioxy having from two to four carbon atoms;
R' is selected from the group consisting of R and R 0 ;
Z is selected from the group consisting of
(a) alkylene having from one to nine carbon atoms;
(b) --(alk 1 ) m --X--(alk 2 ) n -- wherein each of (alk 1 ) and (alk 2 ) is alkylene having from one to nine carbon atoms, with the proviso that the summation of carbon atoms in (alk 1 ) plus (alk 2 ) is not greater than nine; each of m and n is 0 or 1; X is selected from the group consisting of O, S, SO and SO 2 ; and
W is selected from the group consisting of hydrogen, methyl, pyridyl, piperidyl, ##STR5## wherein W 1 is selected from the group consisting of ##STR6## wherein W 2 is selected from the group consisting of hydrogen and ##STR7## a is an integer from 1 to 5 and b is 0 or an integer from 1 to 5; with the proviso that the sum of a and b is not greater than 5; and the ketals of compounds of formulae II, III and IV wherein the ketal moiety has from two to four carbon atoms.
Also included in this invention are pharmaceutically acceptable acid addition salts of compounds of formulae I and II. Representative of such salts are mineral acid salts such as the hydrochloride, hydrobromide, sulfate, nitrate, phosphate; organic acid salts such as the citrate, acetate, sulfosalicylate, tartrate, glycolate, malonate, maleate, fumarate, malate, 2-hydroxy-3-naphthoate, pamoate, salicylate, stearate, phthalate, succinate, gluconate, mandelate, lactate and methane sulfonate.
Compounds having the formulae I, II and III above contain asymmetric centers at the 6a- and/or 10a-positions. There may be additional asymmetric centers in the 3-position substituent (--Z--W), and 5-, 6- and 9-positions. Diastereomers with the 9β-configuration are generally favored over the 9α-isomers because of greater (quantitatively) biological activity. For the same reason, the trans(6a,10a)diastereomers of compounds of formula I are generally favored over the cis (6a,10a)diastereomers. As regards compounds of formula II, when one of R 4 and R 5 is other than hydrogen, the cis-diastereomers are preferred because of their greater biological activity. As regards formula IV compounds, asymmetric centers exist at the 9-position and in the 3-position substituents. Among the enantiomers of a given compound, one will generally be favored over the other and the racemate because of its greater activity. The enantiomer favored is determined by the procedures described herein. For example, the 1-enantiomer of 5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6.beta. -methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline is favored over the d-enantiomer and the racemate because of its greater analgesic activity.
Among the 3-position (ZW) diastereoisomers, one will generally be favored over the other. For example, dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1α-methyl-4-phenylbutoxy)benzo[c]quinoline is favored over dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline and (2'R,6S,6aR,9R,10aR)-(-)-1-acetoxy-5,6,6a,7,8,9,10,10a-octahydro-9-hydroxy-6-methyl-3-(5'-phenyl-2'-pentyloxy)benzo[c]quinoline is favored over (2'S,6S,6aR,9R,10aR)-(-)-1-acetoxy-5,6,6a,7,8,9,10,10a-octahydro-9-hydroxy-6-methyl-3-(5'-phenyl-2'-pentyloxy)benzo[c]quinoline because of their greater analgesic activity. For convenience, the above formulae are considered to be generic to and embracive of the racemic modifications of the compounds of this invention, the diastereomeric mixtures, the pure enantiomers and diastereomers thereof. The utility of the racemic mixtures, the diastereomeric mixtures as well as of the pure enantiomers and diastereomers is determined by the biological evaluations described below.
Further, various intermediates useful in the preparation of compounds of formulae I, II, III and IV are also included in this invention. The intermediates have the formulae ##STR8## wherein
R 4 , R 5 , R 6 and Z-W are as defined above;
R 7 is selected from the group consisting of hydrogen and formyl; and
Y 1 is selected from the group consisting of hydrogen and hydroxy protecting groups, particularly methyl, ethyl or benzyl.
Asymmetric centers may exist in intermediates V, VI and VII at the 2-position and in the 7-position substituent (--Z--W) and, of course, at other positions, e.g. in the 1-position substituent. The 2- and 7-positions in formulae V-VII correspond to the 6- and the 3-positions, respectively, of compounds having formulae I, II, III and IV.
Favored, because of their greater biological activity relative to that of other compounds described herein, are compounds of formulae I and II wherein R and R 0 as defined above;
R 1 is hydrogen or alkanoyl;
R 5 is hydrogen, methyl or ethyl;
and each of R 4 and R 6 is hydrogen or alkyl;
Z and W have the values shown below;
______________________________________ Z m n W______________________________________alkylene having from 5 to 9 -- -- H or CH.sub.3carbon atomsalkylene having from 2 to 5 -- -- C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-carbon atoms ClC.sub.6 H.sub.4, 4-pyridyl(alk.sub.1).sub.mO(alk.sub.2).sub.n 1 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4- 0 1 1 0 ClC.sub.6 H.sub.4, 4-pyridyl(alk.sub.1).sub.mO(alk.sub.2).sub.n 1 1 H or CH.sub.3 0 1 H or CH.sub.3 1 0 H or CH.sub.3______________________________________
Preferred compounds of formula I are those favored compounds described above wherein R represents hydroxy and which have the trans-configuration. Preferred compounds of formula II are those wherein R 0 is oxo.
Especially preferred are those preferred compounds of formulae I and II wherein:
R is hydroxy (formula I only);
R 1 is hydrogen or acetyl;
R 5 is hydrogen;
R 4 is methyl or propyl;
R 6 is hydrogen, methyl or ethyl;
when Z is alkylene having from 2 to 5 carbon atoms W is phenyl or 4-pyridyl;
when Z is --(alk 1 ) m --O--(alk 2 ) n -- wherein m is 0 and n is 1, (alk 2 ) n is alkylene having from four to nine carbon atoms, W is hydrogen or phenyl; and
when Z is alkylene having from five to nine carbon atoms, W is hydrogen.
Additionally, the favored and preferred classes of intermediates of formulae III, IV, V, VI and VII are those compounds having said formulae which serve as intermediates for the favored and preferred compounds of formulae I and II.
Compounds of formulae I and II wherein R 6 is other than hydrogen, alkyl and --(CH 2 ) x --C 6 H 5 also serve as intermediates for formulae I and II compounds wherein R 6 is hydrogen, alkyl or --(CH 2 ) x --C 6 H 5 .
DETAILED DESCRIPTION OF THE INVENTION
The compounds of this invention of formula V are prepared from appropriately substituted anilines, e.g., 3-hydroxy-5-(Z-W-substituted)-anilines (VIII) or derivatives thereof in which the 3-hydroxy group is protected by a group (Y 1 ) easily removable to regenerate the hydroxy group. Suitable protective groups are those which do not interfere with subsequent reactions of said 3-(protected hydroxy)-5-substituted anilines and which can be removed under conditions which do not cause undesired reactions at other sites of said compound or of products produced therefrom. Representative protective groups (Y 1 ) are methyl, ethyl, benzyl, substituted benzyl wherein the substituent is, for example, alkyl having from 1 to 4 carbon atoms, halo (Cl, Br, F, I), and alkoxy having from one to four carbon atoms.
The exact chemical structure of the protecting group is not critical to this invention since its importance resides in its ability to perform in the manner described above.
The selection and identification of appropriate protecting groups can easily and readily be made by one skilled in the art. The suitability and effectiveness of a group as a hydroxy protecting group are determined by employing such a group in the above-illustrated reaction sequence. It should, therefore, be a group which is easily removed to permit restoration of the hydroxy groups. Methyl is favored as a protecting alkyl group since it is easily removed by treatment with pyridine hydrochloride. The benzyl group, also a favored protecting group, is removed by catalytic hydrogenolysis or acid hydrolysis.
When Z is --(alk 1 ) m --X--(alk 2 ) n --, Y 1 is preferably benzyl or a substituted benzyl group since it can subsequently be removed without detriment to the Z group.
The protected aniline derivative (VIII) is then converted to a compound of formula IX by known technology as described herein.
An abbreviated reaction sequence (Flow Sheet A) for preparing representative compounds of formula V beginning with a 3-(protected hydroxy)-5-(Z--W-substituted)aniline (VIII) wherein --Z--W is OCH 3 is given below: ##STR9##
R o in the above flow sheet represents alkyl having from one to six carbon atoms. (R 5 , for the purpose of illustration in the overall Flow Sheet, is represented as hydrogen. However, in the sequence VIII→X or VIII→V-B, R 5 can be hydrogen, methyl or ethyl.)
The 5-substituent of formula VIII compounds can be group --Z--W desired in compounds of formulae II or I, or a group readily convertible to said group. When the Z moiety of group --Z--W is --(alk 1 ) m --X--(alk 2 ) n -- wherein X is O or S and each of m and n is 0, the 5-substituent, when W is hydrogen, is --XH (i.e., OH or SH) or a protected --XH group of the formula --X--Y 1 wherein Y 1 is as defined above. When, of course, --Z--W is --(alk 1 ) m --X--(alk 2 ) n --W wherein m is 1, n is 0 and W is hydrogen, the 5-substituent becomes --(alk 1 ) m --X--H. The --XH group is advantageously protected in the manner described above.
The appropriate 3-hydroxy-5-substituted anilines discussed above are reacted, preferably in the form of derivatives in which the 3-hydroxy group (and 5-hydroxy group if one is present) is protected as mentioned above in order to achieve satisfactory reactions, with an alkyl β-ketoester, e.g., an alkyl acetoacetate, in the presence of acetic acid to provide the corresponding β-[(3-protected hydroxy)-5-substituted anilino]-β-(R 4 )-acrylate (IX). The reaction is generally conducted in a reaction-inert solvent such as benzene or toluene at temperatures of from about 50° C. to the reflux temperature of the solvent under conditions which result in removal of by-product water. Benzene and toluene are efficient solvents when the reaction is conducted at the reflux temperature, since they permit azeotropic removal of by-product water. Other means of water removal--or effective removal of water--such as molecular sieves can be employed, as can other solvents which permit azeotropic removal of water.
Favored protecting groups for the 3-hydroxy-5-substituted aniline reactants are methyl, ethyl and benzyl groups since the ethers are easily prepared, afford satisfactory yields of compounds of formulae IX and X and are conveniently removed.
The alkyl β-ketoester, preferably one in which the alkyl group has from one to six carbon atoms, is generally used in excess to insure maximum conversion of the aniline reactant to the corresponding alkyl β-anilino-β-(R 4 )-acrylate (IX). Ten to twenty percent excess of alkyl β-ketoester is usually sufficient to achieve satisfactory conversions. Acetic acid is used in catalytic amounts to facilitate reaction.
The alkyl β-anilino-β-(R 4 )-acrylate (IX) is then reduced to the corresponding alkyl-3-[(3-protected hydroxy)-5-substituted anilino]-3-(R 4 )-propionate (X) by, for example, sodium borohydride-acetic acid and catalytic hydrogenation. A preferred catalyst is platinum dioxide since it conveniently permits the reaction to be carried out at low pressures, i.e., at pressures under 50 p.s.i. Other catalysts such as noble metals, e.g., platinum, palladium, rhodium, supported or unsupported, can be used along with pressures of hydrogen ranging from about atmospheric to superatmospheric, e.g., 2000 p.s.i. In addition to such catalysts which are heterogeneous catalysts, this step can be carried out using homogeneous catalysts such as Wilkinson's catalyst, tris(triphenylphosphine)chlororhodium(I).
Of course, when the protecting group or groups are benzyl or substituted benzyl, catalytic hydrogenation will result in their removal. For this reason, methyl or ethyl groups are preferred as protecting groups for the 3- and/or 5-hydroxy groups of formula VIII reactants.
Alternatively, compounds of formula X can be prepared directly from compounds of formula VIII by reaction of formula VIII compounds with an alkyl 3,3-R 4 R 5 -acrylate in acetic acid. The reaction is conveniently carried out by reacting equimolar quantities of the alkyl 3,3-R 4 R 5 -acrylate and disubstituted aniline (VIII) is from 0.1 to 2 equivalents of glacial acetic acid at temperatures ranging from 0° C. to the reflux temperature.
Alternatively, compounds of formula V-B may be prepared directly by condensation of equimolar quantities of VIII with the appropriate substituted acrylic acid (R 4 R 5 C═CH--COOH) in pyridine hydrochloride at 150°-200° C.
In addition, when the R 4 ,R 5 groups are both alkyl, treatment of VIII and the alkyl R 4 ,R 5 acrylate in a reaction-inert solvent, e.g. tetrahydrofuran, with mercuric acetate followed by reduction with sodium borohydride gives X.
Direct conversion of compounds of formula VIII to compounds of formula X is also conveniently achieved by treating a 3,5-(diprotected hydroxy)aniline hydrochloride with an excess of an alkyl acetoacetate, e.g. ethyl acetoacetate, in the presence of sodium cyanoborohydride in a solvent such as methanol.
The alkyl 3-anilino-3-(R 4 )-propionate (X) is then cyclized to the corresponding 2-(R 4 )-quinolin-4-one (formula V-A or -B) by means of a suitable cyclizing agent such as polyphosphoric acid (PPA), hydrogen bromide-acetic acid, sulfuric acid, oleum (fuming sulfuric acid), hydrogen fluoride, trifluoroacetic acid, phosphoric acid-formic acid and others known to those skilled in the art. In a modification of this conversion, the alkyl 3-anilino-3-(R 4 )-propionate (X) can be converted to the corresponding acid by, for example, saponification of the ester followed by acidification, prior to cyclization.
The ether protecting, or blocking, groups on the 3-(and 5-)hydroxy groups can be removed at the time of cyclization through the use of hydrobromic acid in acetic acid as cyclizing agent and deblocking agent. Hydrobromic acid, 48% aqueous, is generally used since it affords satisfactory cyclization and deblocking. The reaction is conducted at elevated temperatures and desirably at the reflux temperature. However, when Z is --(alk 1 ) m --X--(alk 2 ) n --cyclization conditions such as polyphosphoric acid or trifluoroacetic acid must be used to avoid cleavage of the ether or thioether linkage.
Alternatively, the protecting group (or groups) can be removed subsequent to the cyclization reaction. Hydrobromic acid-acetic acid is also a favored agent for deblocking at this stage of the overall synthesis. The reaction is carried out as described above.
Other reagents such as hydriodic acid, pyridine hydrochloride or hydrobromide can be used to remove protecting ether groups such as methyl and ethyl groups. When the protecting groups are benzyl or substituted benzyl groups, they can be removed by catalytic hydrogenolysis. Suitable catalysts are palladium or platinum, especially when supported on carbon. Alternatively, they can be removed by solvolysis using trifluoroacetic acid. Of course, when group --Z--W contains sulfur, acid debenzylation is used rather than catalytic debenzylation.
A favored method for the transformation of compounds of formula X to compounds of formula V which affords satisfactory yields and permits use of relatively mild conditions comprises conversion of formula X compounds to N-carbalkoxy derivatives wherein the N-carbalkoxy group has from two to five carbon atoms by reaction with the appropriate alkyl or benzyl chloroformate. The N-carbalkoxy or carbobenzyloxy derivative of formula X is then cyclized by means of a polyphosphoric acid to the corresponding N-carbalkoxy or carbobenzyloxy derivative of formula V compounds. The N-substituted derivatives of formula X compounds can, if desired, be hydrolyzed to the corresponding 3- [(N-substituted)-3-(protected hydroxy)-5-substituted anilino]-3-(R 4 )-propionic acid prior to cyclization. Polyphosphoric acid generally produces maximum cyclization and is a preferred cyclizing agent.
Compounds of formula V in which the hydroxy group or groups are protected and in which the nitrogen atom is substituted with carbalkoxy are treated with hydrobromic acid-acetic acid to give compounds of formula V-A. When the hydroxy protecting group or groups are benzyl or substituted benzyl, regeneration of the hydroxy groups is accomplished by catalytic hydrogenolysis. A carbalkoxy group if present on the nitrogen atom is unchanged by this reaction. It can, if desired, be subsequently removed by treatment with hydrobromic acid-acetic acid or any of a variety of acids or bases. Removal of the benzyl protecting group by treatment with trifluoroacetic acid also removes any N-carbalkoxy group present.
When the --Z--W substituent of formula V compounds is --XH (X=O or S), and it is desired to have said --Z--W substituent represent, in compounds of formulae II or I, a group --X--(alk 2 ) n --W wherein X is O, S, SO or SO 2 , and W is as previously defined, conversion of group --XH to group --X--(alk 2 ) n --W is conveniently and advantageously undertaken at this point in the overall reaction sequence. Thus, the 7-XH group of formula V-B above represented, for the purposes of illustration, as --OH, is transformed by the Williamson reaction with the appropriate bromide [Br-(alk 2 ) n --W], mesylate or tosylate, to group --O--(alk 2 ) n --W (formula V-C).
Similarly, when group --Z--W of formula V is --(alk 1 )--X--H, its conversion to --(alk 1 )--X--(alk 2 ) n --W wherein n is 0 or 1 and W is other than hydrogen is conveniently undertaken at this stage of the reaction sequence via the Williamson reaction.
A variety of groups, such as those included within the definition of R 6 , can be used in place of carbalkoxy or carbobenzyloxy in this favored method to mask the nitrogen against protonation.
Group R 6 , if not already present in compounds of formulae V-A, V-B or V-C, can be introduced prior to formation of the hydroxymethylene derivative (formula VI) by reaction with the appropriate Cl-R 6 or Br-R 6 reactant according to known procedures. Of course, when an acyl, e.g., acetyl, group R 6 is desired in products of formulae I or II, such groups are generally introduced at that point in the reaction sequence (Flow Sheet B) following formation of formula II compounds wherein R 6 is hydrogen, e.g., by acylation with the appropriate acyl halide according to known procedures.
Compounds of formula V and, of course, of formulae V-A, V-B and V-C, are converted by the following illustrative sequence (Flow Sheet B) to representative compounds of formulae II and I (R 5 =H in the illustration). ##STR10##
The quinolines of formula V are converted to hydroxymethylene derivatives of formula VI by reaction with ethyl formate and sodium hydride. This reaction, a formylation reaction, produces the bis-formylated derivative (VI) in excellent yield. Treatment of the bis-formylated derivative with methyl vinyl ketone gives a mixture of the corresponding mono-N-formylated Michael adduct (VII) and 1,3-bis-formylated Michael adduct. The two products are conveniently separated by column chromatography on silica gel.
The conversion of compounds of formula VII to compounds of formula III is achieved by an aldol condensation of the mono-N-formyl compound of formula VII. The 1,3-bis-formylated Michael adduct when subjected to the aldol condensation produces a spiro-annelation product (III-A) as the major product. However, VII-A can be converted to VII by treatment with an equivalent of ##STR11## potassium carbonate in methanol.
In addition to the spiro-annelation product, small amounts of the desired enone (formula III) and (V) are also produced.
The enone of formula III is converted by Birch reduction to the compound of formula II. Both the cis- and trans-isomers are produced. This reduction is conveniently carried out using lithium as the metal. Sodium or potassium can also be used. The reaction is conducted at a temperature of from about -35° C. to about -80° C. The Birch reduction is favored because it offers stereoselectivity resulting in formation of the desired trans-ketone of formula II as the major product.
The hydroxy ketones of formula II (compounds wherein R 0 is oxo and R 1 is hydrogen) and the dihydroxy compounds of formula I (R=OR 1 =OH) appear to be rather unstable. Upon standing they undergo oxidation as evidenced by formation of purple to red colors. Formation of the colored by-products occurs even when the hydroxy ketone is subjected to sodium borohydride reduction. It has been found that formation of the colored by-products can be prevented by acylation, particularly acetylation, of the 1-hydroxyl group (OR 1 ) with acetic anhydride in pyridine, and by formation of acid addition salts, e.g., hydrochlorides. The acetyl derivatives are stable upon standing and even when subjected to further reaction.
The aforesaid colored by-products are believed to have a quinonoid structure arising from oxidation of the 1-hydroxy group (OR 1 ) to oxo and introduction of a second oxo group at the 2- or the 4-position. The by-products are themselves active as CNS agents, especially as analgesics and tranquilizers, and as hypotensives, and are used in the same manner and at the same dosage levels as are compounds of formulae I and II.
Reduction of the 9-oxo group of compounds of formula II, and preferably for reasons of stability mentioned above, of the acetylated derivative of formula II, via metal hydride reduction affords compounds of formula I wherein the hydroxyl group at the 1-position is present as its acetylated derivative. Sodium borohydride is favored as reducing agent in this step since it not only affords satisfactory yields of the desired product, but retains the acetoxy group at the 1-position, and reacts slowly enough with hydroxylic solvents (methanol, ethanol, water) to permit their use as solvents. A temperature of from about 0° C. to about 30° C. is generally used. Lower temperatures, even down to about -70° C., can be used to increase selectivity of the reduction. Higher temperatures cause reaction of the sodium borohydride with the hydroxylic solvent and deacetylation. If higher temperatures are desired, or required for a given reduction, isopropyl alcohol or the dimethyl ether of diethylene glycol are used as solvents. A preferred reducing agent is potassium tri-sec-butyl borohydride since it favors stereoselective formation of the 9α-hydroxy group. The reduction is conducted in dry tetrahydrofuran at a temperature below about -50° C. using equimolar quantities of the 9-oxo compound and reducing agent.
Reducing agents such as lithium borohydride or lithium aluminum hydride require anhydrous conditions and non-hydroxylic solvents, such as 1,2-dimethoxyethane, tetrahydrofuran, ether, dimethyl ether of ethylene glycol.
Alternately, and more desirably, compounds of formula III, especially those wherein the 1-hydroxy group is protected as an ester or benzyl ether, are converted to compounds of formula I by catalytic hydrogenation. A convenient procedure comprises catalytic hydrogenation over palladium, e.g. palladium-on-carbon, or other noble metal, supported or unsupported. An especially preferred procedure for producing the compounds of formula I having an R 4 and R substituent β and a trans (6a,10a) ring structure in good yield with a high degree of stereoselectivity comprises reducing the corresponding formula III compound (R 4 is β, R 5 =H) in methanol with from 1/2 to equal amounts by weight of Pd/C in a hydrogen atmosphere.
The acetylated derivatives of formula I thus produced are converted to the corresponding hydroxy derivatives by cleavage of the acetyl group by standard methods.
The isomeric 9-α- and 9-β-hydroxy compounds having formula I are produced in the above-described reducing steps. Treatment of the keto compounds of formula II-IV with the appropriate alkylene glycol or alkylene dithiol having two to four carbon atoms in the presence of a dehydrating agent such as p-toluenesulfonic acid, or other acid, used in ketalization (oxalic, adipic), affords the corresponding ketals or thioketals (Fahrenholtz et al., J. Am. Chem. Soc., 89, 5934 [1967]).
Compounds of formula I wherein R is hydroxymethyl are prepared via the Wittig reaction of the corresponding 9-oxo compound of formula II with methylenetriphenylphosphorane or other appropriate methylide. The reaction is conducted under relatively mild conditions to produce the corresponding 9-methylene compound. Hydroboration-oxidation of the 9-methylene compound then affords the hydroxymethyl derivative. Borane in tetrahydrofuran is favored for the hydroboration step since it is commercially available and gives satisfactory yields of the desired hydroxymethyl compound. The reaction is generally conducted in tetrahydrofuran or diethylene glycol dimethyl ether (diglyme). The borane product is not isolated but is directly oxidized with alkaline hydrogen peroxide to the hydroxymethyl compound.
Compounds of formulae I and II, including those wherein each of R 4 and R 5 is alkyl, are also prepared by the sequence of Flow Sheet C below: ##STR12##
The first step of this sequence comprises conversion of the previously described enones (formula III, Flow Sheet B) to the corresponding ketals by reaction with an appropriate alkylene glycol (e.g., ethylene glycol) in the presence of approximately equivalent amounts of p-toluenesulfonic acid or other acid commonly used for ketal formation as described above in benzene with azeotropic removal of water. A mixture of two ketals is obtained; II-A, the reduced form, and IV-A, the oxidized form. Formation of IV-A is favored by addition of agents such as air, Pd/C, sulfur or 2,3-dichloro-5,6-dicyanobenzoquinone to the reaction mixture. The exclusion of oxidizing agents from the reaction mixture or the addition of reducing agents to the reaction mixture favors formation of II-A.
Deketalization of formulae II-A and IV-A compounds by procedures known to those skilled in the art affords compounds of formulae II and IV. These latter compounds are then converted to compounds of formulae I and IV by the procedures of Flow Sheet B.
The reduced formula II-A compounds are oxidized (dehydrogenated) by a variety of oxidants, including iodine, by standard techniques to produce formula IV-A compounds.
The heteroaromatic system of compounds of formula IV-A readily adds organometallic reagents to the azomethine bond. Organolithium reagents, e.g. methyl and ethyl lithium, react with IV-A to produce adducts of formula III-B. Oxidation of the thus-formed adduct by various oxidizing agents, conveniently air, aromatizes the adduct to give formula IV-B substituted in the 6-position. Further reaction of the 6-substituted IV-B compounds with organolithium reagents affords the 6,6-disubstituted products of formula II-B.
The addition of the second group (R 5 ) to the 6-position, particularly when R 5 is larger than methyl, is facilitated by activation of the azomethine bond by quaternization. Activation is conveniently achieved by reaction of formula III-B with an alkyl halide (e.g. methyl or ethyl iodide), or an aralkyl halide, desirably an aralkyl bromide [C 6 H 5 (CH 2 ) x Br] such as benzyl bromide to give formula III-C compounds substituted in the 5-position. The thus-activated compounds readily react with an excess of organolithium or Grignard reagents (see Hoops, et al., J. Org. Chem., 33, 2995-6, 1968) to provide trisubstituted formula II-B compounds. Hydrolysis of the ketals of formulae II-B and III-C affords the corresponding enones which are converted to formulae II and I compounds by procedures described above. Of course, when R 6 of formulae III or III-C compounds is benzyl, lithium-ammonia reduction of the enone also cleaves the benzyl group.
A further procedure for introduction of alkyl groups at the 6-position with ultimate production of compounds of formulae I and II is that of Flow Sheet D: ##STR13##
The 6-oxohexahydrobenzo[c]quinolines of formulae IV-C and IV-E are prepared from compounds of formula IV-A and IV-D by reacting them with sodium or potassium hydroxide at elevated temperatures, e.g. at about 200°-300° C. Quaternization of the nitrogen of IV-A, by reacting IV-A with methyl or ethyl iodide, benzyl bromide or other aralkyl halide, permits the reaction with sodium or potassium hydroxide to be carried out under milder conditions. The intermediate adduct formed is easily oxidized with mild oxidizing agents, including air, to the oxo compound of formula IV-E but which, of course, as a result of the quaternization reaction, bears a substituent (methyl, ethyl, aralkyl) on the nitrogen atom.
An alternative procedure comprises treating IV-A with a peracid, e.g. m-chloroperbenzoic acid, peracetic, to form the corresponding N-oxide which is then reacted with acetic anhydride in an N-oxide rearrangement to give IV-C (Boekelheide Rearrangement). Other methods known to those skilled in the art can be used for the conversion of N-oxides to lactams.
Compounds of formula IV-C or IV-E are then treated with an excess of an appropriate Grignard reagent, e.g. methyl or ethyl magnesium bromide, to give the corresponding 6,6-dialkyl compound II-B.
The 3-hydroxy-5-(Z-W-substituted)anilines are prepared from corresponding 5-(Z-W-substituted)resorcinols via the Bucherer Reaction which comprises reacting the appropriate 5-(Z-W-substituted)resorcinol with aqueous ammonium sulfite or bisulfite. The reaction is conducted in an autoclave at elevated temperatures, e.g. from about 150° to about 230° C. The aniline product is isolated by acidifying the cooled reaction mixture and extracting the acid mixture with, for example, ethyl acetate. The acid solution is neutralized and extracted with a suitable solvent, e.g. chloroform, to recover the aniline product. Alternatively, the aniline product is isolated by extracting the cooled reaction mixture with an appropriate solvent followed by column chromatography of the crude product.
The 5-(Z-W-substituted)resorcinols, if not known, are prepared from 3,5-dihydroxybenzoic acid. The procedure comprises esterifying 3,5-dihydroxybenzoic acid in which the hydroxy groups are protected (e.g., as methyl, ethyl or benzyl ethers); or alternatively, amidating the 3,5-[di(protected hydroxy)]benzoic acid.
The overall abbreviated sequence is illustrated below (Flow Sheet E): ##STR14##
The starting material, 3,5-dihydroxybenzoic acid XI is converted to a compound of formula XII wherein Y 2 represents an alkoxy group, desirably methoxy or ethoxy for ease of preparation, or an amino group; and Y 1 is a hydroxy protecting group, by methods described in the literature.
The disprotected benzoic acid derivative XII is then converted to a compound of formula XIV by known technology. In one procedure XII is hydrolyzed to the corresponding acid (Y 2 =OH), or lithium salt, and reacted with the appropriate alkyl lithium to produce an alkyl disubstituted phenyl ketone (Y 2 =alkyl). When methyl lithium is used, the resulting acetophenone derivative is treated with a Grignard Reagent (W--Z'--MgBr). The intermediate adduct is hydrolyzed to the corresponding alcohol which is then hydrogenolyzed to replace the hydroxy group with hydrogen. This procedure is especially useful for those compounds wherein Z is alkylene.
The ether groups are deblocked by suitable means: treatment with pyridine hydrochloride (Y 1 =methyl) or catalytic hydrogenolysis (Y 1 =benzyl), or by treatment with an acid such as trifluoroacetic acid, hydrochloric, hydrobromic or sulfuric acids. Acid debenzylation is, of course, used when the group --Z--W contains sulfur.
A further method for converting compounds of formula XII to those of formula XIV comprises reaction of a ketone of formula XII (Y 2 =alkyl) with the appropriate triphenyl phosphonium bromide derivative [(C 6 H 5 ) 3 P + --Z--W[Br - in the presence of a base (e.g., sodium hydride). The reaction proceeds via an alkene which is subsequently catalytically hydrogenated to the corresponding alkane (Z--W) and deblocked to the dihydroxy compound XIV. Of course, when --Z-- is (alk 1 ) m --X--(alk 2 ) n and Y 1 is benzyl, the catalytic hydrogenation also results in cleavage of the benzyl ethers.
Alternatively, conversion of structure XII compounds to those of structure XIV can be achieved by the sequence XII→XIII→XIV. In this sequence, the diprotected benzamide (XII,Y 2 =NH 2 ) is converted to the ketone (XIII,Z'=Z less one CH 2 group) by reaction with the appropriate Grignard reagent (BrMg--Z'--W) followed by reaction with methyl- or ethyl-magnesium halide to form the corresponding carbinol. Dehydration of the carbinol, e.g., with p-toluenesulfonic acid, affords the corresponding alkene which is then catalytically hydrogenated (Pd/C) to the alkane (XIV). The ether groups are deblocked (converted to hydroxy) as described above.
When Z is alkylene, Y 1 is desirably alkyl having from one to four carbon atoms or benzyl. The function of group Y 1 is to protect the hydroxy groups during subsequent reactions. It is its ability to perform a specific function; i.e., protection of the hydroxy groups, rather than its structure which is important. The selection and identification of appropriate protecting groups can easily and readily be made by one skilled in the art. The suitability and effectiveness of a group as a hydroxy protecting group are determined by employing such a group in the above-illustrated reaction sequence. It should, therefore, be a group which is easily removed to permit restoration of the hydroxy groups. Methyl is favored as a protecting alkyl group since it is easily removed by treatment with pyridine hydrochloride. The benzyl group, if used as a protecting group, is removed by catalytic hydrogenolysis or acid hydrolysis.
When Z is --(alk 1 ) m --X--(alk 2 ) n --, Y 1 is preferably benzyl or a substituted benzyl group since it can subsequently be removed without detriment to the Z group.
Formula VIII-A compounds can, alternatively, be prepared from 3-amino-5-hydroxybenzoic acids via the procedure of Flow Sheet F below.
Compounds of formula VIII-A wherein --Z--W is --alkylene--W or --(alk 1 )-- X'--(alk) 2 --W wherein (alk 1 ), (alk 2 ), W and n are as defined above and X' is O or S, are obtained by the following sequence (Flow Sheet F): ##STR15##
The first step in the above sequence (the Wittig reaction) provides opportunity, by choice of appropriate reactants, to produce compounds having straight or branched alkylene groups. The amino group is protected by acetylation according to standard procedures. In the given illustration, the value of R" as methyl or ethyl permits formation of a compound having alkyl substitution on the carbon atom (α) adjacent to the phenyl group. Substitution of a methyl or ethyl group at other sites, e.g., the β-carbon atoms of the alkylene group, is achieved by choice of the appropriate carboalkoxy alkylidene triphenylphosphorane, e.g. (C 6 H 5 ) 3 P═C(R")--COOC 2 H 5 . The unsaturated ester thus produced is reduced to the corresponding saturated alcohol by reaction with lithium aluminum hydride. The presence of a small amount of aluminum chloride sometimes accelerates this reaction. Alternatively, when Y 1 is other than benzyl (e.g. methyl), the alcohol is produced by catalytic reduction of the unsaturated ester using palladium-carbon, followed by treatment of the saturated ester thus produced with lithium aluminum hydride. Conversion of the alcohol to the corresponding tosylate or mesylate followed by alkylation of the tosylate or mesylate with an alkali metal salt of the appropriate HX'--(alk 2 ) n --W reactant, and finally removal of the protecting groups (Y 1 ) affords the desired compound VIII-A. When X' is sulfur, the protecting group Y 1 is methyl.
A variation of the above sequence comprises bromination of the alcohol rather than converting it to a tosylate or mesylate. Phosphorous tribromide is a convenient brominating agent. The bromo derivative is then reacted with the appropriate HX'--(alk 2 ) n --W in the presence of a suitable base (Williamson reaction).
The bromo compounds also serve as valuable intermediates for increasing the chain length of the alkylene moiety in the above sequence to give compounds wherein Z is --alkylene--W. The process comprises treating the bromo derivative with triphenyl phosphine to produce the corresponding triphenylphosphonium bromide. Reaction of the triphenylphosphonium bromide with the appropriate aldehyde or ketone in the presence of a base such as sodium hydride or n-butyl lithium affords an unsaturated derivative which is then catalytically hydrogenated to the corresponding saturated compound.
In this variation, the value of the protecting group (Y 1 ) selected depends upon the particular sequence followed. When the vertical sequence on the right is used, benzyl is the preferred protecting group by reason of the catalytic hydrogenation step. Methyl is the preferred protecting group when the left vertical sequence is followed, since it is conveniently removed by treatment with acid as described herein.
Compounds of formula II wherein --Z--W is --(alk 1 ) m --X--(alk 2 ) n --W and X is --SO-- or --SO 2 -- are obtained by oxidation of the corresponding compounds in which X is --S--. Hydrogen peroxide is a convenient agent for oxidation of the thio ethers to sulfoxides. Oxidation of the thio ethers to corresponding sulfones is conveniently accomplished by means of a peracid such as perbenzoic, perphthalic or m-chloroperbenzoic acid. This latter peracid is especially useful since the by-product m-chlorobenzoic acid is easily removed.
Esters of compounds of formulae II-IV wherein R 1 is alkanoyl or --CO--(CH 2 ) p --NR 2 R 3 are readily prepared by reacting formulae II-IV compounds with the appropriate alkanoic acid or acid of formula HOOC--(CH 2 ) p --NR 2 R 3 in the presence of a condensing agent such as dicyclohexylcarbodiimide. Alternatively they are prepared by reaction of a formula II--IV compound with the appropriate alkanoic acid chloride or anhydride, e.g., acetyl chloride or acetic anhydride, in the presence of a base such as pyridine.
Esters of formula I compounds in which each of the R and R 1 groups is esterified are prepared by acylation according to the above-described procedures. Compounds in which only the 9-hydroxy group is acylated are obtained by mild hydrolysis of the corresponding 1,9-diacyl derivative, advantage being taken of the greater ease of hydrolysis of the phenolic acyl group. Formula I compounds in which only the 1-hydroxy group is esterified are obtained by borohydride reduction of the corresponding formula II ketone esterified at the 1-position. The thus-produced formula I compounds bearing 1-acyl-9-hydroxy substitution or 1-hydroxy-9-acyl substitution can then be acylated further with a different acylating agent to produce a diesterified compound of formula I in which the ester group at the 1- and the 9-positions are different.
The presence of a basic group in the ester moiety (OR 1 ) in the compounds of this invention permits formation of acid-addition salts involving said basic group. When the herein described basic esters are prepared via condensation of the appropriate amino acid hydrochloride (or other acid addition salt) with the appropriate compound of formulae I-IV in the presence of a condensing agent, the hydrochloride salt of the basic ester is produced. Careful neutralization affords the free base. The free base form can then be converted to other acid addition salts by known procedures.
Acid addition salts can, of course, as those skilled in the art will recognize, be formed with the nitrogen of the benzo[c]quinoline system. Such salts are prepared by standard procedures. The basic ester derivatives are, of course, able to form mono- or di-acid addition salts because of their dibasic functionality.
The analgesic properties of the compounds of this invention are determined by tests using thermal nociceptive stimuli, such as the mouse tail flick procedure, or chemical nociceptive stimuli, such as measuring the ability of a compound to suppress phenylbenzoquinone irritant-induced writhing in mice. These tests and others are described below.
Tests Using Thermal Nociceptive Stimuli
(a) Mouse Hot Plate Analgesic Testing
The method used is modified after Woolfe and MacDonald, J. Pharmacol. Exp. Ther., 80, 300-307 (1944). A controlled heat stimulus is applied to the feet of mice on a 1/8" thick aluminum plate. A 250 watt reflector infrared heat lamp is placed under the bottom of the aluminum plate. A thermal regulator, connected to thermistors on the plate surface, programs the heat lamp to maintain a constant temperature of 57° C. Each mouse is dropped into a glass cylinder (61/2" diameter) resting on the hot plate, and timing is begun when the animal's feet touch the plate. At 0.5 and 2 hours after treatment with the test compound the mouse is observed for the first "flicking" movements of one or both hind feet, or until 10 seconds elapse without such movements. Morphine has an MPE 50 =4-5.6 mg./kg. (s.c.).
(b) Mouse Tail Flick Analgesic Testing
Tail flick testing in mice is modified after D'Amour and Smith, J. Pharmacol. Exp. Ther., 72, 74-79 (1941), using controlled high intensity heat applied to the tail. Each mouse is placed in a snug-fitting metal cylinder, with the tail protruding through one end. This cylinder is arranged so that the tail lies flat over a concealed heat lamp. At the onset of testing, an aluminum flag over the lamp is drawn back, allowing the light beam to pass through the slit and focus onto the end of the tail. A timer is simultaneously activated. The latency of a sudden flick of the tail is ascertained. Untreated mice usually react within 3-4 seconds after exposure to the lamp. The end point for protection is 10 seconds. Each mouse is tested at 0.5 and 2 hours after treatment with morphine and the test compound. Morphine has an MPE 50 of 3.2-5.6 mg./kg. (s.c.).
(c) Tail Immersion Procedure
The method is a modification of the receptacle procedure developed by Benbasset, et. al., Arch. int. Pharmacodyn., 122, 434 (1959). Male albino mice (19-21 g.) of the Charles River CD-1 strain are weighed and marked for identification. Five animals are normally used in each drug treatment group with each animal serving as its own control. For general screening purposes, new test agents are first administered at a dose of 56 mg./kg. intraperitoneally or subcutaneously, delivered in a volume of 10 ml./kg. Preceding drug treatment and at 0.5 and 2 hours post drug, each animal is placed in the cylinder. Each cylinder is provided with holes to allow for adequate ventilation and is closed by a round nylon plug through which the animal's tail protrudes. The cylinder is held in an upright position and the tail is completely immersed in the constant temperature waterbath (56° C.). The endpoint for each trial is an energetic jerk or twitch of the tail coupled with a motor response. In some cases, the endpoint may be less vigorous post drug. To prevent undue tissue damage, the trial is terminated and the tail removed from the waterbath within 10 seconds. The response latency is recorded in seconds to the nearest 0.5 second. A vehicle control and a standard of known potency are tested concurrently with screening candidates. If the activity of a test agent has not returned to baseline values at the 2-hour testing point, response latencies are determined at 4 and 6 hours. A final measurement is made at 24 hours if activity is still observed at the end of the test day.
Test Using Chemical Nociceptive Stimuli
Suppression of Phenylbenzoquinone Irritant-Induced Writhing
Groups of 5 Carworth Farms CF-1 mice are pretreated subcutaneously or orally with saline, morphine, codeine or the test compound. Twenty minutes (if treated subcutaneously) or fifty minutes (if treated orally) later, each group is treated with intraperitoneal injection of phenylbenzoquinone, an irritant known to produce abdominal contractions. The mice are observed for 5 minutes for the presence or absence of writhing starting 5 minutes after the injection of the irritant. MPE 50 's of the drug pretreatments in blocking writhing are ascertained.
Tests Using Pressure Nociceptive Stimuli
Effect on the Haffner Tail Pinch Procedure
A modification of the procedure of Haffner, Experimentelle Prufung Schmerzstillender. Mittel Deutch Med. Wschr., 55, 731-732 (1929) is used to ascertain the effects of the test compound on aggressive attacking responses elicited by a stimulus pinching the tail. Male albino rats (50-60 g.) of the Charles River (Sprague-Dawley) CD-strain re used. Prior to drug treatment, and again at 0.5, 1, 2 and 3 hours after treatment, a Johns Hopkins 2.5-inch "bulldog" clamp is clamped onto the root of the rat's tail. The endpoint at each trial is clear attacking and biting behavior directed toward the offending stimulus, with the latency for attack reported in seconds. The clamp is removed in 30 seconds if attacking has not yet occurred, and the latency of response is recorded as 30 seconds. Morphine is active 17.8 mg./kg. (i.p.).
Tests Using Electrical Nociceptive Stimuli
The "Flinch-Jump" Test
A modification of the flinch-jump procedure of Tenen, Psychopharmacologia, 12, 278-285 (1968) is used for determining pain thresholds. Male albino rats (175-200 g.) of the Charles River (Sprague-Dawley) CD strain are used. Prior to receiving the drug, the feet of each rat are dipped into a 20% glycerol/saline solution. The animals are then placed in a chamber and presented with a series of 1-second shocks to the feet which are delivered in increasing intensity at 30-second intervals. These intensities are 0.26, 0.39, 0.52, 0.78, 1.05, 1.31, 1.58, 1.86, 2.13, 2.42, 2.72, and 3.04 mA. Each animal's behavior is rated for the presence of (a) flinch, (b) squeak and (c) jump or rapid forward movement at shock onset. Single upward series of shock intensities are presented to each rat just prior to, and at 0.5, 2, 4 and 24 hours subsequent to drug treatment.
Results of the above tests are recorded as percent maximum possible effect (% MPE). The % MPE of each group is statistically compared to the % MPE of the standard and the predrug control values. The % MPE is calculated as follows: ##EQU1##
In the tables below, the analgesic activity is reported in terms of MPE 50 , the dose at which half of the maximal possible analgesic effect is observed in a given test.
The compounds of the present invention are active analgesics via oral and parenteral administration and are conveniently administered in composition form. Such compositions include a pharmaceutical carrier selected on the basis of the chosen route of administration and standard pharmaceutical practice. For example, they may be administered in the form of tablets, pills, powders or granules containing such excipients as starch, milk sugar, certain types of clay, etc. They may be administered in capsules, in admixtures with the same or equivalent excipients. They may be administered in the form of oral suspensions, solutions, emulsions, syrups and elixirs which may contain flavoring and coloring agents. For oral administration of the therapeutic agents of this invention, tablets or capsules containing from about 0.01 to about 100 mg. are suitable for most applications.
The physician will determine the dosage which will be most suitable for an individual patient and it will vary with the age, weight and response of the particular patient and the route of administration. Generally, however, the initial analgesic dosage in adults may range from 0.01 to 500 mg. per day in single or divided doses. In many instances, it is not necessary to exceed 100 mg. daily. The favored oral dosage range is from about 0.01 to about 300 mg./day; the preferred range is from about 0.10 to about 50 mg./day. The favored parenteral dose is from about 0.01 to about 100 mg./day; the preferred range from about 0.01 to about 20 mg./day.
By means of the above procedures, the analgesic activity of several compounds of this invention and of certain prior art compounds are determined.
The following abbreviations are used in the tables:
PBQ=phenylbenzoquinone-induced writhing; TF=tail flick; HP=hot plate; RTC=rat tail clamp; FJ=flinch jump; and TI=tail immersion assays.
TABLE I__________________________________________________________________________Analgesic Activity (MPE.sub.50 -mg./kg.,s.c.) ##STR16##R R.sub.1 R.sub.4 R.sub.5 R.sub.6 ZW 6a,10a PBQ TF HP__________________________________________________________________________H H CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 cis/trans 1.05 1.32 10-32H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans 1.0-1.78 1.0 5.6H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans* 100 @ 10 5.6 5.6H H CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans 0.5 3.2 10COCH.sub.3COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans 1.78-3.2 10 >10COCH.sub.3COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans* <10 5.6-10 >10H H CH.sub.3 H COCH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10 >10 >10COCH.sub.3COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans 100 @ 10 1-3.2 3.2-5.6H H CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 0.1-0.56 1-3.2 1-3.2H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.25 0.42 1-3.2H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 cisub.5 0.56-1.0 1-3.2 3.2-10H H CH.sub.3 H C.sub.2 H.sub.5 OCH(CH.sub.3)C.sub.5 H.sub.11 trans 0.09H COCH.sub.3 H H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans 10 >10 >10H COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.05H COCH.sub. 3 H H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 0.83H COCH.sub.3 H H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 0.1 0.32-0.56 0.56-1.0H COCH.sub.3 H H CH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans 100 @ 3.2 100 <100morphine 0.8 3.2-5.6 4.0-5.6H H CH.sub.3 H COC.sub.6 H.sub.5 OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10H COCH.sub.3 H H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 0.098 0.32H COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.05 0.016H COCH.sub.3 CH.sub.3 H H O(CH.sub.2).sub.4 C.sub.6 H.sub.5 trans 6.09COCH.sub.3COCH.sub.3 CH.sub.3 H H O(CH.sub. 2).sub.4 C.sub.6 H.sub.5 trans >56H COCH.sub.3 CH.sub.3 H CH.sub.3 O(CH.sub.2).sub.4 C.sub.6 H.sub.5 trans 0.28 1.46H H CH.sub.3 H CH.sub.3 O(CH.sub.2).sub.4 C.sub.6 H.sub.5 trans 0.80 2.1COCH.sub.3COCH.sub.3 H H i-C.sub.4 H.sub.9 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 >10H.sup.+COCH.sub.3 H H H OCH(CH.sub.3)C.sub.5 H.sub.11 cis ≦10 >10H.sup.+COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 1.64 7.65H COCH.sub.3 H CH.sub.3 H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 0.11H COCH.sub.3 H CH.sub.3 H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 cisub.5 0.22H.sup.+COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 cisub.5 0.46H.sup.+COCH.sub.3 H CH.sub.3 H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 0.78H COCH.sub.3 n-C.sub.3 H.sub.7 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.14 0.34H COCH.sub.3 n-C.sub.3 H.sub.7 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 cis*b.5 0.12 0.44 0.61H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.sup.(a) 0.14 0.26H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.sup.(b) 7.40H OH CH.sub.3 H C.sub.2 H.sub.5 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.21 1.47 3.64H OH CH.sub.3 H (CH.sub.2).sub.2 C.sub.6 H.sub.5 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 14.33H OH CH.sub.3 H (CH.sub.2).sub.3 C.sub.6 H.sub.5 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 29 @ 10H OH CH.sub. 3 H CH.sub.2 C.sub.6 H.sub.5 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 0.50H OH CH.sub.3 H n-C.sub.3 H.sub.7 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 100 @ 0.32H OH CH.sub.3 H C.sub.6 H.sub.13 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 1.29H OH CH.sub.3 H C.sub.5 H.sub.11 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 27.85H OH CH.sub.3 H (CH.sub.2).sub.4 C.sub.6 H.sub.5 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 60 @ 56H OH CH.sub.3 H C.sub.4 H.sub.9 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 42.36H OH CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans.5 100 @ 56H COCH.sub.3 C.sub.2 H.sub.5 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.15 0.73 1.59H COCH.sub.3 C.sub.6 H.sub.13 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 32H.sup.+COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.11H.sup.+COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 cis*b.5 0.82H COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 cis*b.5 45 @ 56H COCH.sub.3 (CH.sub.2).sub.2 C.sub.6 H.sub.5 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 3.56H COCH.sub.3 CH.sub.3 H H O(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans* 50 @ 10H COCH.sub.3 C.sub.5 H.sub.11 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 18.01H COCH.sub.3 C.sub.4 H.sub.9 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 3.05 7.94H COCH.sub.3 H C.sub.4 H.sub.9 H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 1.32 3.76H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(c) trans* 0.22 0.23H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(d) trans* 1.73 1.69H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(d) trans.sup.(a) 1.50H COCH.sub.3 CH.sub.3 H H OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(c) trans.sup.(b) 0.07 0.21 0.44H COCH.sub.3 CH.sub.3 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(c) trans 0.01 0.04 0.09H COCH.sub.3 CH.sub.3 H H C(CH.sub.3).sub.2 (CH.sub.2).sub.4 CH.sub.3 trans 0.19H COCH.sub.3 CH.sub.3 H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.4 CH.sub.3 trans* 0.13H COCH.sub.3 CH.sub.3 H H O(CH.sub.2).sub.2 C.sub.6 H.sub.7 trans* 16 @ 56H COCH.sub.3 C.sub.4 H.sub.9 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.89H COCH.sub.3 C.sub.3 H.sub.7 H CH.sub.3 OCH(CH.sub.3) (CH.sub.2).sub.3 C.sub.6 trans*5 0.08__________________________________________________________________________ .sup.(a) = 6S,6aR,9R,10aR .sup.(b) = 6R,6aS,9S,10aS ##STR17## ##STR18## [* = hydrochloride salt]- [+ = 9α-OH]-
TABLE II__________________________________________________________________________Analgesic Activity (MPE.sub.50 -mg./kg.,s.c.) ##STR19##R.sub.1R.sub.4 R.sub.5 R.sub.6 ZW 6a,10a PBQ TF HP__________________________________________________________________________H CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 cis/trans 3.2COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 cis 100 @ 10COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans 10 >10 >10COCH.sub.3CH.sub.3 H COCH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10 >10 >10H CH.sub.3 H CH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans 100 @ 10 ˜10 ˜10COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2 ).sub.3 C.sub.6 H.sub.5 cis 0.1-0.56 3.2-5.6 10COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 1.78 2.4 <10COCH.sub.3H H CH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans 100 @ 10COCH.sub.3H H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 100 @ 10 1.0-3.2 >10COCH.sub.3H H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 100 @ 28COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis* 0.31 3.9H CH.sub.3 H COCH.sub.3 OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10 >10COCH.sub.3H H H OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10, <56 >10COCH.sub.3CH.sub.3 H COC.sub.6 H.sub.5 OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10H CH.sub.3 H COC.sub.6 H.sub.5 OCH(CH.sub.3)C.sub.5 H.sub.11 trans >10COCH.sub.3CH.sub.3 H CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans* 0.17COCH.sub.3H H CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 2.07 ˜5.6H CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 1.33COCH.sub.3H H H OCH(CH.sub.3)C.sub.5 H.sub.11 cis <10 >10COCH.sub.3CH.sub.3 H H O(CH.sub.2).sub.4 C.sub.6 H.sub.5 trans ≦56COCH.sub.3CH.sub.3 H CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis* 5.3 >10COCH.sub.3CH.sub.3 H CH.sub.3 O(CH.sub.2).sub.4 C.sub.6 H.sub.5 trans >10COCH.sub.3CH.sub.3 H H O(CH.sub.2).sub.4 C.sub.6 H.sub.5 >56 >10COCH.sub.3H CH.sub.3 H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 2.31COCH.sub.3H CH.sub.3 H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 5.59COCH.sub.3n-C.sub.3 H.sub.7 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans* 0.38 2.37 83 @ 10COCH.sub.3n-C.sub.3 H.sub.7 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis* 0.16 1.76COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis*.sup.(a) 25 @ 10COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis*.sup.(b) 0.62COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans*.sup.(a) 2.11COCH.sub.3CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans*.sup.(b) 7.28COCH.sub.3C.sub.2 H.sub.5 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 0.17 0.78 1.62COCH.sub.3C.sub.6 H.sub.13 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 35 @ 10COCH.sub.3C.sub.2 H.sub.5 H H OCH(CH.sub.3 )(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans* 1.60COCH.sub.3C.sub.6 H.sub.13 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 21 @ 10COCH.sub.3(CH.sub.2).sub.2 C.sub.6 H.sub.5 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 100 @ 10COCH.sub.3(CH.sub.2).sub.2 C.sub.6 H.sub.5 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 34 @ 10COCH.sub.3CH.sub.3 H H O(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 22 @ 56COCH.sub.3CH.sub.3 H H O(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 12 @ 56COCH.sub.3C.sub.5 H.sub.11 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 trans 14 @ 10COCH.sub.3C.sub.5 H.sub.11 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 14 @ 10COCH.sub.3C.sub.4 H.sub.9 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub. transub.5 4.36COCH.sub.3C.sub.4 H.sub.9 H H OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 cis 16 @ 10__________________________________________________________________________ .sup.(a) = 6S,6aR,9R,10aR .sup.(b) = 6R,6aS,9S,10aS [* = hydrochloride salt]-
Their antihypertensive utility is determined by their ability to lower the blood pressure of conscious hypertensive rats and dogs a statistically significant degree when administered orally to said hosts at the above-mentioned dosages.
Their tranquilizer activity is demonstrated by oral administration to rats at doses of from about 0.01 to 50 mg./kg. with subsequent decreases in spontaneous motor activity. The daily dosage range in mammals is from about 0.01 to about 100 mg.
The use of these compounds for the treatment of glaucoma is believed to be due to their ability to reduce intraocular pressure. Their effects on intraocular pressure are determined by tests on dogs. The test drug is instilled into the eye of a dog in the form of a solution or is administered systemically at various periods of time after which the eye is anesthetized by instillation of tetracaine hydrochloride, 1/2%, 2 drops. A few minutes after this local anesthesia, intraocular pressure readings are taken with a Schiotz mechanical tonometer and, after fluorescein dye is administered, with a Holberg hand application tonometer. The test drug is conveniently used in a solution such as the following: test drug (1 mg.), ethanol (0.05 ml.), Tween 80 (polyoxyalkylene derivative of sorbitan mono-oleate, available from Atlas Powder Co., Wilmington, Del. 19899) (50 mg.) and saline (to make 1 ml.), or in a more concentrated solution wherein the ingredients are present in proportions of 10 mg., 0.10 ml., 100 mg. and 1 ml., respectively. For human use, concentrations of drug from 0.01 mg./kg. to 10 mg./kg. are useful.
Their activity as diuretic agents is determined by the procedure of Lipschitz et al., J Pharmacol., 79, 97 (1943) which utilizes rats as the test animals. The dosage range for this use is the same as that noted above with respect to the use of the herein described compounds as analgesic agents.
This invention also provides pharmaceutical compositions, including unit dosage forms, valuable for the use of the herein described compounds as analgesics and other utilities disclosed herein. The dosage form may be given in single or multiple doses, as previously noted, to achieve the daily dosage effective for a particular utility.
The compounds (drugs) described herein can be formulated for administration in solid or liquid form for oral or parenteral administration. Capsules containing drugs of this invention; i.e.; compounds of formulae I or II are prepared by mixing one part by weight of drug with nine parts of excipient such as starch or milk sugar and then loading the mixture into telescoping gelatin capsules such that each capsule contains 100 parts of the mixture. Tablets containing compounds of formulae I or II are prepared by compounding suitable mixtures of drug and standard ingredients used in preparing tablets, such as starch, binders and lubricants, such that each tablet contains from 0.01 to 100 mg. of drug per tablet.
Suspensions and solutions of these drugs, particularly those wherein R 1 (formulae I and II) is hydroxy, are generally prepared just prior to use in order to avoid problems of stability of the drug (e.g. oxidation) or of suspensions or solution (e.g. precipitation) of the drug up on storage. Compositions suitable for such are generally dry solid compositions which are reconstituted for injectable administration.
EXAMPLE 1
Ethyl dl-3-(3,5-Dimethoxyanilino)butyrate
A mixture of 3,5-dimethoxyaniline (95.7 g., 0.624 mole), ethyl acetoacetate (87.2 ml., 0.670 mole), benzene (535 ml.) and glacial acetic acid (3.3 ml.) is refluxed for 15 hours under an atmosphere of nitrogen and water collected by means of a Dean-Stark trap. The reaction mixture is cooled to room temperature, decolorized with activated charcoal, filtered, and then concentrated under reduced pressure to give the product, ethyl 3-[3,4-dimethoxy)anilino]-2-butenoate, as an oil (168.7 g.).
A mixture of ethyl 3-(3,5-dimethoxyanilino)-2-butenoate (5.0 g., 18.7 mmole) in glacial acetic acid (42 ml.) and platinum oxide (250 mg.) is hydrogenated in a Parr shaker at 50 p.s.i. for 1.5 hours. The reaction mixture is filtered through filter-aid, benzene (50 ml.) added and the solution concentrated under reduced pressure to an oil. The oil is taken up in chloroform, the solution washed successively with saturated sodium bicarbonate solution (2×50 ml.) and saturated sodium chloride solution. It is then dried (MgSO 4 ), filtered and concentrated under reduced pressure to give the product as an oil (5.1 g.).
Repetition of the above procedure but using 168.7 g. of ethyl 3-(3,5-dimethoxyanilino)-2-butenoate, glacial acetic acid (320 ml.) and platinum oxide (2.15 g.) gives 160.8 g. of product.
EXAMPLE 2
Ethyl dl-3-(3,5-Dimethoxyanilino)butyrate
To a solution of 3,5-dimethoxyaniline hydrochloride (370 g., 1.45 mole), reagent grade methanol (4.5 l.) and ethyl acetoacetate (286.3 g., 2.64 mole) in a 12 liter round bottom, 3 neck flask fitted with mechanical stirrer and reflux condenser is added sodium cyanoborohydride (54 g., 0.73 mole) in one portion. After the refluxing subsides (10 minutes) the mixture is heated on a steam bath for an additional 20 minutes. To the cooled reaction mixture is added additional sodium cyanoborohydride (5.4 g., 0.07 mole) and ethyl acetoacetate (28.6 g., 0.26 mole) and the mixture refluxed for 30 minutes. This latter process is repeated once more.
The reaction mixture is isolated in portions by pouring ca. 500 ml. onto 1 liter of ice-water/500 ml. methylene chloride, separating the layers and backwashing the aqueous phase with additional methylene chloride (100 ml.). (This process is repeated using 500 ml. portions until the entire reaction mixture is worked up.)
The methylene chloride layers are combined and dried (MgSO 4 ), decolorized with charcoal, filtered and evaporated to yield a yellow colored oil.
The excess ethyl acetoacetate is distilled (at 130° C. oil bath temperature and 1-5 mm. pressure) leaving the crude ethyl 3-(3,5-dimethoxyanilino)butyrate (an amber colored viscous oil): 376 g. (72% yield) which is used without further purification.
It has the following spectral characteristics:
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 5.82-6.0 (m,3H,aromatic), 4.20(q,2H, ester methylene), ##STR20## 3.78 (s, 6H, --OCH 3 ), 2.40-2.55 (m,2H, --CH 2 COOEt), 1.78 (d,3H,methyl) and 1.29 (t,3H,methyl).
EXAMPLE 3
dl-Ethyl 3-(3,5-Dimethoxyanilino)hexanoate
Following the procedure of Example 2, condensation of 3,5-dimethoxyaniline hydrochloride and ethyl butyrylacetate gives ethyl d,l-3-(3,5-dimethoxyanilino)hexanoate. It is converted to the hydrochloride salt by addition of hydrogen chloride to a methylene chloride solution thereof; m.p. 127°-129.5° C. Recrystallization from cyclohexane/benzene (5:1) gives the analytical sample, m.p. 126°-128.5° C.
Analysis: Calc'd for C 16 H 25 O 4 N.HCl: C, 57.91; H, 7.90; N, 4.22%. Found: C, 57.89; H, 7.74; N, 4.40%.
m/e--295 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 10.76-11.48 (b, variable, 2H, NH 2 +), 6.77 (d, J=2 Hz, 2H, meta H's), 6.49, 6.45 (d of d, J=2 Hz, 1H, meta H), 4.08 (q, 2H, OCH 2 ), 3.77 (s, 6H, [OCH 3 ] 2 ), ca. 3.5-4.8 (m, 1H, CH--N), 2.90 (t, 2H, CH 2 --C═O), ca. 1.4-2.2 (m, 4H, [CH 2 ] 2 ), 1.21 (t, 3H, O--C--CH 3 ), 0.84 (t, 3H, --C--CH 3 ).
EXAMPLE 4
d,l-Ethyl 3-[(3,5-Dimethoxy-N-ethoxycarbonyl)anilino]butyrate
Method A
Ethyl chloroformate (71.4 ml. 0.75 mole) is added dropwise over a 45 minute period to a mixture of ethyl 3-(3,5-dimethoxyanilino)butyrate (159.8 g., 0.598 mole), methylene chloride (100 ml.), and pyridine (100 ml., 1.24 moles) at 0° C. under a nitrogen atmosphere. The mixture is stirred for 40 minutes following addition of the ethyl chloroformate and is then poured into a mixture of chloroform (750 ml.) and ice-water (500 ml.). The chloroform layer is separated, washed successively with 10% hydrochloric acid (3×500 ml.), saturated aqueous sodium bicarbonate (1×300 ml.) and saturated aqueous sodium chloride (1×400 ml.) and then dried (MgSO 4 ). It is then decolorized with activated charcoal and concentrated under reduced pressure to an oil (215 g.). The product is used as is.
Method B
Under a positive nitrogen atmosphere a mixture of ethyl 3-(3,5-dimethoxyanilino)butyrate (376 g., 1.4 mole), methylene chloride (1.4 liters) and anhydrous potassium carbonate (388.8 g., 2.81 mole) is stirred and cooled in an ice bath to 0°→5° C. Ethyl chloroformate (153 g., 1.41 mole) is added in one portion. The mixture is allowed to warm to room temperature over a period of one hour, ethyl chloroformate (153 g., 1.41 mole) is added once more and the mixture is refluxed on a steam bath for one hour. It is then allowed to cool to room temperature and the potassium carbonate removed by filtration. The red colored filtrate is washed successively with water (2×1000 ml.), brine (1×500 ml.), dried (MgSO 4 ), and then decolorized and evaporated under reduced pressure to afford 439 g. of crude product which is used without further purification.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 6.2-6.42 (m, 3H, aromatic), 4.65 (sextet, 1H, --N--CH--, CH 3 ), 4.10-4.15 (2 quartets, 4H, ester methylenes), 3.70 (s, 6H, --OCH 3 ), 2.30-2.60 (m, 2H, --CH 2 COOEt), 1.00-1.40 (m, 9H, 3 methyl).
EXAMPLE 5
d,l-3-[(3,5-Dimethoxy-N-ethoxycarbonyl)anilino]butyric Acid
Method A
Ethyl 3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyrate (202 g., 0.595 mole), aqueous sodium hydroxide (595 ml. of 1 N) and ethanol (595 ml.) are combined and stirred at room temperature overnight. The reaction mixture is concentrated to about 600 ml. volume under reduced pressure, the concentrate diluted with water to 1200 ml. volume and extracted with ethyl acetate (3×750 ml.). The aqueous layer is then acidified with 10% hydrochloric acid to pH 2 and extracted again with ethyl acetate (3×750 ml.). These latter extracts are combined, washed with brine, dried (MgSO 4 ), filtered and concentrated in vacuo to yield the title product as an oil (163.5 g., 88.2%).
Method B
A 5 liter 3 neck, round bottom flask equipped with mechanical stirrer and reflux condensor is charged with a solution of ethyl 3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]-butyrate (439 g., 1.41 moles) in ethanol (2 liters). Sodium hydroxide (2 liters of 1 N) is added and the mixture refluxed on a steam bath for 3 hours. The reaction mixture is poured onto 5 liters of ice-water and extracted in one liter portions with diethyl ether (500 ml./portion). The aqueous layer is cooled by adding ca. one liter of ice and then acidified with concentrated hydrochloric acid (1.75 ml., 2.1 moles). It is extracted in portions of one liter with methylene chloride (250 ml./portion). The methylene chloride layers are combined and dried over magnesium sulfate, decolorized with charcoal and evaporated to dryness to yield a viscous yellow oil. Crystallization from ether/cyclohexane (1:2) affords 224 g. (55.3%) of crystalline product, m.p. 78°-80° C. This material is used without further purifications in the following step.
1 N NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 6.24-6.53 (m, 3H, aromatic), 4.65 (sextet, 1H, --N(COOC 2 H 5 )CH(CH 3 )CH 2 COOC 2 H 5 ), 4.10 (quartet, 2H, ester methylene), 3.78 (s, 6H, --OCH 3 ), 2.40-2.60 (m, 2H, --CH 2 COOH), 1.18 (t), 1.28 (d, 6H,methyl), 10.8 (bs, variable, 1H, COOH).
MS (mol.ion) m/e--311.
An analytical sample, obtained by recrystallization from ethyl acetate/hexane (1:5), melted at 89°-91° C.
Analysis: Calc'd for C 15 H 21 O 6 N: C, 57.86; H, 6.80; N, 4.50%. Found: C, 58.08; H, 6.65; N, 4.46%.
EXAMPLE 6
d- and l-3[(3,5-Dimethoxy-4-N-ethoxycarbonyl)anilino]butyric Acids
A mixture of d,l-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid (136.6 g., 0.44 mole) and 1-ephedrine (72.5 g., 0.44 mole) is dissolved in methylene chloride (500 ml.). The methylene chloride is then removed in vacuo to yield the 1-ephedrine salt of d,l-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid as an oil, [α] D 25 =-20.0 (c=1.0, CHCl 3 ). Addition of ether (1500 ml.) causes crystallization of a white solid which is separated by filtration and dried (102 g.), m.p. 114°-116° C. Recrystallization from ethyl acetate/hexane (1:1) affords 71.1 g. (34%) of the 1-ephedrine salt of 1-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid; m.p. 126°-127° C.
Analysis: Calc'd for C 25 H 36 O 7 N 2 : C, 63.00; H, 7.61; N, 5.88%. Found: C, 62.87; H, 7.64; N, 5.88%.
[α] D 25 =-43.5° (c=1.0, CHCl 3 ).
The 1-ephedrine salt of the 1-isomer is stirred in a mixture of ethyl acetate (1000 ml.) and 10% hydrochloric acid (400 ml.) for ten minutes. The organic phase is separated, washed with 10% hydrochloric acid (2×400 ml.), dried and concentrated under reduced pressure to an oil. Crystallization of the oil from ethyl acetate/hexane (400 ml. of 1:1) affords 34.6 g. of 1-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid, m.p. 96°-97° C.
Analysis: Calc'd for C 15 H 21 O 6 N: C, 57.86; H, 6.80; N, 4.50%. Found: C, 57.90; H, 6.66; N, 4.45%.
[α] D 25 =-25.4° (c=1.0, CHCl 3 ).
The mother liquor remaining from recrystallization of the 1-ephedrine salt of the 1-isomer is treated with hydrochloric acid as described above to give crude d-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid. Treatment of the crude acid with d-ephedrine affords, after crystallization from ether, the d-ephedrine salt of the d-isomer, m.p. 124°-125° C.
Analysis: Calc'd for C 25 H 36 O 7 N 2 : C, 63.00; H, 7.61; N, 5.88%.
Found: C, 62.82; H, 7.47; N, 5.97%.
[α] D 25 =+44.0° (c=1.0, CHCl 3 ).
The d-ephedrine salt is converted to d-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid in the same manner as described above for conversion of the 1-ephedrine salt to the free acid. M.p. 96°-97° C. after recrystallization from ethyl acetate/hexane (3:5).
Analysis: Calc'd for C 15 H 21 O 6 N: C, 57.86; H, 6.80; N, 4.50%. Found: C, 57.95; H, 6.57; N, 4.35%. [α] D 25 =+25.3° (c=1.0, CHCl 3 ).
EXAMPLE 7
Methyl 3-(3,5-Dimethoxyanilino)propionate
A mixture of 3,5-dimethoxyaniline (114.9 g., 0.75 mole), methyl acrylate (69.73 g., 0.81 mole) and glacial acetic acid (2 ml.) is refluxed for 20 hours. Reflux is discontinued and the reaction mixture is concentrated and then distilled in vacuo, to yield 106.8 g. (73.9%) of the title product, b.p. 174°-179° C. (0.7 mm.).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 5.62-5.95 (m, 3H, aromatic), 4.1 (variable, bs, 1H, --NH), 3.74 (s, 6H, --OCH 3 ), 3.68 (s, 3H, COOCH 3 ), 3.41 and 2.59 (two 2H triplets, --NCH 2 CH 2 CO 2 ).
Repetition of this procedure but using the appropriate aniline reactant in place of 3,5-dimethoxyaniline affords the following compounds.
______________________________________ ##STR21## Y.sub.1 ZW______________________________________ C.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.7 H.sub.7 OC.sub.7 H.sub.7 C.sub.7 H.sub.7 SCH.sub.3 CH.sub.3 SCH.sub.3 C.sub.2 H.sub.5 SCH.sub.3______________________________________
EXAMPLE 8
Methyl 3-(3,5-Dimethoxyanilino)alkanoates
The procedure of Example 7 is repeated but using the appropriate ester R 4 R 5 C═CH--COOCH 3 in place of methyl acrylate and the appropriate protected aniline reactant to give the following compounds.
When R 5 is hydrogen, the same products are obtained by the procedure of Examples 1 and 2 but using methyl acetoacetate and methyl propionylacetate in place of ethyl acetoacetate and the appropriate protected aniline reactant.
______________________________________ ##STR22##Y.sub.1 ZW R.sub.4 R.sub.5______________________________________CH.sub.3 OCH.sub.3 CH.sub.3 HCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 HC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CH.sub.3 CH.sub.3CH.sub.3 SCH.sub.3 CH.sub.3 HCH.sub.3 SCH.sub.3 C.sub.2 H.sub.5 HC.sub.7 H.sub.7 SCH.sub.3 C.sub.2 H.sub.5 HC.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3C.sub.7 H.sub.7 OC.sub.7 H.sub.7 CH.sub.3 HC.sub.7 H.sub.7 OC.sub.7 H.sub.7 C.sub.2 H.sub.5 HC.sub.2 H.sub.5 SCH.sub.3 CH.sub.3 CH.sub.3C.sub.7 H.sub.7 SCH.sub.3 CH.sub.3 HCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5CH.sub.3 SCH.sub.3 C.sub.2 H.sub.5 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.3CH.sub. 3 OCH.sub.3 n-C.sub.3 H.sub.7 HCH.sub.3 OCH.sub.3 n-C.sub.4 H.sub.9 HCH.sub.3 OCH.sub.3 n-C.sub.6 H.sub.13 HCH.sub.3 SCH.sub.3 n-C.sub.3 H.sub.7 HCH.sub.3 SCH.sub.3 n-C.sub.5 H.sub.11 CH.sub.3C.sub.7 H.sub.7 OC.sub.7 H.sub.7 i-C.sub.3 H.sub.7 HCH.sub.3 OCH.sub.3 n-C.sub.4 H.sub.9 CH.sub.3CH.sub.3 OC.sub.2 H.sub.5 n-C.sub.6 H.sub.13 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 HCH.sub.3 OCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 OCH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 SCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 OCH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 SCH.sub.3 (CH.sub.2).sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5CH.sub.3 SCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 HC.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5C.sub.7 H.sub.7 SCH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5 C.sub.2 H.sub.5C.sub.7 H.sub.7 OC.sub.7 H.sub.7 CH.sub.3 CH.sub.3C.sub.2 H.sub.5 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 C.sub.6 H.sub.5 CH.sub.3______________________________________
EXAMPLE 9
d.l-Methyl 3-{[3-hydroxy-5-(5-phenyl-2-pentyl)]anilino}propionate
A mixture of 3-hydroxy-5-(5-phenyl-2-pentyl)-aniline (1.0 g.), methyl acrylate (345 mg.), and acetic acid (0.1 ml.) is heated at 106°-110° C. overnight. The cooled residue is dissolved in 100 ml. ethyl acetate and washed twice with 100 ml. of saturated sodium bicarbonate solution. The organic phase is then dried (MgSO 4 ) and evaporated to a crude residue which is chromatographed on 130 g. of silica gel using benzene-ether (2:1) as the eluant. After elution of less polar impurities, 540 mg. (40%) d,l-methyl 3-{[3-hydroxy-5-(5-phenyl-2-pentyl)]anilino}propionate is collected. It has the following spectral characteristics:
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.14 (s, 5H, aromatic), 5.83-6.13 (m, 3H, aromatic), 3.66 (s, 3H, --COOCH 3 ), 3.37 (t, 2H, --NCH 2 ), 2.16--2.78 (m, 5H, ##STR23##
EXAMPLE 10
Methyl 3-[(3,5-Dimethoxy-N-ethoxycarbonyl)anilino]propionate
Ethyl chloroformate (2.0 g., 8.4 mmole) is added dropwise over a 10 minute period to a mixture of methyl 3-(3,5-dimethoxyanilino)propionate (1.0 ml., 10.5 mmole), methylene chloride (5 ml.) and pyridine (5 ml.) at 0° C. under a nitrogen atmosphere. The mixture is stirred at 0° C. for 20 minutes following addition of the ethyl chloroformate and then at room temperature for an additional 20 minutes, and is then poured into a mixture of methylene chloride (75 ml.) and ice-water (50 ml.). The methylene chloride layer is separated, washed successively with 10% hydrochloric acid (2×50 ml.), saturated aqueous sodium bicarbonate (1×30 ml.) and saturated aqueous sodium chloride (1×40 ml.) and dried (MgSO 4 ). It is then decolorized with activated charcoal and concentrated under reduced pressure to an oil (2.72 g.). The product is used as is.
Similarly, d,l-methyl-3-[3-hydroxy-5-(5-phenyl-2-pentyl)anilino]-propionate is converted to d,l-methyl-3-{[3-hydroxy-5-(5-phenyl-2-pentyl)-N-ethoxycarbonyl]anilino}propionate and the following compounds are prepared from compounds of Examples 7 and 8 by reaction with the appropriate alkyl chloroformate or other reactant of formula R 6 Br where R 6 is other than hydrogen:
______________________________________ ##STR24##Y.sub.1 ZW R.sub.4 R.sub.6 R.sub.5______________________________________CH.sub.3 OCH.sub.3 H COOn-C.sub.4 H.sub.9 HC.sub.2 H.sub.5 OC.sub.2 H.sub.5 H CH.sub.2 COOC.sub.2 H.sub.5 HC.sub.7 H.sub.7 OC.sub.7 H.sub.7 H COOCH.sub.3 HC.sub.7 H.sub.7 SCH.sub.3 H COOC.sub.2 H.sub.5 HCH.sub.3 SCH.sub.3 H COOn-C.sub.3 H.sub.7 HC.sub.2 H.sub.5 SCH.sub.3 H (CH.sub.2).sub.2 COOCH.sub.3 HCH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.2 COOC.sub.2 H.sub.5 HCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 COOCH.sub.3 HC.sub.2 H.sub.5 SCH.sub.3 CH.sub.3 COOCH.sub.3 HCH.sub.3 SCH.sub.3 CH.sub.3 COOC.sub.2 H.sub.5 HC.sub.2 H.sub.5 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 COOn-C.sub.4 H.sub. 9 HC.sub.7 H.sub.7 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 COOC.sub.2 H.sub.5 HC.sub.7 H.sub.7 OC.sub.7 H.sub.7 CH.sub.3 COOCH.sub.3 HC.sub.7 H.sub.7 SCH.sub.3 C.sub.2 H.sub.5 COOC.sub.2 H.sub.5 HC.sub.7 H.sub.7 OC.sub.7 H.sub.7 C.sub.2 H.sub.5 COOCH.sub.3 HC.sub.2 H.sub.5 SCH.sub.3 CH.sub.3 COOi-C.sub.3 H.sub.7 HC.sub.7 H.sub.7 SCH.sub.3 CH.sub.3 (CH.sub.2).sub.3 COOC.sub.2 H.sub.5 HCH.sub.3 OCH.sub.3 H COOC.sub.7 H.sub.7 HCH.sub.3 OCH.sub.3 CH.sub.3 COOC.sub.7 H.sub.7 HCH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.3 HCH.sub.3 OCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 HCH.sub.3 OCH.sub.3 CH.sub.3 n-C.sub.4 H.sub.9 HC.sub.2 H.sub.5 SCH.sub.3 H i-C.sub.3 H.sub.7 HC.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 HCH.sub.3 OC.sub.2 H.sub.5 CH.sub.3 (CH.sub.2).sub.2 C.sub.6 H.sub.5 HC.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 (CH.sub.2).sub.4 C.sub. 6 H.sub.5 HC.sub.2 H.sub.5 SCH.sub.3 H CH.sub.3 HCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 HCH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 HCH.sub.3 SCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub.5 HC.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 COOC.sub.2 H.sub.5 CH.sub.3C.sub.2 H.sub.5 OCH.sub.3 CH.sub.3 COOCH.sub.3 C.sub.2 H.sub.5CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 COOC.sub.2 H.sub.5 C.sub.2 H.sub.5C.sub.2 H.sub.5 SCH.sub.3 CH.sub.3 COOC.sub.2 H.sub.5 CH.sub.3CH.sub.3 OC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3CH.sub.3 SCH.sub.3 C.sub.2 H.sub.5 COOC.sub.2 H.sub.5 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.3 COOCH.sub.2 C(CH.sub.3).sub.3 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.3 CH.sub.2 COOCH.sub.3 HCH.sub.3 OCH.sub.3 CH.sub.3 (CH.sub.2).sub.4 COOCH.sub.3 HCH.sub.3 OCH.sub.3 CH.sub.3 n-C.sub.6 H.sub.13 HCH.sub.3 OCH.sub.3 n-C.sub.3 H.sub.7 COOCH.sub.3 HCH.sub.3 OCH.sub.3 n-C.sub.4 H.sub.9 COOCH.sub.3 HCH.sub.3 OCH.sub.3 n-C.sub.6 H.sub.13 COOCH.sub.3 HCH.sub.3 OC.sub.7 H.sub.7 n-C.sub.4 H.sub.9 CH.sub.3 CH.sub.3CH.sub.3 SCH.sub.3 n-C.sub.5 H.sub.11 CH.sub.2 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 OC.sub.7 H.sub.7 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5 CH.sub.3C.sub.2 H.sub.5 OC.sub.2 H.sub.5 (CH.sub.2).sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 CH.sub.3C.sub.7 H.sub.7 SCH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5 n-C.sub.5 H.sub.11 C.sub.2 H.sub.5CH.sub.3 OCH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.3 COCH.sub.3 CH.sub.3CH.sub.3 SCH.sub.3 (CH.sub.2).sub.2 C.sub.6 H.sub.5 CHO CH.sub.3C.sub.7 H.sub.7 OC.sub.7 H.sub.7 CH.sub.3 COC.sub.5 H.sub.11 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.3 COCH.sub.2 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 OCH.sub.3 CH.sub.3 CO(CH.sub.2).sub.3 C.sub.6 H.sub.5 HCH.sub.3 SCH.sub.3 H COCH.sub.3 HCH.sub.3 SCH.sub.3 H n-C.sub.6 H.sub.13 HCH.sub.3 SCH.sub.3 n-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 HCH.sub.3 OCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 COOCH.sub.3 HC.sub.7 H.sub.7 OC.sub.7 H.sub.7 i-C.sub.3 H.sub.7 COOC.sub.2 H.sub.5 HCH.sub.3 OC.sub.2 H.sub.5 n-C.sub.6 H.sub.13 i-C.sub.3 H.sub.7 CH.sub.3CH.sub.3 SCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 COOC.sub.7 H.sub.7 CH.sub.3CH.sub.3 OCH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 COCH.sub.2 C.sub.6 H.sub.5 CH.sub.3CH.sub.3 SCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 COOn-C.sub.4 H.sub.9 HC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CH.sub.3 COOC.sub.7 H.sub.7 CH.sub.3______________________________________
EXAMPLE 11
3-[(3,5-Dimethoxy-N-ethoxycarbonyl)anilino]propionic Acid
Methyl 3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]propionate (2.72 g., 8.36 mmoles), aqueous sodium hydroxide (8.4 ml. of 1 N) and ethanol (8.4 ml.) are combined and stirred overnight under nitrogen at room temperature. The reaction mixture is then concentrated under reduced pressure to half-volume, diluted with water (35 ml.) and then extracted with ethyl acetate. The aqueous phase is acidified to pH 2 with 10% hydrochloric acid and extracted with methylene chloride (3×50 ml.). The combined extracts are washed with brine, dried (MgSO 4 ) and concentrated to give the product as an oil (2.47 g.) which is used as is.
In like manner, the remaining compounds of Example 10 are hydrolyzed to their corresponding alkanoic acids having the formula ##STR25##
EXAMPLE 12
1-Carbethoxy-5,7-dimethoxy-4-oxo-1,2,3,4-tetrahydroquinoline
A mixture of 3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]propionic acid (1.10 g., 3.7 mmole) and polyphosphoric acid (4 g.) is heated at 65° C. for 45 minutes under an atmosphere of nitrogen and is then cooled to 0° C. It is then taken up in a mixture of methylene chloride-water (200 ml. of 1:1). The organic layer is separated and the aqueous phase extracted again with methylene chloride (2×100 ml.). The combined extracts are washed with saturated sodium bicarbonate (3×100 ml.), brine (1×100 ml.) and then dried (MgSO 4 ). Concentration of the dried extract gives the product as an oil which crystallizes from benzene. Yield=645 mg., m.p. 109°-111° C.
Analysis: Calc'd for C 14 H 17 O 5 N: C, 60.21; H, 6.14; N, 5.02%. Found: C, 60.11; H, 6.14; N, 4.80%.
EXAMPLE 13
5,7-Dihydroxy-4-oxo-1,2,3,4-tetrahydroquinoline
A mixture of glacial acetic acid (60 ml.), 48% hydrobromic acid (60 ml.) and 1-carbethoxy-5,7-dimethoxy-4-oxo-1,2,3,4-tetrahydroquinoline (4.0 g., 14.3 mmole) is refluxed overnight and is then concentrated in vacuo to a dark oil. The oil is dissolved in water (50 ml.) and the aqueous solution neutralized to pH 6-7 with 1 N sodium hydroxide. A saturated solution of salt water (50 ml.) is added and the resulting mixture extracted with ethyl acetate (3×150 ml.). The extracts are combined, dried (MgSO 4 ) and concentrated under reduced pressure to an oil. The oil is taken up in benzene-ethyl acetate (1:1) and the solution charged to a silica gel column. The column is eluted with a volume of benzene equal to the volume of the column and then with benzene-ethyl acetate (250 ml. of 4:1) and benzene-ethyl acetate (250 ml. of 1:1). Fractions (75 ml.) are collected. Fractions 4-9 are combined and evaporated under reduced pressure. The oily residue is crystallized from ethanol-hexane (1:10). Yield=1.86 g., m.p. 166°-169° C.
Further recrystallization raises the melting point to 171°-172.5° C.
m/e--179 (m + ).
Analysis: Calc'd for C 9 H 9 O 3 N: C, 60.33; H, 5.06; N, 7.82%. Found: C, 60.25; H, 4.94; N, 7.55%.
By means of the procedure of Example 12 and this procedure, 3-{[3-hydroxy-5-(5-phenyl-2-pentyl)-N-ethoxycarbonyl]anilino}propionic acid is transformed to 5-hydroxy-7-(5-phenyl-2-pentyl)-4-oxo-1,2,3,4-tetrahydroquinoline, and the following compounds are prepared from compounds of Example 11:
______________________________________ ##STR26##R.sub.6 R.sub.4 XH R.sub.5______________________________________H C.sub.2 H.sub.5 OH HH H SH HH CH.sub.3 SH HH C.sub.2 H.sub.5 SH HCH.sub.3 H OH HCH.sub.3 CH.sub.3 OH HC.sub.2 H.sub.5 CH.sub.3 OH Hn-C.sub.4 H.sub.9 CH.sub.3 OH Hi-C.sub.3 H.sub.7 H SH HCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 OH H(CH.sub.2).sub.2 C.sub.6 H.sub.5 CH.sub.3 OH H(CH.sub.2).sub.4 C.sub.6 H.sub.5 CH.sub.3 OH HCH.sub.3 H SH HCH.sub.3 C.sub.2 H.sub.5 OH HCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 SH H(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5 SH HC.sub.2 H.sub.5 H OH HCH.sub.3 CH.sub.3 SH HH CH.sub. 3 OH CH.sub.3H C.sub.2 H.sub.5 OH C.sub.2 H.sub.5H CH.sub.3 OH C.sub.2 H.sub.5n-C.sub.6 H.sub.13 CH.sub.3 OH HH CH.sub.3 SH CH.sub.3H C.sub.2 H.sub.5 SH C.sub.2 H.sub.5CH.sub.2 COOH H OH HCH.sub.2 COOH C.sub.2 H.sub.5 OH HCH.sub.2 COOH CH.sub.3 OH H(CH.sub.2).sub.2 COOH H SH H(CH.sub.2).sub.3 COOH CH.sub.3 SH H(CH.sub.2).sub.4 COOH CH.sub.3 OH HH n-C.sub.3 H.sub.7 OH HH n-C.sub.4 H.sub.9 SH HH n-C.sub.6 H.sub.13 OH HH CH.sub.3 OH CH.sub.3H n-C.sub.4 H.sub.9 OH CH.sub.3H n-C.sub.4 H.sub.9 OH C.sub.2 H.sub.5H n-C.sub.6 H.sub.13 OH CH.sub.3H CH.sub.2 C.sub.6 H.sub.5 OH CH.sub.3H (CH.sub.2).sub.2 C.sub.6 H.sub.5 OH CH.sub.3H (CH.sub.2).sub.4 C.sub.6 H.sub.5 OH CH.sub.3H CH.sub.2 C.sub.6 H.sub.5 SH CH.sub.3H (CH.sub.2).sub.3 C.sub.6 H.sub.5 SH C.sub.2 H.sub.5CH.sub.3 CH.sub.3 OH CH.sub.3n-C.sub.3 H.sub.7 CH.sub.3 OH CH.sub.3n-C.sub.6 H.sub.13 CH.sub.3 OH CH.sub.3n-C.sub.4 H.sub.9 CH.sub.2 C.sub.6 H.sub.5 OH CH.sub.3CH.sub.3 n-C.sub.4 H.sub.9 OH CH.sub.3CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 OH CH.sub.3(CH.sub.2).sub.4 C.sub.6 H.sub.5 CH.sub.3 OH CH.sub.3CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub.5 OH CH.sub.3CH.sub.2 COOH CH.sub.3 OH CH.sub.3(CH.sub.2).sub.2 COOH CH.sub.3 OH CH.sub.3(CH.sub.2).sub.4 COOH C.sub.2 H.sub.5 OH CH.sub.3CH.sub.3 CH.sub.3 OH CH.sub.3CH.sub.2 COOH C.sub.2 H.sub.5 OH CH.sub.3CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 SH CH.sub.3(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 SH CH.sub.3CH.sub.3 CH.sub.3 SH CH.sub.3CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 SH CH.sub.3i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 SH C.sub.2 H.sub.5CH.sub.2 COOH (CH.sub.2 ).sub.2 C.sub.6 H.sub.5 SH C.sub.2 H.sub.5n-C.sub.5 H.sub.11 CH.sub.3 SH CH.sub.3(CH.sub.2).sub.4 COOH CH.sub.3 SH CH.sub.3CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub.5 SH CH.sub.3H n-C.sub.6 H.sub.13 SH CH.sub.3CH.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.5 OH Hn-C.sub.4 H.sub.9 C.sub.2 H.sub.5 OH HCH.sub.2 C.sub.6 H.sub.5 H OH H(CH.sub.2).sub.2 COOH CH.sub.3 SH H(CH.sub.2).sub.4 COOH H OH HH CH.sub.2 C.sub.6 H.sub.5 SH Hi-C.sub.3 H.sub.7 CH.sub.3 SH CH.sub.3(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 SH CH.sub.3______________________________________
EXAMPLE 14
d,l-1-Carbethoxy-5,7-dimethoxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline
A solution of 3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid (4.0 g., 12.8 mmole) in chloroform (2 ml.) is added dropwise with stirring to polyphosphoric acid (5.0 g.) heated to 60° C. on a steam bath. The reaction mixture is held at 60°-65° C. for two hours and is then poured into a mixture of ice (100 g.) and ethyl acetate (100 ml.). The aqueous layer is further extracted with ethyl acetate (2×100 ml.) and the combined organic extracts washed successively with saturated sodium bicarbonate solution (3×100 ml.), brine (1×100 ml.), and then dried over anhydrous magnesium sulfate. Concentration of the dried extract under reduced pressure gives 2.6 g. of crude product.
Purification is accomplished by column chromatography of a benzene solution of the crude product (2.5 g.) on silica gel (95 g.). The column is eluted with a volume of benzene equal to one-half the volume of the column, followed by benzene/ethyl acetate (1:1). Fractions (40 ml.) are collected. Fractions 9-18 are combined and evaporated in vacuo to give 1.55 g. of product which is purified further by recrystallization from petroleum ether--1.33 g., m.p. 92.5°-94° C.
Recrystallization of this product from hot ethyl acetate/hexane (1:1) affords an analytical sample; m.p. 94°-95° C.
Analysis: Calc'd for C 15 H 19 O 5 N: C, 61.42; H, 6.53; N, 4.78%. Found: C, 61.54; H, 6.55; N, 4.94%.
m/e--293 (m + ).
IR (KBr)-- ##STR27##
EXAMPLE 15
d,l-5,7-Dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline
Method A
A mixture of glacial acetic acid (240 ml.), 48% hydrobromic acid (240 ml.) and 1-carbethoxy-5,7-dimethoxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline (16.0 g., 55 mmole) is refluxed overnight and is then concentrated in vacuo to a dark oil. The oil is dissolved in water (200 ml.) and the aqueous solution neutralized to pH 6-7 with 1 N sodium hydroxide. A saturated solution of salt water (200 ml.) is added and the resulting mixture extracted with ethyl acetate (3×500 ml.). The extracts are combined, dried (MgSO 4 ) and concentrated under reduced pressure to a dark oil (12.8 g.). Hexane-ethyl acetate (10:1) is added to the oil and the resulting crystals recovered by filtration (3.8 g.); m.p. 158°-165° C. Trituration of the crystals in ethyl acetate gives 1.65 g. of product; m.p. 165°-168° C.
Additional material separates from the mother liquors on standing (2.9 g.); m.p. 168°-170° C. Column chromatography of the filtrate on silica gel using benzene-ether (1:1) as solvent gives an additional 4.6 g. of product, m.p. 167°-169° C.
Further purification is achieved by recrystallizing the product from ethyl acetate; m.p. 173°-174° C.
Analysis: Calc'd for C 10 H 11 O 3 N: C, 62.16; H, 5.74; N, 7.25%. Found: C, 62.00; H, 5.83; N, 7.14%.
m/e--193 (m + ).
Method B
A mixture of d,l-3-[(3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid (100 g., 0.32 mole) and 48% hydrobromic acid (500 ml.)/glacial acetic acid (300 ml.) is heated in an oil bath at 110° C. for 2 hours. The oil-bath temperature is then increased to 145° C. and heating is continued for an additional 2 hours. During this last heating period an azeotropic mixture distills (boiling point 42°→100° C., ˜200-300 ml.) and the deep-red homogeneous solution is allowed to cool to room temperature. The mixture is poured onto icewater (3 liters) and ether (2 liters), the layers are separated and the aqueous solution is washed with ether (2×1000 ml.). The ether layers are combined and washed successively with water (2×1000 ml.), brine (1×500 ml.), saturated NaHCO 3 solution (4×250 ml.) and brine (1×500 ml.) and then dried (MgSO 4 ). Decolorization with charcoal and evaporation of the ether affords a yellow foam which is crystallized from ca. 300 ml. methylene chloride to give 31.3 g. (50.4%) of pure 5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline. Additional product can be isolated from the mother liquor by silica gel chromatography.
1 H NMR (60 MHz) δ TMS (100 mg. sample/0.3 ml. CDCl 3 /0.2 ml. CD 3 SOCD 3 ) (ppm): 12.40 (s,1H,C 5 --OH), 5.72 (d,2H,meta H), 5.38-5.60(bs,1H,C 7 --OH), 3.50-4.00(m,1H,C2H), 2.38-2.60(m,2H,C 3 --H 2 ), 1.12(d,3H,methyl).
m/e--193 (m + ).
Analysis: Calc'd for C 10 H 11 O 3 N: C, 62.16; H, 5.74; N, 7.25%. Found: C, 62.01; H, 5.85; N, 7.02%.
Similarly, methyl dl-3-{[3-hydroxy-5-(5-phenyl-2-pentyl)]anilino}propionate is converted to dl-5-hydroxy-7-(5-phenyl-2-pentyl)-4-oxo-1,2,3,4-tetrahydroquinoline which is purified by column chromatography using silica gel and benzene/ether (5:1) as eluant.
m/e--309 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.22 (s, 1H, 50H), 7.14 (s, 5H, C 6 H 5 ), 6.04 (d, J=2.5 Hz, 1H meta H), 5.87 (d, J=2.5Hz, 1H meta H), 4.19-4.60 (b, 1H, NH), 3.48 (t, 2H, CH 2 N), 2.18-2.89 (m, 5H, ArCH, ArCH 2 , CH 2 --C═O), 1.38-1.86 (m, 4H, --[CH 2 ] 2 --), 1.13 (d, 3H, CH 3 ).
and ethyl dl-3-(3,5-dimethoxyanilino)hexanoate hydrochloride is converted to dl-5,7-dihydroxy-2-propyl-4-oxo-1,2,3,4-tetrahydroquinoline; m.p. 117°-119° C. (from methylene chloride).
m/e--221 (m + ), 135 (base peak, m + --propyl).
and 1-3-[(3,5-dimethoxy-(N-ethoxy carbonyl)anilino]butyric acid is converted to d-5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline, m.p. 167°-168° C.
[α] D 25 =+167.8°(c=1.0, CH 3 OH).
m/e--193 (m + ).
Analysis: Calc'd for C 10 H 11 O 3 N: C, 62.16; H, 5.74; N, 7.25%. Found: C, 61.87; H, 5.62; N, 6.96%.
and d-3-[3,5-dimethoxy-N-ethoxycarbonyl)anilino]butyric acid is converted to 1-5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline; m.p. 166°-168° C.
[α] D 25 =-168.5° (c=1.0, CH 3 OH).
m/e--193 (m + )
Analysis: Calc'd for C 10 H 11 O 3 N: C, 62.16; H, 5.74; N, 7.25%. Found: C, 61.82; H, 5.83; N, 7.22%.
EXAMPLE 16
d,l-5,7-Dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline
A mixture of 3,5-dimethoxyaniline (230 g., 1.5 moles), methyl crotonate (150 g., 1.5 moles) and glacial acetic acid (90 g., 1.5 moles) is heated at reflux for 6 hours. Additional glacial acetic acid (90 g., 1.5 moles) is added and the mixture refluxed overnight. Hydrobromic acid (1000 ml. of 48% solution) and glacial acetic acid (850 ml.) are added to the reaction mixture which is heated at reflux for 4.5 hours. The title product is isolated and purified according to the procedure of Example 13. Yield=36 g., m.p. 166°-170° C.
Repetition of this procedure but replacing methyl crotonate with methyl acrylate, methyl 3-ethyl acrylate or methyl 3,3-dimethylacrylate affords 5,7-dihydroxy-4-oxo-1,2,3,4-tetrahydroquinoline, 5,7-dihydroxy-2-ethyl-4-oxo-1,2,3,4-tetrahydroquinoline, and 5,7-dihydroxy-2,2-dimethyl-4-oxo-1,2,3,4-tetrahydroquinoline, respectively.
EXAMPLE 17
dl-5,7-Dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline
A mixture of 3,5-dimethoxyaniline (4.6 g., 0.03 mole), crotonic acid (2.54 g., 0.03 mole) and pyridine hydrochloride (3.0 g., 1.26 moles) is heated at 185°-200° C. for 45 minutes. The cooled reaction mixture is suspended in water (500 ml. ) (pH ˜3) and the pH adjusted to 7 and the resultant mixture stirred for 10 minutes. The organic layer is separated, dried (MgSO 4 ) and concentrated to 3.2 g. of a yellow oil.
A mixture of glacial acetic acid (110 ml.), 48% hydrobromic acid (110 ml.) and the yellow oil is refluxed for one hour and is then concentrated in vacuo to a dark oil. The oil is dissolved in water and the aqueous solution neutralized to pH 6-7 with 1 N sodium hydroxide. A saturated solution of salt water is added and the resulting mixture extracted with ethyl acetate. The extracts are combined, dried (MgSO 4 ) and concentrated under reduced pressure to a dark oil (2.8 g.). Column chromatography of the crude residue on silica gel using benzene-ether (4:1) as eluant gives an additional 510 mg. of product, m.p. 168°-170° C.
Further purification is achieved by recrystallizing the product from ethyl acetate; m.p. 173°-174° C.
Analysis: Calc'd for C 10 H 11 O 3 N: C, 62.16; H, 5.74; N, 7.25%. Found: C, 62.00; H, 5.83; N, 7.14%.
m/e--193 (m + ), 178 (m + --methyl, base peak).
In a similar manner, 3,3-dimethyl acrylic acid and 3,5-dimethoxyaniline gives after purification by silica gel chromatography (benzene/ether 1:1 as eluant) 5,7-dihydroxy-2,2-dimethyl-4-oxo-1,2,3,4-tetrahydroquinoline as a yellow oil.
______________________________________Analysis (MS)______________________________________Parent peak (m.sup.+)Calc'd for C.sub.11 H.sub.13 O.sub.3 N: 207.0895Found: 207.089515)e peak (m.sup.+Calc'd for C.sub.10 H.sub.10 O.sub.3 N: 192.0661Found: 192.0655______________________________________
Similarly, styryl acetic acid and 3,5-dimethoxyaniline are condensed to yield dl-5,7-dihydroxy-2-benzyl-4-oxo-1,2,3,4-tetrahydroquinoline as an oil after purification using benzene/ether (3:1) as eluant.
m/e=269 (m + ) and 178 (m + --benzyl, base peak).
NMR (CDCl 3 ) δ (ppm): 8.76 (s, 1H, 5-OH), 7.18-7.6 (m, 5H, C 6 H 5 ), 5.84 (d, J=3 Hz, 1H) and 5.62 (d, J=3 Hz, 1H) for the meta coupled aromatics, and 2.14-4.82 (4m, 7H), for the remaining protons (7-OH, CH-N, CH 2 --C═O, --CH 2 --C 6 H 5 and N--H).
EXAMPLE 18
Following the procedures of Examples 9-15, the compounds tabulated below are prepared from appropriate 3-hydroxy-5-(Z-W)anilines and appropriate esters of the formula R 4 R 5 C═CH-COOCH 3 wherein each of R 4 ,R 5 is hydrogen, methyl or ethyl.
__________________________________________________________________________ ##STR28##R.sub.5 R.sub.4 Z W__________________________________________________________________________H H CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H H (CH.sub.2).sub.3 C.sub.6 H.sub.5H H (CH.sub.2).sub.4 C.sub.6 H.sub.5H C.sub.2 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5H H (CH.sub.2).sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 C.sub.6 H.sub.5H H C(CH.sub.3).sub.2 C.sub.6 H.sub.5H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub. 2).sub.3 C.sub.6 H.sub.5H H (CH.sub.2).sub.6 C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.8 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5H H CH.sub.2 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.5H H CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4H C.sub.2 H.sub.5 CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.5H CH.sub.3 CH.sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.3 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)CH.sub.2 C.sub.5 H.sub.9H H CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.5 H.sub.9H H CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.5 H.sub.9H H CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.5H H CH(CH.sub.3)CH(CH.sub.3) C.sub.6 H.sub.11H C.sub.2 H.sub.5 CH(CH.sub.3)CH(CH.sub.3) C.sub.6 H.sub.11H H CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11H H (CH.sub.2).sub.4 C.sub.3 H.sub.5H H (CH.sub.2).sub.8 C.sub.6 H.sub.11H C.sub.2 H.sub.5 (CH.sub.2).sub.8 C.sub.6 H.sub.11H H (CH.sub.2).sub.3 CH(CH.sub.3) C.sub.6 H.sub.11H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.11H H CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.11H CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.11H H (CH.sub.2).sub.3 2-pyridylH H (CH.sub.2).sub.3 4-pyridylH H (CH.sub.2).sub.4 2-pyridylH CH.sub.3 (CH.sub.2).sub.4 4-pyridylH C.sub.2 H.sub.5 (CH.sub.2).sub.4 3-pyridylH CH.sub.3 CH.sub.2 CH(CH.sub.3)CH.sub.2 4-pyridylH C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 3-pyridylH CH.sub.3 CH(CH.sub.3)CH(C.sub.2 H.sub.5)CH.sub.2 4-pyridylH H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 3-pyridylH H CH.sub.2 CH(C.sub.2 H.sub.5)CH.sub.2 3-pyridylH H CH(CH.sub.3)(CH.sub.2).sub.2 4-pyridylH CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 2-piperidylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) 4-piperidylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13H H CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13H CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.4 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HH H CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HH H CH.sub.2 HH CH.sub.3 CH.sub.2 CH.sub.3H H (CH.sub.2).sub.3 CH.sub.3H H (CH.sub.2).sub.6 CH.sub.3H CH.sub.3 (CH.sub.2).sub.6 CH.sub.3H H CH(CH.sub.3) CH.sub.3H CH.sub.3 (CH.sub.2).sub.3 HH H CH(CH.sub.3) C.sub.6 H.sub.11H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub. 3H H (CH.sub.2).sub.3O C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.3O 4-FC.sub.6 H.sub.4H CH.sub.3 (CH.sub.2).sub.3O C.sub.6 H.sub.11H C.sub.2 H.sub.5 (CH.sub.2).sub.3O C.sub.4 H.sub.7H H (CH.sub.2).sub.3O CH.sub.3H CH.sub.3 (CH.sub.2).sub.3O 4-(4-FC.sub.6 H.sub.4)C.sub.6 H.sub.10H C.sub.2 H.sub.5 (CH.sub.2).sub.3O(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4H H (CH.sub.2).sub.3O(CH.sub.2).sub.2 C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.3OCH(CH.sub.3) 4-piperidylH CH.sub.3 (CH.sub.2).sub.3OCH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.3OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3H H CH(CH.sub.3)(CH.sub.2).sub.2O C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH.sub.3H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2O(CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH(CH.sub.3) C.sub.7 H.sub.13H H CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH CH.sub.3 (C.sub.2 H.sub.5)H CH.sub.3 (CH.sub.2).sub.4O C.sub.6 H.sub.5H H (CH.sub.2).sub.4OCH(CH.sub.3)CH.sub.2 3-piperidylH C.sub.2 H.sub.5 (CH.sub.2).sub.4O(CH.sub.2).sub.5 4-piperidylH C.sub.2 H.sub.5 (CH.sub.2).sub.4OCH.sub.2 4-FC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.3O 2-(4-FC.sub.6 H.sub.5)C.sub.2 H.sub.8H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3O(CH.sub.2).sub.2 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3O(CH.sub.2).sub.2 CH.sub.3H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O(CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2OCH(CH.sub.3) 4-piperidylH H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O (CH.sub.2).sub.2 C.sub.7 H.sub.13 CH(CH.sub.3)H CH.sub.3 CH(CH.sub.3)OCH.sub.2 C.sub.5 H.sub.9H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O C.sub.3 H.sub.5H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O 2-(4-FC.sub.6 H.sub.11)C.sub.7 H.sub.12H H (CH.sub.2).sub.3S C.sub.6 H.sub.5H C.sub.2 H.sub.5 (CH.sub.2).sub.3SCH.sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 (CH.sub.2).sub.3S C.sub.5 H.sub.9H C.sub.2 H.sub.5 (CH.sub.2).sub.3S(CH.sub.2).sub.2 CH.sub.3H H (CH.sub.2).sub.3S(CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-piperidylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S(CH.sub.2).sub.4 4-pyridylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S(CH.sub.2).sub.4 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2S C.sub.6 H.sub.11H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2S(CH.sub.2).sub.2 CH.sub.3 CH(CH.sub.3)H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2SCH(CH.sub.3) 4-ClC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.3S(CH.sub.2).sub.4 4-FC.sub.6 H.sub.4H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3S(CH.sub.2).sub.4 4-pyridylH H CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.6 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.6 C.sub.6 H.sub.5H H CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.4 CH.sub.3H H CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)CH.sub.2OCH.sub.2 4-FC.sub.6 H.sub.4H CH.sub. 3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.2 4-pyridylH H CH(CH.sub.3)CH.sub.2OCH(CH.sub.3) CH.sub.3H H CH.sub.2 CH(CH.sub.3)3CH.sub.2 CH.sub.3H C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.3)OCH.sub.2 CH.sub.3H CH.sub.3 CH.sub.2 CH(CH.sub.3)O(CH.sub.2).sub.6 CH.sub.3H CH.sub.3 CH.sub.2 CH(CH.sub.3)OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H H CH.sub.2 CH(CH.sub.3)O(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HH C.sub.2 H.sub.5 C(CH.sub.3l ).sub.2 (CH.sub.2).sub.6 HCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.2 H.sub.5 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub. 5H n-C.sub.6 H.sub.13 (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5H (CH.sub.2).sub.4 C.sub.6 H.sub.5 (CH.sub.2).sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.6 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.8 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5H n-C.sub.4 H.sub.9 CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4CH.sub.3 n-C.sub.6 H.sub.13 CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4H (CH.sub.2).sub.2 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.5H CH.sub.3 CH.sub.2 C.sub.6 H.sub.5H CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub. 3 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2 C.sub.5 H.sub.9CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.5H (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH.sub.3 n-C.sub.4 H.sub.9 (CH.sub.2).sub.4 C.sub.3 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.9 C.sub.6 H.sub.11CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 2-pyridylCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 4-pyridylCH.sub.3 CH.sub.3 (CH.sub.2).sub.4 4-pyridylC.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.4 3-pyridylCH.sub.3 CH.sub.3 CH(CH.sub.3)CH(C.sub.2 H.sub.5)CH.sub.2 4-pyridylH n-C.sub.5 H.sub.11 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 3-pyridylH i-C.sub.3 H.sub.7 CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylCH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub. 2 2-piperidylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) 4-piperidylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13H n-C.sub.4 H.sub.9 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.4 CH.sub.3CH.sub.3 CH.sub.3 CH(CH.sub.3)CH(CH.sub.3) H (CH.sub.2).sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3)CH(CH.sub.3) H (CH.sub.2).sub.5CH.sub.3 CH.sub.3 CH.sub.2 HCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.3 C.sub.3H n-C.sub.6 H.sub.13 (CH.sub.2).sub.6 CH.sub.3CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH(CH.sub.3) CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 HH n-C.sub.4 H.sub.9 CH(CH.sub.3) C.sub.6 H.sub.11CH.sub.3 CH.sub.3 (CH.sub.2).sub.3O C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2 ).sub.3O 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 (CH.sub.2).sub.3O C.sub.6 H.sub.11C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3O C.sub.4 H.sub.7H CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3O CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.3O 4-(4-FC.sub.6 H.sub.4)C.sub.6 H.sub.10C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3O(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH.sub.3 CH.sub.3 (CH.sub.2).sub.3OCH(CH.sub.3) 4-piperidylH n-C.sub.5 H.sub.11 CH(CH.sub.3)(CH.sub.2).sub.2O C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH.sub.3CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2O C.sub.6 H.sub.5 (CH.sub.2).sub.4CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH C.sub.7 H.sub.13 (CH.sub.3)CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH.sub.3 CH(C.sub.2 H.sub.5)CH.sub.3 CH.sub.3 (CH.sub.2).sub.4O C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.4OCH(CH.sub.3)CH.sub.2 3-piperidylCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.4OCH.sub.2 4-FC.sub.6 H.sub.4H n-C.sub.3 H.sub.7 CH(CH.sub.3)(CH.sub.2).sub.3O 2-(4-FC.sub.6 H.sub.5)C.sub.2 H.sub.8CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3O C.sub.6 H.sub.5 (CH.sub.2).sub.2CH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O 4-piperidyl CH(CH.sub.3)CH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O C.sub.3 H.sub.5CH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O 2-(4-FC.sub.6 H.sub.11)C.sub.7 H.sub.12CH.sub.3 CH.sub.3 (CH.sub.2).sub.3S C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3SCH.sub.2 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 (CH.sub.2).sub.3S C.sub.5 H.sub.9CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3S(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-piperidylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-pyridyl (CH.sub.2).sub.4CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S C.sub.6 H.sub.5 (CH.sub.2).sub.4C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2SO C.sub.6 H.sub.11H n-C.sub.6 H.sub.13 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2S 4-ClC.sub.6 H.sub.4 CH(CH.sub.3)CH.sub.3 n-C.sub.4 H.sub.9 CH(CH.sub.3)(CH.sub.2).sub.3S 4-FC.sub.6 H.sub.4 (CH.sub.2).sub.4CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3S 4-pyridyl (CH.sub.2).sub.4CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.6 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.2 H.sub. 5 C.sub.2 H.sub.5 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H__________________________________________________________________________
Of course, when Z contains an ether or thioether linkage, the procedure of Example 14 is used for the cyclization step.
EXAMPLE 19
d,l-5-Hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline
Potassium hydroxide pellets (325 mg., 52 mmole) is added to a solution of d,l-5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline (1.0 g., 52 mmole) in N,N-dimethylformamide (10 ml.). The mixture is slowly heated to 100° C. and to the resulting solution d,l-2-bromoheptane (1.08 g., 60 mmole) is added all at once with good stirring. After 10 minutes additional potassium hydroxide (160 mg.) is added followed by additional d,l-2-bromoheptane (500 mg.). The addition of potassium hydroxide and d,l-2-bromoheptane was repeated two more times using 80 mg. potassium hydroxide and 250 mg. d,l-2-bromoheptane each time. The reaction mixture is stirred an additional 10 minutes and is then cooled. Chloroform (50 ml.) and aqueous sodium hydroxide (25 ml. of 1N) are added, the mixture stirred for 10 minutes and the layers separated. The chloroform extraction is repeated, the extracts combined, dried (MgSO 4 ) and concentrated under reduced pressure to a dark oil. The oil is chromatographed on silica gel (120 g.) using benzene as solvent. Fractions of 30 ml. each are collected. The 12th-18th fractions are combined and concentrated under reduced pressure to a light yellow oil (850 mg.) which crystallizes upon standing. The desired product is separated by filtration and recrystallized from hot hexane, m.p. 76°-77° C.
The above procedure is repeated on a 20-fold scale but using benzene-ethyl acetate (9:1) as chromatographic solvent. Fractions of 750 ml. each are collected. Combination of the 2nd-6th fractions affords 32 g. of oil which partially crystallizes from hexane upon standing and cooling to give 18.2 g. of product. An additional 3.2 g. is obtained by concentrating the mother liquor and allowing it to crystallize by standing in the cold. Total yield=21.4 g.
Analysis: Calc'd for C 17 H 25 O 3 N: C, 70.07; H, 8.65; N, 4.81%. Found: C, 69.82; H, 8.67; N, 4.93%.
m/e--291 (m + ).
IR (KBr): 6.01μ (═O).
In like manner, 5,7-dihydroxy-4-oxo-1,2,3,4-tetrahydroquinoline converted to d,l-5-hydroxy-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline, an oil.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 13.3 (s, 1H, phenolic), 5.5 and 5.7 (d, 2H, J=2 Hz, aromatic), 4.6 (bs, 1H,--NH), 4.1-4.6 (m, 1H, --O--CH--), 3.3 (t, 2H, J=7 Hz, --CH 2 --), 2.6 (t, 2H, J=7 Hz, --CH 2 --), 2.0-0.7 (m, remaining protons).
EXAMPLE 20
The following compounds are prepared according to the procedure of Example 19 but using the appropriate Br-(alk 2 ) n -W reactant and the appropriate 5,7-dihydroxy-2-R 4 R 5 -4-oxo-1,2,3,4-tetrahydroquinoline or 5-hydroxy-7-thiol-2-R 4 R 5 -4-oxo-1,2,3,4-tetrahydroquinoline.
__________________________________________________________________________ ##STR29##R.sub.5 R.sub.4 X alk.sub.2 W R.sub.6__________________________________________________________________________H H O CH.sub.2 H HH CH.sub.3 O CH.sub.2 H HH CH.sub.3 O (CH.sub.2).sub.2 H HH H O (CH.sub.2).sub.4 H CH.sub.3H CH.sub.3 O (CH.sub.2).sub.6 H HH CH.sub.3 O (CH.sub.2).sub.9 H HH H O CH(CH).sub.3 CH.sub.2 H C.sub.2 H.sub.5H CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 H CH.sub.3H H O CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 HH C.sub.2 H.sub.5 O CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5H H O (CH.sub.2).sub.2 C.sub.6 H.sub.5 CH.sub.2 COOHH CH.sub.3 O (CH.sub.2).sub.4 C.sub. 6 H.sub.5 CH.sub.2 COOHH C.sub.2 H.sub.5 O CH.sub.2 4-ClC.sub.6 H.sub.4 HH H O CH.sub.2 4-FC.sub.6 H.sub.4 HH CH.sub.3 O CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5 CH.sub.3H H O CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5 CH.sub.3H CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 HH C.sub.2 H.sub.5 O (CH.sub.2).sub.7 C.sub.6 H.sub.5 HH H O CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 HH H O (CH.sub.2).sub.2 4-pyridyl C.sub.2 H.sub.5H CH.sub.3 O (CH.sub.2).sub.3 4-pyridyl HH C.sub.2 H.sub.5 O (CH.sub.2).sub.3 3-pyridyl n-C.sub.4 H.sub.9H CH.sub.3 O CH(CH.sub.3)CH.sub.2 2-pyridyl HH H O CH.sub.2 C.sub.3 H.sub.5 HH CH.sub.3 O CH.sub.2 C.sub.3 H.sub.5 HH CH.sub.3 O CH(CH.sub.3) C.sub.4 H.sub.7 HH CH.sub.3 O (CH.sub.2).sub.2 C.sub.5 H.sub.9 HH CH.sub.3 O CH.sub. 2 C.sub.6 H.sub.11 HH CH.sub.3 O (CH.sub.2).sub.3 C.sub.6 H.sub.11 HH C.sub.2 H.sub.5 O (CH.sub.2).sub.3 C.sub.5 H.sub.9 HH CH.sub.3 O (CH.sub.2).sub.4 C.sub.7 H.sub.13 HH H O -- C.sub.6 H.sub.5 HH CH.sub.3 O -- C.sub.6 H.sub.5 CH.sub.3H H O -- 4-FC.sub.6 H.sub.4 HH H O -- 4-ClC.sub.6 H.sub.4 (CH.sub.2).sub.2 C.sub.6 H.sub.5H C.sub.2 H.sub.5 O -- C.sub.6 H.sub.5 HH H O -- C.sub.5 H.sub.9 HH C.sub.2 H.sub.5 O -- C.sub.5 H.sub.9 HH CH.sub.3 O -- C.sub.6 H.sub.11 HH H O -- C.sub.7 H.sub.13 HH H O -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4 HH C.sub.2 H.sub.5 O -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4 CH.sub.3H C.sub.2 H.sub.5 O -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub. H0H H O -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.12 HH H O -- 4-pyridyl C.sub.2 H.sub.5H CH.sub.3 O -- 4-pyridyl HH C.sub.2 H.sub.5 O -- 4-piperidyl HH CH.sub.3 O -- 2-pyridyl HH CH.sub.3 O -- 3-piperidyl HH H S CH.sub.2 H HH CH.sub.3 S CH.sub.2 H HH H S (CH.sub.2).sub.3 H (CH.sub.2).sub.2 COOHH CH.sub.3 S (CH.sub.2).sub.3 H (CH.sub.2).sub.2 COOHH H S (CH.sub.2).sub.5 H HH CH.sub.3 S (CH.sub.2).sub.5 H HH C.sub.2 H.sub.5 S (CH.sub.2).sub.4 H HH H S (CH.sub.2).sub.9 H HH CH.sub.3 S CH(CH.sub.3)(CH.sub.2).sub.5 H (CH.sub.2).sub.3 COOHH H S CH(CH.sub.3)(CH.sub.2).sub.3 H HH CH.sub.3 S CH.sub.2 C.sub.3 H.sub.5 HH H S CH.sub.2 C.sub.6 H.sub.11 HH CH.sub.3 S (CH.sub.2).sub.3 C.sub.6 H.sub.11 HH C.sub.2 H.sub.5 S (CH.sub.2).sub.4 C.sub.7 H.sub.13 HH H S CH(CH.sub.3) C.sub.4 H.sub.7 HH H S CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 HH CH.sub.3 S CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 HH H S C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3 HH CH.sub.3 S C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3 HH CH.sub.3 S CH.sub.2 C.sub.6 H.sub.5 HH CH.sub.3 S (CH.sub.2).sub.4 C.sub.6 H.sub.5 HH H S CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5 HH CH.sub.3 S CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3H CH.sub.3 S CH.sub.2 4-FC.sub.6 H.sub.4 HH H S CH.sub.2 4-ClC.sub.6 H.sub.4 HH CH.sub.3 S (CH.sub.2).sub.3 4-pyridyl HH C.sub.2 H.sub.5 S CH(CH.sub.3)CH.sub.2 2-pyridyl HH H S -- C.sub.6 H.sub.5 HH CH.sub.3 S -- 4-FC.sub.6 H.sub.5 HH C.sub.2 H.sub.5 S -- C.sub.5 H.sub.9 HH CH.sub.3 S -- C.sub.6 H.sub.11 HH H S -- 4-pyridyl HH CH.sub.3 S -- 4-piperidyl CH.sub.2 C.sub.6 H.sub.5H CH.sub.3 S -- C.sub.7 H.sub.13 HH CH.sub.3 S -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4 HH CH.sub.3 S -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10 HH H S -- 4-ClC.sub.6 H.sub.4 HH H S CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 CH.sub.3H CH.sub.3 S CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3H H S C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3 i-C.sub.3 H.sub.7H C.sub.2 H.sub.5 S (CH.sub.2).sub.4 CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 n-C.sub.4 H.sub.9H CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.2 COOHH H O CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.2 COOHH H O CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 (CH.sub.2).sub.4 COOHCH.sub.3 CH.sub.3 O CH.sub.2 H HC.sub.2 H.sub.5 CH.sub.3 O (CH.sub.2).sub.4 H CH.sub.3CH.sub.3 CH.sub.3 O (CH.sub.2).sub.9 H HCH.sub.3 CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 CH.sub.3 HCH.sub.3 CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 HCH.sub.3 n-C.sub.6 H.sub.13 O CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 HC.sub.2 H.sub.5 C.sub.2 H.sub.5 O C(CH.sub.3).sub.2 (CH.sub.2).sub.4 CH.sub.3 HCH.sub.3 CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 HH n-C.sub.6 H.sub.13 O CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 CH.sub.3CH.sub.3 CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4 n-C.sub.3 H.sub.7H CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 n-C.sub.6 H.sub.13H C.sub.2 H.sub.5 O CH(CH.sub.3)(CH.sub.2).sub.3 CH.sub.3 CH.sub.2 COOHH CH.sub.3 O CH(CH.sub.3)(CH.sub.2).sub.3 4-ClC.sub.6 H.sub.4 (CH.sub.2).sub.4 COOHCH.sub.3 CH.sub.3 O (CH.sub.2).sub.3 4-pyridyl CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 O CH(CH.sub.3)(CH.sub.2).sub.3 3-pyridyl HCH.sub.3 n-C.sub.4 H.sub.9 O -- C.sub.6 H.sub.5 HCH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 O -- 4-FC.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 O -- 4-pyridyl (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 O -- C.sub.5 H.sub.9 HC.sub.2 H.sub.5 C.sub.2 H.sub.5 O -- C.sub.7 H.sub.13 HH C.sub.2 H.sub.5 O -- 3-piperidyl HCH.sub.3 CH.sub.3 O -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4 CH.sub.3CH.sub. 3 CH.sub.3 O -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.12 HCH.sub.3 CH.sub.3 O CH.sub.2 C.sub.3 H.sub.5 HCH.sub.3 CH.sub.3 O (CH.sub.2).sub.3 C.sub.6 H.sub.11 (CH.sub.2).sub.2 COOHCH.sub.3 C.sub.2 H.sub.5 O (CH.sub.2).sub.4 C.sub.7 H.sub.13 (CH.sub.2).sub.4 COOHCH.sub.3 CH.sub.3 S -- C.sub.6 H.sub.5 n-C.sub.5 H.sub.11CH.sub.3 CH.sub.3 S -- 4-ClC.sub.6 H.sub.4 HCH.sub.3 CH.sub.3 S -- C.sub.7 H.sub.13 HCH.sub.3 CH.sub.3 S -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10 HH n-C.sub.4 H.sub.9 S -- C.sub.6 H.sub.5 HCH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 S -- 4-pyridyl CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 S -- C.sub.6 H.sub.11 CH.sub.3C.sub.2 H.sub.5 (CH.sub.2).sub.2 C.sub.6 H.sub.5 S -- 4-FC.sub.6 H.sub.4 CH.sub.2 COOHCH.sub.3 CH.sub.3 S -- 4-(C.sub. 6 H.sub.5)C.sub.6 H.sub.10 (CH.sub.2).sub.4 COOHCH.sub.3 n-C.sub.6 H.sub.13 S -- C.sub.6 H.sub.5 HCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 S -- C.sub.6 H.sub.5 HC.sub.2 H.sub.5 C.sub.2 H.sub.5 S CH.sub.2 H HCH.sub.3 CH.sub.3 S (CH.sub.2).sub.5 H CH.sub.3CH.sub.3 CH.sub.3 S (CH.sub.2).sub.9 H i-C.sub.3 H.sub.7CH.sub.3 CH.sub.3 S C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H (CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 S CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 S CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 HC.sub.2 H.sub.5 n-C.sub.4 H.sub.9 S CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.11 i-C.sub.3 H.sub.7H CH.sub.2 C.sub.6 H.sub.5 S C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H HCH.sub.3 (CH.sub.2).sub.2 C.sub.6 H.sub.5 S 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4 H HH n-C.sub.3 H.sub.7 O C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H HC.sub.2 H.sub.5 n-C.sub.4 H.sub.9 O CH.sub.2 4-pyridyl HCH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5 O (CH.sub.2).sub.4 CH.sub.3 HC.sub.2 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub.5 S -- C.sub.6 H.sub.5 HCH.sub.3 CH.sub.3 O CH.sub.2 C.sub.6 H.sub.5 n-C.sub.6 H.sub.13CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 O (CH.sub.2).sub.6 4-FC.sub.6 H.sub.5 n-C.sub.4 H.sub.9CH.sub.3 n-C.sub.4 H.sub.9 O CH(CH.sub.3)(CH.sub.2).sub.3 H CH.sub.3CH.sub.3 CH.sub.3 O C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3 CH.sub.2 COOH__________________________________________________________________________
EXAMPLE 21
d,l-5-Hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline
A mixture of 5-phenyl-2-(R,S)-pentanol (16.4 g., 100 mmole), triethylamine (28 ml., 200 mmole) and dry tetrahydrofuran (80 ml.) under a nitrogen atmosphere is cooled in an ice/water bath. Methanesulfonyl chloride (8.5 ml., 110 mM) in dry tetrahydrofuran (20 ml.) is added dropwise at such a rate that the temperature holds essentially constant. The mixture is allowed to warm to room temperature and is then filtered to remove triethylamine hydrochloride. The filter cake is washed with dry tetrahydrofuran and the combined wash and filtrate evaporated under reduced pressure to give the product as an oil. The oil is dissolved in chloroform (100 ml.) and the solution washed with water (2×100 ml.) and then with saturated brine (1×20 ml.). Evaporation of the solvent affords 21.7 g. (89.7%) yield of the mesylate of d,l-5-phenyl-2-pentanol which is used in the next step without further purification.
A mixture of d,l-5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline (1.0 g., 5.2 mmole), potassium carbonate (14.35 g., 0.104 mole), N,N-dimethylformamide (60 ml.) and d,l-5-phenyl-2-pentanol mesylate (13.68 g., 57 mmole), under a nitrogen atmosphere, is heated to 80°-82° C. in an oil bath for 1.75 hours. The mixture is cooled to room temperature and then poured into ice/water (300 ml.). The aqueous solution is extracted with ethyl acetate (2×50 ml.) and the combined extracts washed successively with water (3×50 ml.) and saturated brine (1×50 ml.). The extract is then dried (MgSO 4 ), decolorized with charcoal and evaporated to give the product.
m/e--339 (m + ).
The above procedure is repeated but using 114.8 g. (0.594 mole) of d,l-5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline, 612 ml. of N,N-dimethylformamide, 174.8 g. (1.265 moles) of potassium carbonate and 165.5 g. (0.638 mole) of d,l-5-phenyl-2-pentanol mesylate. The reaction mixture is cooled and poured onto ice water (4 liters) and the aqueous solution extracted with ethyl acetate (2×4 liters). The combined extract is washed with water (4×2 liters), brine (1×2 liters) and dried (MgSO 4 ). Evaporation affords 196 g. of the title product. It is used without further purification.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.73 (s, 1H, OH), 7.22 (s, 5H, aromatic), 5.80 (d, J=3 H 3 , 1H, meta H), 5.58 (d, J=3 H 3 , 1H, meta H), 1.25 (d, 6H, CH 3 --CH--N and CH 3 --CH--O--), 1.41-4.81 (m, 11H, remaining protons).
EXAMPLE 22
d,l-5-Hydroxy-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline
Repetition of the procedure of Example 21 but using 5,7-dihydroxy-4-oxo-1,2,3,4-tetrahydroquinoline in place of the 5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline affords d,l-5-hydroxy-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline as an oil in 74% yield.
m/e--325 (m + ).
Analysis: Calc'd for C 20 H 23 NO 3 : C, 73.70; H, 7.12; N, 4.31%. Found: C, 73.69; H, 7.15; N, 4.08%.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.6 (bs, 1H, phenolic), 7.3 (s, 5H, aromatic), 5.8 (d, 1H, aromatic, J=2 Hz), 5.6 (d, 1H, aromatic, J=2 Hz), 4.7-4.1 (m, 2H, NH and O--CH), 3.5 (t, 2H, CH 2 , J=7 Hz), 3.1-2.1 (m, 4H, 2-CH 2 --), 2.1-1.5 (m, 4H, 2-CH 2 ), 1.3 (d, 3H, --CH--CH 3 , J=6 Hz).
Similarly, d,l-5,7-dihydroxy-2-methyl-4-oxo-1,2,3,4-tetrahydroquinoline (27 g., 0.14 mole) is alkylated with 4-phenylbutyl methanesulfonate (35.2 g., 0.154 mole) to yield 41.1 g. (90%) of the desired d,l-5-hydroxy-2-methyl-7-(4-phenylbutyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline, m.p. 88°-90° C. Recrystallization from ethyl acetate-hexane (1:2) gives the analytical sample, m.p. 90°-91° C.
Calc'd for C 20 H 23 O 3 N: C, 73.82; H, 7.12; N, 4.30%. Found: C, 73.60; H, 7.09; N, 4.26%.
m/e--325 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.58 (s, 1H, --OH), 7.21 (s, 5H, C 6 H 5 ), 5.74 (d, J=2.5 Hz, 1H, meta H), 5.5 (d, J=2.5 Hz, 1H, meta H), 4.36 (bs, 1H, NH), 3.33-4.08 (m, 3H, --O--CH 2 , --CH--N), 2.29-2.83 (m, 4H, --CH 2 --C═O, C 6 H 5 --CH 2 ), 1.51-1.92 (m, 4H, --[CH 2 ] 2 ), 1.23 (d, 3H, CH 3 --).
In like manner, alkylation of d-5,7-dihydroxy-4-oxo-1,2,3,4-tetrahydroquinoline with d-2-octylmethanesulfonate gives d-5-hydroxy-2-methyl-7-(2-(R)-octyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline, m.p. 64°-68° C.
[α] D 25 =+110.2° (c=1.0, CHCl 3 ).
and alkylation of d,l-5,7-dihydroxy-2-propyl-4-oxo-1,2,3,4-tetrahydroquinoline with d,l-5-phenyl-2-pentanol mesylate gives d,l-5-hydroxy-7-(5-phenyl-2-pentyloxy)-2-propyl-4-oxo-1,2,3,4-tetrahydroquinoline; m/e--367 (m + ).
EXAMPLE 23
The following compounds are prepared from appropriate reactants by the procedure of Example 21. The necessary alkanol reactants not previously described in the literature are prepared from appropriate aldehydes or ketones by the procedures of Preparations G and H.
__________________________________________________________________________ ##STR30##R.sub.5 R.sub.4 alk.sub.2 W__________________________________________________________________________H CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2 (CH.sub.2).sub.4 CH.sub.3H CH.sub.3 CH.sub.2 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.2 CH(CH.sub.3) CH.sub.3H H CH(CH.sub.3)(CH.sub.2).sub.2 C(CH.sub.3).sub.2 CH.sub.3H C.sub.2 H.sub.5 CH.sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5H CH.sub.3 CH.sub.2 CH.sub.2 CH(CH.sub.3) C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.7 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.5H C.sub.2 H.sub.5 (CH.sub.2).sub.9 C.sub.6 H.sub.5H H (CH.sub.2).sub.9 CH.sub.3H H CH(CH.sub.3)CH.sub.2 2-pyridylH C.sub.2 H.sub.5 (CH.sub.2).sub.2 2-pyridylH C.sub.2 H.sub.5 (CH.sub.2).sub.4 2-pyridylH H (CH.sub.2).sub.3 2-piperidylH CH.sub.3 (CH.sub.2).sub.3 4-piperidylH CH.sub.3 (CH.sub.2).sub.3 4-FC.sub.6 H.sub.4H H (CH.sub.2).sub.3 4-ClC.sub.6 H.sub.4H C.sub.2 H.sub.5 (CH.sub.2).sub.4 4-FC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.2 2-pyridylH C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 3-pyridylH CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-pyridylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylH C.sub.2 H.sub.5 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-piperidylH H CH(CH.sub.3)(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4H H CH.sub.2 C.sub.6 H.sub.5H CH.sub.3 CH.sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 -- 4-FC.sub.6 H.sub.4H C.sub.2 H.sub.5 -- 4-ClC.sub.6 H.sub.4H H -- 4-FC.sub.6 H.sub.4H CH.sub.3 -- C.sub.3 H.sub.5H H -- C.sub.3 H.sub.5H CH.sub.3 -- C.sub.4 H.sub.7H C.sub.2 H.sub.5 -- C.sub.5 H.sub.9H CH.sub.3 -- C.sub.6 H.sub.11H CH.sub.3 -- C.sub.7 H.sub.13H CH.sub.3 -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4H CH.sub.3 -- 1-(C.sub.6 H.sub.5)C.sub.4 H.sub.6H CH.sub.3 -- 2-(C.sub.6 H.sub.5)C.sub.5 H.sub.8H CH.sub.3 -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H C.sub.2 H.sub.5 -- 3-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H CH.sub.3 -- 4-pyridylH CH.sub.3 -- 4-piperidylH CH.sub.3 -- 2-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H H -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H CH.sub.3 -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.12H CH.sub.3 CH.sub.2 CH.sub.3H CH.sub.3 (CH.sub.2).sub.3 CH.sub.3H CH.sub.3 (CH.sub. 2).sub.6 CH.sub.3H CH.sub.3 (CH.sub.2).sub.9 CH.sub.3H H (CH.sub.2).sub.6 CH.sub.3H C.sub.2 H.sub.5 (CH.sub.2).sub.3 CH.sub.3H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 CH.sub.3 -- C.sub.6 H.sub.5CH.sub.3 CH.sub.3 -- 4-ClC.sub.6 H.sub.4CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 2-pyridylH CH.sub.2 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.4 HH CH.sub.2 C.sub.6 H.sub.5 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 CH.sub. 2 C.sub.6 H.sub.5 -- 4-FC.sub.6 H.sub.5H (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5H (CH.sub.2).sub.4 C.sub.6 H.sub.5 (CH.sub.2).sub.6 CH.sub.3C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5C.sub.2 H.sub.5 CH.sub.3 CH.sub.2 4-FC.sub.6 H.sub.5H i-C.sub.3 H.sub.7 CH(CH.sub.3)(CH.sub.2).sub.3 4-piperidylH n-C.sub.4 H.sub.9 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HH n-C.sub.6 H.sub.13 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 n-C.sub.6 H.sub.13 (CH.sub.2).sub.3 CH.sub.3CH.sub.3 CH.sub.3 -- C.sub.5 H.sub.9CH.sub.3 CH.sub.3 -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10__________________________________________________________________________
EXAMPLE 24
d,l-1-Formyl-5-hydroxy-3-hydroxymethylene-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline
A solution of d,l-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline (195 g., ca. 0.58 mole) in ethyl formate (1140 g., 14.6 moles) is added dropwise to sodium hydride (72 g., 3.0 moles, obtained by washing 144 g. of 50% sodium hydride with hexane, 3×500 ml.), with good stirring. After about 1.5 hours when 2/3 of the ethyl formate solution is added, the addition is discontinued to allow the vigorous foaming to subside. Diethyl ether (600 ml.) is added and the mixture stirred for 15 minutes before adding the remainder of the ethyl formate solution. When addition is complete, diethyl ether (600 ml.) is added, the reaction mixture stirred for an additional 10 minutes and then poured onto ice water (2 liters). It is acidified to pH 1 with 10% HCl and the phase separated and extracted with ethyl acetate (2×2 liters). The combined organic solutions are washed successively with water (2× 2 liters), brine (1×one liter) and dried (MgSO 4 ). Concentration gives 231 g. of red-brown oil which is used without further purification.
R f =0.1-5 (stretched) on thin layer chromatography, silica gel plates, benzene/ether (1:1).
Similarly, d,l-5-hydroxy-7-(5-phenyl-2-pentyloxy)-2-propyl-4-oxo-1,2,3,4-tetrahydroquinoline is converted to d,l-1-formyl-5-hydroxy-3-hydroxymethylene-7-(5-phenyl-2-pentyloxy)-2-propyl-4-oxo-1,2,3,4-tetrahydroquinoline. It is used in subsequent examples as is.
EXAMPLE 25
d,l-1-Formyl-5-hydroxy-3-hydroxymethylene-2-methyl-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline
To sodium hydride (18.2 g., 0.38 mol) obtained by washing 50% sodium hydride in mineral oil dispersion with pentane is added dropwise, over a half-hour period, a solution of d,l-5-hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline (11.1 g., 0.038 mole) in ethyl formate (110 g., 1.48 moles). Exothermic reaction occurs with vigorous evolution of hydrogen and formation of a yellow precipitate. The reaction mixture is cooled, ether (750 ml.) added and the resulting mixture then heated at reflux and stirred for 3 hours. It is then cooled to 0° C. and neutralized by addition of 1 N hydrochloric acid (400 ml.). The ether layer is separated and the aqueous phase extracted with ether (2×150 ml.). The ether extracts are combined, washed successively with saturated sodium bicarbonate solution (2×100 ml.) and brine (1×150 ml.) and then dried (MgSO 4 ). Concentration of the dried extract affords an orange foam (10.8 g.). An additional 2.3 g. is obtained by acidifying the sodium bicarbonate wash solutions with concentrated hydrochloric acid followed by extraction of the acid solution with ether (2×100 ml.). Concentration of the combined ethereal extracts after drying gives 2.3 g. of product (Total=13.1 g.). The product is used as is.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.27 (bs, 1H, ArOH), 8.8-11.9 (m, 1H, variable, ═COH), 8.73 (s, 1H, N--CHO), 7.41 (s, 1H, ═CH), 6.32 (s, 2H, aromatic), 5.52 (q, 1H, --CN--N), 4.18-4.77 (m, 1H, --O--CH), 0.6-2.08 (m, 17H, CH 3 --C--C 5 H 11 and CH 3 --C--N).
In like manner, d,l-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline is converted to d,l-1-formyl-5-hydroxy-3-hydroxymethylene-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline.
1 H NMR: (60 MHz) δ CDCl .sbsb.3 TMS (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.22 (bs, 1H, ArOH), 8.8-11.6 (variable, 1H, ═COH), 8.64 (s, 1H, --CHO), 7.21 (bs, shoulder at 7.30, 6H, aromatic and ═CH), 6.23 and 6.17 (two 1H doublets, J;32 2 Hz, meta), 5.42 (bq, 1H, N--CH), 4.18-4.70 (m, 1H, --OCH), 2.4-3.0 (m, 2H, Ar--CH 2 ), 1.53-2.0 (m, 4H, --(CH 2 ) 2 --), 1.29 (overlapping doublets, 6H, CH 3 --C--N and CH 3 --C--O).
d,l-5-hydroxy-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline is converted to d,l-1-formyl-5-hydroxy-3-hydroxymethylene-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline, an oil.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.1 (bs, 1H, phenolic), 8.8 (s, 1H, --N--CHO), 8.1 (s, 1H), 7.3 (s, 1H), 6.1 (s, 2H, aromatic), 4.5 (bs, 2H, --CH 2 --), 4.2-4.8 (m, --O--CH 2 --), 2.0-0.7 (remaining protons).
d,l-5-hydroxy-7-(5-pentyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline is converted to d,l-1-formyl-5-hydroxy-3-hydroxymethylene-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.4 (bs, 1H, phenolic), 8.5 (s, 1H, CHO), 7.2 (m, 6H, aromatic and ═CH--), 6.2 (m, 2H, aromatic), 4.5 (s, 2H, --CH 2 --), 4.4 (m, 1H, --CH--CH 3 ), 2.6 (bt, 2H, --CH 2 --), 1.7 (m, 5H, remaining protons), 1.3 (d, 3H, --CH--CH 3 , J=6Hz).
and d,l-5-hydroxy-2-methyl-7-(4-phenylbutyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline is converted to d,l-1-formyl-5-hydroxy-3-hydroxymethylene-2-methyl-7-(4-phenylbutyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline, m.p. 132°-135° C. (from hexane). Recrystallization from hot methanol provides the analytical sample, m.p. 131°-132° C.
Calc'd for C 22 H 23 O 5 N: C, 69.27; H, 6.08; N, 3.67%. Found: C, 69.25; H, 5.88; N, 3.88%.
m/e--381 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): ##STR31## 12.26 (s, 1H, 5--OH), 8.62 (s, 1H, --C(═O)--H), ##STR32## 7.27 (s, 5H, C 6 H 5 ), 6.26 (bs, 2H, meta H's) 5.46 (q, 1H, CH--N), 3.82-4.23 (m, 3H, --CH 2 --O), 2.49-2.80 (m, 3H, ArCH 2 ), 1.67-2.02 (m, 4H, --[CH 2 ] 2 --), 1.27 (d, 3H, CH 3 ).
EXAMPLE 26
dl-1-Formyl-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline
To a solution of dl-1-formyl-3-hydroxymethylene-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline (229 g., ca. 0.58 mole) in methanol (880 ml.) under a nitrogen atmosphere is added triethylamine (27.2 ml.) with stirring. Methyl vinyl ketone (97.0 ml.) is then added and the mixture stirred overnight at room temperature.
The reaction is complete at this point and comprises a mixture of the title compound and dl-1,3-diformyl-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline. The following steps are required to convert the diformyl compound to the desired title compound.
The reaction mixture is diluted with ether (6 liters) and then washed successively with 10% aqueous sodium carbonate (4×1700 ml.), brine (1×2 liters) and then dried (MgSO 4 ). Concentration of the solution affords 238 g. of a red-brown oil. The oil is dissolved in methanol (1920 ml.) and the solution cooled to 0° C. Potassium carbonate (21.2 g.) is added, the mixture stirred for 3 hours at 0° C. and then treated with acetic acid (18.7 g.) The methanol is removed under reduced pressure and the resultant oil stirred with water (2 liters) and ethyl acetate (2 liters) for 10 minutes. The aqueous phase is separated, extracted with ethyl acetate (1×2 liters) and the combined ethyl acetate solutions washed with water (2×2 liters), brine (1×2 liters) and dried (MgSO 4 ). Concentration under reduced pressure and chromatography of the concentrate on silica gel (1.8 kg.) gives 159 g. of the title product.
m/e--437 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 1.72 (s, 1H, OH), 8.78 (bs, 1H, --CHO), 7.22 (s, 5H, aromatic), 6.22 (bs, 2H, meta H's), 2.12, 2.07 (s, 3H, --CH 3 --CO--), 1.31 (d, 3H, --CH 3 --C--O--), and 1.57-5.23 (m, 13H, remaining protons).
Similar treatment of 35 g. (0.09 mole) of dl-1-formyl-5-hydroxy-3-hydroxymethylene-2-methyl-7-(4-phenylbutyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline gives 22.7 g. (60%) of dl-1-formyl-5-hydroxy-2-methyl-7-(4-phenylbutyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline, m.p. 101°-103° C. The analytical sample is obtained by recrystallization from methanol, m.p. 104°-105° C.
Calc'd for C 25 H 29 O 5 N: C, 70.90; H, 6.90; N, 3.31%. Found: C, 70.77; H, 6.81; N, 3.46%.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 12.88 (s, 1H, --OH), 9.08 (bs, 1H, --CHO), 7.29 (s, 5H, C 6 H 5 ), 6.25 (bs, 2H, meta H's), 4.88-5.43 (m, 1H, --CHN), 3.86-4.21 (m, 2H, --CH 2 --O--), ca. 2.49-3.02 [m, 7H, ArCH 2 , --(CH 2 ) 2 --C(═O)--, --CH--C(═O)], 2.18 [s, 3H, CH 3 --C(═O)], 1.68-2.03 [m, 4H, --(CH 2 ) 2 --], 1.13 (d, 3H, CH 3 ).
m/e--423 (m + );
and d,l-1-formyl-5-hydroxy-3-hydroxymethylene-7-(5-phenyl-2-pentyloxy)-2-propyl-4-oxo-1,2,3,4-tetrahydroquinoline affords d,l-1-formyl-5-hydroxy-7-(5-phenyl-2-pentyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline which is used as is.
EXAMPLE 27
d,l-1-Formyl-5-hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline and d,l-1,3-Diformyl-5-hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline
To a solution of d,l-5-hydroxy-3-hydroxymethylene-2-methyl-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline (13.1 g., 37.7 mmol.), in methanol (56 ml.) and methyl vinyl ketone (5.52 mg., 68 mmol.) is added triethylamine (1.3 ml., 9.3 mmol.). The mixture is stirred for 18 hours under a nitrogen atmosphere at room temperature and is then diluted with ether (550 ml.). The solution is washed with 10% aqueous sodium bicarbonate solution (4×60 ml.), followed by brine (1×100 ml.) and dried (MgSO 4 ). Removal of the ether by evaporation gives a dark oil (16 g.). The oil is dissolved in a minimum volume of benzene and the solution charged to a column of silica gel (500 g.). The column is then eluted with a volume of benzene equal to the volume of the column. The eluting solvent is then changed to 15% ether-benzene and 100 ml. fractions collected when the first color band begins to elute off the column. Fractions 5- 13 are combined and concentrated under reduced pressure to give d,l-1,3-diformyl-5-hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline as a yellow oil (8.7 g.).
The column is eluted further with 15% ether-benzene. Fractions 19-37 are combined and concentrated under reduced pressure to give d,l-1-formyl-5-hydroxy-2-methyl-7-(2-heptyloxy)-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline as an oil (4.6 g.). Additional monoformyl product is obtained in the following manner:
1 g. of diformyl product is stirred with 200 mg. potassium carbonate in methanol (25 ml.) for two hours at 0° C. The solvent is then evaporated in vacuo and the residue suspended in ether and filtered. The filtrate is concentrated and the residue partitioned between ether and water. The organic layer is separated, the aqueous phase acidified with 10% hydrochloric acid and extracted with ether. The combined ether extracts are washed successively with saturated sodium bicarbonate and brine, and then dried (MgSO 4 ), filtered and concentrated to yield additional monoformyl product.
The monoformyl derivative has the following NMR spectrum:
1 H NMR (60 MH 2 ) δ CDCl .sbsb.3 TMS (ppm): 12.73 (S, 1H, ArOH), 8.87 (S, 1H, N--CHO), 6.12 (S, 2H, Aromatic), 4.78-5.50 (M, 1H, N--CH), 4.11-4.72 (M, 1H, --O--CH), 2.21 (S, 3H, CH 3 --C(═O)--), 0.63-3.12 (M, 22H, remaining hydrogens).
Similarly, the following compounds are prepared from appropriate reactants:
d,l-1-formyl-5-hydroxy-7-(2-heptyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline, an oil.
1 H NMR (60 MH 2 ) δ CDCl .sbsb.3 TMS (ppm): 12.8 (S, 1H, phenolic), 8.7 (S, 1H, N--CHO), 6.1 (S, 2H, aromatic), 4.1-4.6 (m, 1H, --O--CH), 4.1 (d, 2H, J=5H 2 , --CH 2 --), 2.3-3.0 (m, 3H, CH 2 and CH--C(═O)), 2.2 (S, 3H, --C(═O)--CH 3 ), 2.3-0.7 (remaining protons).
d,l-1-formyl-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline.
1 H NMR (60 MH 2 ) δ CDCl .sbsb.3 TMS (ppm): 12.68 (S, 1H, --OH), 8.82 (b, s, 1H, --C(O)H), 7.20 (b, s, 5H, C 6 H 5 ), 6.18 (b, s, 2H, aromatic), 4.78-5.34 (m, 1H, --N--CH), 4.18-4.68 (m, 1H, --O--CH), 2.17 (S, 3H, --C(O)CH 3 ), 1.30 (d, 3H, --O--C--CH 3 ), 1.12 (d, 3H, --N--C--CH 3 ), 1.4-3.1 (m, 11H, remaining H's).
d,l-1-formyl-5-hydroxy-7-(5-phenyl-2-pentyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline.
m/e--423 (m + ).
Also produced as by-product in each of these preparations is the corresponding 1,3-diformyl derivative.
EXAMPLE 28
Following the procedures of Examples 25 and 27, the 5-hydroxy-2-R 4 -7-(Z-W)-4-oxo-1,2,3,4-tetrahydroquinolines of Examples 18, 20 and 23 are converted to compounds having the formula below wherein R 4 , R 5 , Z and W are as defined in Examples 18, 20 and 23. When R 6 of the tetrahydroquinoline reactants is hydrogen, it is converted to formyl (CHO). ##STR33##
EXAMPLE 29
d,l-5,6,6a,7-Tetrahydro-1-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one
A solution of d,l-1-formyl-5-hydroxy-2- methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline (174 g., 0.398 mole) in methanolic 2 N KOH (5.9 liters) and methanol (5.9 liters) is stirred and heated at reflux overnight under a nitrogen atmosphere. To the cooled solution is added acetic acid (708 g.) dropwise with stirring over a 15 minute period. The resulting solution is concentrated by rotary evaporation (in vacuo, water aspirator) to a semisolid which is filtered and washed first with water to remove potassium acetate and then with ethyl acetate until all the black tar is removed. Yield=68 g. (44%) yellow solids, m.p. 188°-190° C. Recrystallization from hot ethyl acetate affords the pure product, m.p. 194°-195° C.
m/e--391 (m + )
Analysis: Calc'd for C 25 H 29 O 3 N: C, 76.09; H, 7.47; N, 3.58%. Found: C, 76.43; H, 7.48; N, 3.58%.
1 H NMR (60 MHz) δ TMS (100 mg. dissolved in 0.3 ml. CD 3 OD and 0.3 ml. CD 3 S(O)CD 3 ) (ppm): 7.21 (s, 5H, aromatic), 5.80 (s, 2H, meta H's), 1.20 (d, 6H, CH 3 --CHO and CH 3 --CH--N).
From the mother liquors, a small amount of the corresponding axial methyl derivative is obtained upon evaporation. It is purified by column chromatography on silica gel using benzene/ether (1:1) as eluant. Evaporation of the eluate and recrystallization of the residue from ether/hexane (1:1) affords analytically pure material, m.p. 225°-228° C.
Its R f value upon thin layer chromatography on silica gel using 2.5% methanol in ether as eluant and visualization with fast blue is 0.34. The 6β-methyl derivative exhibits R f =0.41.
m/e--391 (m + ).
1 H NMR (60 MHz) δ TMS (100 mg. dissolved in 0.3 ml. CD 3 OD and 0.3 ml. CD 3 S(O)CD 3 ) (ppm): 7.19 (s, 5H, aromatic), 5.75 (s, 2H, meta H's), 1.21 (d, 3H, CH 3 --CHO--), and 0.95 (d, 3H, CH 3 --CH--N).
Similar treatment of 22 g. of d,l-1-formyl-5-hydroxy-2-methyl-7-(4-phenylbutyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinolines gives 17.1 g. (87%) of d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinolin-9(8H)-one, m.p. 222°-224° C. The analytical sample is obtained by recrystallization from methanol, m.p. 224°-225° C.
Calc'd for C 24 H 27 O 3 N: C, 76.36; H, 7.21; N, 3.71%. Found: C, 76.03; H, 7.08; N, 3.68%.
1 H NMR (60 MHz) [1:1 mixture of (CD 3 ) 2 SO and DC 3 OD]: 1.24 (d, 3H, 6β-CH 3 ).
m/e--377 (m + ).
Evaporation of the mother liquor gives 2.8 g. (m.p. 185°-195° C.) of product shown by NMR to be a mixture of the 6β-methyl derivative (ca. 40%) and d,l-5,6,6a,7-tetrahydro-1-hydroxy-6α-methyl-3-(4-phenyl butyloxy)-benzo[c]quinoline-9(8H)-one.
1 H NMR (60 MHz) [1:1 mixture of (CD 3 ) 2 SO and CD 3 OD): 1.24 (d, 1.2H, 6β-CH 3 ] and 0.95 (d, 1.8H, 6α-CH 3 ).
EXAMPLE 30
d,l-5,6,6a,7-Tetrahydro-1-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one
A solution of d,l-1-formyl-5-hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-3-(3-oxobutyl)-1,2,3,4-tetrahydroquinoline (4.5 g., 11.5 mmol.) in methanol (150 ml.) is treated with 2 N methanolic potassium hydroxide solution (150 ml.). The mixture is stirred for one hour at room temperature and then heated at reflux under a nitrogen atmosphere for 20 hours. The dark red mixture is allowed to cool to room temperature, neutralized with acetic acid and concentrated under pressure to about 100 ml. The concentrate is diluted with water (400 ml.) and the brown-red solid separated by filtration, washed with water and dried (6 g.). It is triturated first in ether and then in methanol, filtered and dried (1.96 g.); m.p. 223°-229° C. Recrystallization from hot methanol affords crystals melting at 235°-237° C.
Analysis: Calc'd for C 21 H 29 O 3 N: C, 73.43; H, 8.51; N, 4.08%. Found: C, 73.22; H, 8.30; N, 4.11%.
Additional material is recovered by evaporation of all mother liquors and by chloroform extraction of the aqueous solution from which the brown-red crude product is obtained and subsequent evaporation of the extract. The combined residues are purified by silica gel chromatography using ether as eluant.
In like manner, the following compounds are prepared from appropriate reactants:
__________________________________________________________________________ ##STR34## mle (°C.) Calc'd FoundZW R.sub.4 R.sub.5 R.sub.6 (m.sup.+) m.p. Formula C, H, N C, H, N__________________________________________________________________________ C-77.00 C-76.86OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5 H H 405 155-6 C.sub.26 H.sub.31 O.sub.3 N H-7.71 H-7.62 N-3.45 N-3.45 C-78.05 C-78.16OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.13 H H 461 139-141 C.sub.30 H.sub.39 O.sub.3 N H-8.52 H-8.53 N-3.03 N-3.09 C-77.81 C-77.73OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.5 H.sub.11 H H 447 150-3 C.sub.29 H.sub.37 O.sub.3 N H-8.33 H-8.19 N-3.18 N-3.13 C-77.56 C-77.28OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.4 H.sub.9 H H 433 160-2 C.sub.28 H.sub.35 O.sub.3 N H-8.14 H-7.92 N-3.23 N-3.18 C-77.56 C-77.86OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 H C.sub.4 H.sub.9 H 433 95-98 C.sub.28 H.sub.35 O.sub.3 N H-8.14 H-8.37 N-3.23 N-3.17 C-79.80 C-79.64OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 (CH.sub.2).sub.2C.sub.6 H.sub.5 H H 481 200-201 C.sub.32 H.sub.35 O.sub.3 N H-7.33 H-7.34 N-2.91 N-2.93 C-77.70 C-77.94C(CH.sub. 3).sub.2C.sub.6 H.sub.3 CH.sub.3 H H 355 261-2 C.sub.23 H.sub.33 O.sub.2 N H-9.36 H-9.21 N-3.94 N-3.99 C-75.62 C-75.26O(CH.sub.2).sub.2 C.sub.6 H.sub.5 CH.sub.3 H H 349 248-250 C.sub.22 H.sub.23 O.sub.3 N H-6.63 H-6.66 N-4.01 N-3.93 C-76.36 C-76.38OCH(CH.sub.3)(CH.sub.).sub.3 C.sub.6 H.sub.5 H H H 377 170-173 C.sub.24 H.sub.27 O.sub.3 N H-7.21 H-7.21 N-3.71 N-3.85 C-72.92 C-72.92OCH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3 H H H 329 208-209 C.sub.20 H.sub.27 O.sub.3 N H-8.26 H-8.31 N-4.25 N-4.42 C-77.29 C-76.97OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 n-C.sub.3 H.sub.7 H H -- 164-166 C.sub.27 H.sub.33 O.sub.3 N H-7.93 H-7.98 N-3.34 N-3.41 C-76.69 C-76.32OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(a) CH.sub.3 H H 391 176-178 C.sub.25 H.sub.29 O.sub.3 N H-7.47 H-7.36 N-3.58 N-3.33 C-76.69 C-76.40OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5.sup.(b) CH.sub.3 H H 391 172-174 C.sub.25 H.sub.29 O.sub.3 N H-7.47 H-7.39 N-3.58 N-3.51__________________________________________________________________________ .sup.(a) l-enantiomer; [α].sub.D.sup.25 = -416.0° (C = 0.33, CH.sub.3 OH) .sup.(b) d-enantiomer; [α].sub.D.sup.25 = +412.9° (C = 1.0, CH.sub.3 OH)
EXAMPLE 31
The compounds of Example 28 are reacted according to the procedure of Example 30, to produce compounds having the formula shown below wherein R 4 , R 5 , R 6 , Z and W are as defined in Example 28. ##STR35##
EXAMPLE 32
d,l-5,6,6a,7,10,10a-Hexahydro-1-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one
A suspension of d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one (1.0 g., 2.91 mmole) in tetrahydrofuran (20 ml.) is added dropwise via an addition funnel to a rapidly stirred solution of lithium (0.1 g.) in liquid ammonia (75 ml., distilled through potassium hydroxide pellets). The addition funnel is rinsed with tetrahydrofuran (10 ml.). The mixture is stirred for 10 minutes and then solid ammonium chloride is added to discharge the blue color. The excess ammonia is allowed to evaporate and the residue taken up in water (100 ml.) and ethyl acetate (50 ml.). The ethyl acetate layer is separated and the aqueous phase extracted with ethyl acetate (2×50 ml.). The combined extracts are washed with brine, dried (MgSO 4 ) and concentrated under reduced pressure to a brown semisolid product (1.35 g.). Trituration of the semi-solid in pentane/ether (1:1) gives a light brown solid (0.884 g.); m.p. 130°-138° C.
The above procedure is repeated but using 1.84 g. (5.36 mmole) of the benzo[c]quinolin-9-one reactant, 0.184 g. of lithium, 140 ml. of liquid ammonia and 45 ml. of tetrahydrofuran. The residue (2.1 g.) remaining after evaporation of the ammonia is dissolved in benzene and charged to a chromatography column (3.8×61 cm) containing silica gel (250 g.). The column is eluted with a volume of degassed benzene equal to the volume of the column and then with 1700 ml. of degassed benzene-ether (9:1). Continued elution (1100 ml.) gives a brilliant red eluate which is concentrated to a light purple solid (580 mg.) under reduced pressure and triturated in benzene-ether (1:1) to give 370 mg. of solid; m.p. 154°-156° C. It is stored under nitrogen and in the dark. The isolated solids are mixtures of the cis- and transforms of the title product.
m/e--345 (m + ).
1 H NMR (100 MHz) δ CDCl .sbsb.3 TMS (ppm): 6.85 and 7.49 (1H, broad variable, OH), 5.67, 5.71, 5.85, 5.93 (d, J=2 Hz, 2H total, aromatic hydrogens for cis/trans mixture), 0.90 (t, 3H, terminal CH 3 ), 1.12-4.43 (m, remaining H).
EXAMPLE 33
Following the procedure of Example 32, the compounds of Example 30 and 31 are converted to products having the formula ##STR36## wherein R 4 , R 5 , R 6 , Z and W are as defined in Examples 30 and 31. Both cis- and trans-forms are produced.
EXAMPLE 34
Isomeric 5,6,6a,7,10,10a-Hexahydro-1-acetoxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-ones
Pyridine (2.2 ml.) is added to a suspension of 5,6,6a,7,10,10a-hexahydro-1-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one (222 mg., 0.642 mmole) in acetic anhydride (2.2 ml.) under a nitrogen atmosphere. The mixture is stirred for 1.5 hours at room temperature and is then poured onto ice (50 ml.). The gum which separates is extracted with ether (3×50 ml.) and the combined extracts washed first with water (4×50 ml.) and then with brine (1×60 ml.). The extract is dried (MgSO 4 ) and evaporated under reduced pressure to a red oil (250 mg.).
The oil is dissolved in a minimum of hot ether and charged to a silica gel (45 g.) column, packed and eluted with pentane-ether (3:1). The column is eluted with pentane-ether (3:1, 200 ml.). Elution is continued and fractions (10 ml.) collected. Fractions 22-32 are combined and concentrated to a foam (113.5 mg.) which is crystallized from petroleum ether as white crystals; m.p. 112°-114° C.
Fractions 33-50 are combined and concentrated to a foam (89.7 mg.) which is recrystallized from petroleum ether as white crystals; m.p. 78°-82° C.
The products are the isomeric mono-acetylated compounds.
By means of this procedure the products of Example 33 are converted to their isomeric 1-acetoxy derivatives. Compounds having the formula below are thus prepared. ##STR37## wherein R 4 , R 5 , R 6 , Z and W are as defined in Example 33.
Substitution of acetic anhydride by benzoic anhydride, propionic anhydride, butyric anhydride or valeric anhydride in this procedure affords the corresponding isomeric 1-benzoyloxy, 1-propionyloxy, 1-butyryloxy and 1-valeryloxy derivatives.
EXAMPLE 35
dl-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-acetyl-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline-9(8H)-one
3.49 g. (0.008 mole) of dl-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one is dissolved in 20 ml. (alcohol-free) chloroform, the solution is cooled in an ice-water-bath then added 14 ml. pyridine (dried over potassium hydroxide pellets) followed by 0.95 ml. (0.013 mole) of acetyl chloride which is dissolved in 5 ml. chloroform. The homogeneous solution is then stirred at ambient temperature for 18 hours. The reaction mixture is poured onto 50 ml. ice-water and extracted twice with chloroform (25 ml. each). The combined organic layers are washed with 25 ml. sat. sodium bicarbonate, 25 ml. water, 25 ml. brine, dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. Purification is achieved via chromatography (200 g. Brinkman silica gel, solvent: cyclohexane 3, ether 1) to afford 2.20 g. (83.8% yield) of the above title compound.
Analysis: Calc'd for C 29 H 35 O 5 N: C, 72.90; H, 7.39; N, 2.80%. Found: C, 72.69; H, 7.48; N, 2.49%.
I.R. (KBr): 2.90μ (m), 3.38μ (s), 3.48μ (s), 5.62μ (s), 5.78μ (s), 6.00μ (s), 6.15μ (s), 6.30μ (s).
m/e--477 (m + ). 1 HNMR (60 MHz) δ CDCl .sbsb.3 TMS : 7.20 (m, 5H, arom.), 6.53 (d, 1H, C -2 ), 6.39 (d, 1H, C -4 ), 4.71-4.08 (m, 2H, methines), 2.29 (s, 3H, acetate Me), 2.02 & 2.04 (2s, 3H, amide Me), 1.25 & 1.23 (2d, 3H, C -6 Me), 1.12 (d, 3H, side chain Me), 3.20-1.36 (variable remaining protons).
In like manner, dl-cis-5,6,6aβ,7,10aβ-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one is converted to dl-cis-5,6,6aβ,7,10aβ-hexahydro-1-acetoxy-5-acetyl-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one.
m.p. 125°-128° C., yield 82%.
Analysis: Calc'd for C 29 H 35 O 5 N: C, 72.90; H, 7.39; N, 2.80%. Found: C, 72.80; H, 7.35; N, 2.70%.
1 HNMR (60 MHz) δ CDCl .sbsb.3 TMS : 7.22 (m, 5H, arom.), 6.55 (2d, 2H, C 2 & C 4 ), 5.02-4.62 (m, 1H, C -6 methine), 4.52-4.12 (m, 1H, side chain methine), 2.28 (s, 3H, acetate Me), 2.11 & 2.13 (3H, amide Me), 1.26 & 1.28 (3H, C -6 Me), 1.22 (d, 3H, side chain Me), 3.42-1.65 (variable remaining protons).
I.R. (KBr): 2.95μ (w), 3.43μ (s), 5.65μ (s), 5.81μ (s), 6.02μ (s), 6.16μ (s), 6.32μ (s), 6.70μ (s).
m/e--477 (m + ).
EXAMPLE 36
d,l-5,6,6aβ,7,10,10aα-Hexahydro-1-acetoxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one
The procedure of Example 32 is repeated but using double the quantities of reactants. The product (2.22 g.) is then directly acetylated according to the procedure of Example 34 to give 2.35 g. of acetylated product. This product is triturated in pentane-ether (3:1) to a tan solid (905 mg.) which when recrystallized from ethanol gives 404 mg. of light tan crystals; m.p. 112°-113.5° C.
The mother liquors from which each of the above solids is separated are combined and concentrated. The residue is dissolved in a minimum of benzene-ether-methylene chloride (1:1:1) and charged to a silica gel (275 g.) column (packed and eluted with petroleum ether-ether [3:1]). The column is eluted first with 2 liters of petroleum ether-ether (3:1) followed by 1.5 liters of petroleum ether-ether (2:1) and 2 liters of petroleum ether-ether (1:1). Fractions 2-11 (50 ml. each) of eluate from the 1:1 solvent system are collected and concentrated under reduced pressure to a foam (496 mg.). Crystallization from petroleum ether affords white crystals; m.p. 100°-113° C. (410 mg.). Recrystallization from ethanol-water (1:1) gives d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one melting at 111°-112° C.
m/e--387 (m + ).
Analysis: Calc'd for C 23 H 33 O 4 N: C, 71.29; H, 8.58; N, 3.61%. Found: C, 70.95; H, 8.64; N, 3.58%.
Fractions 12-18 and 19-27 (50 ml. each) are collected and concentrated to afford 273 mg. and 208 mg., respectively, of acetylated product. Crystallization of the residue from fractions 19-27 from petroleum ether gives white crystals (119 mg.); m.p. 84°-88° C. Recrystallization from ethyl acetate-hexane (1:10) gives d,l-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-3-(2-heptyloxy)-6.beta.-methyl-benzo[c]quinolin-9(8H)-one, m.p. 84°-86° C.
Analysis: Calc'd for C 23 H 33 O 4 N: C, 71.29; H, 8.58; N, 3.61%. Found: C, 71.05; H, 8.48; N, 3.56%.
Similarly, the following compounds are prepared from appropriate reactants:
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one, m.p. 80°-82° C.
m/e--435 (m + ).
Analysis: Calc'd for C 27 H 33 O 4 N: C, 74.45; H, 7.64; N, 3.22%. Found: C, 74.43; H, 7.73; N, 3.28%.
d,l-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one, m.p. 172°-176° C. as the hydrochloride salt from acetone-ether (1:1).
Analysis: Calc'd for C 27 H 33 O 4 N.HCl: C, 68.71; H, 7.26; N, 2.97%. Found: C, 68.86; H, 7.16; N, 2.97%.
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)-6β-propylbenzo[c]quinolin-9(8H)-one; m.p. 79°-80° C.
m/e--463 (m + ).
d,l-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)-6β-propylbenzo[c]quinolin-9(8H)-one; m.p. 144°-146° C., as the HCl salt.
m/e--463 (m + ).
d-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)-6β-methylbenzo[c]quinolin-9(8H)-one; m.p. 90°-94° C. (dec.) as the hydrochloride salt.
[α] D 25 =+22.8° (c=0.31, CH 3 OH).
m/e--435 (m + ).
Analysis: Calc'd for C 27 H 33 O 4 N.HCl: C, 68.71; H, 7.26; N, 2.97%. Found: C, 69.24; H, 7.30; N, 3.01%.
d-trans-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)-6β-methylbenzo[c]quinolin-9(8H)-one; m.p. 90°-95° C. (dec.) as the hydrochloride salt.
[α] D 25 =+78.46° (c=0.13, CH 3 OH).
m/e--435 (m + ).
Analysis: Calc'd for C 27 H 33 O 4 N.HCl: C, 68.71; H, 7.26; N, 2.97%. Found: C, 70.20; H, 7.23; N, 3.07%.
1-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)-6β-methylbenzo[c]quinolin-9(8H)-one; m.p. 90°-92° C. as the hydrochloride.
[α] D 25 =-20.5° (c=0.19, CH 3 OH).
m/e--435 (m + ).
Analysis: Calc'd for C 27 H 33 O 4 N.HCl: C, 68.71; H, 7.26; N, 2.97%. Found: C, 68.92; H, 7.23; N, 3.09%.
l-trans-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)-6β-methylbenzo[c]quinolin-9(8H)-one; m.p. 92°-96° C. as the hydrochloride.
[α] D 25 =-79.0° (c=0.10, CH 3 OH)
m/e--435 (m + ).
Analysis: Calc'd for C 27 H 33 O 4 N.HCl: C, 68.71; H, 7.26; N, 2.97%. Found: C, 68.67; H, 7.23; N, 3.02%.
EXAMPLE 37
d,l-5,6,6a,7,10,10a-Hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one, trans- and cis- isomers
Ammonia (1150 ml.) is condensed directly into a flame-dried 3 liter/3 neck flask (under a nitrogen atmosphere) equipped with mechanical stirrer, a 500 ml. dropping funnel and solid CO 2 /acetone cooling (˜-75° C.). Lithium wire (2.2 g., cut into 1/4" pieces) is added and a characteristic blue color forms immediately. To the stirred blue solution at -78° C. is added d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (21.5 g., 0.055 mole) dissolved in tetrahydrofuran (250 ml.) dropwise over a 10 minute period. After an additional 5 minutes of stirring at -78° C., the reaction mixture is quenched by the addition of dry ammonium chloride (20 g.). The cooling is then discontinued and the reaction mixture warmed slowly on a steam bath to evaporate the ammonia. When almost dry, ethyl acetate (2 liters) and water (1 liter) are added and the mixture stirred for 10 minutes. The layers are then separated and the aqueous phase is extracted once more with ethyl acetate (500 ml.). The combined organic extracts are washed once with water (1 liter), dried (MgSO 4 ) and concentrated to a brown semi-solid (˜28 g.). This residue is immediately dissolved in methylene chloride (200 ml.), 4-dimethylaminopyridine (7.5 g., 0.061 mole) and triethylamine (6.1 g., 0.061 mole) added and the stirred solution cooled to 0° C. (ice/water cooling) under a nitrogen atmosphere. Acetic anhydride (6.1 g., 0.061 mole) is then added dropwise over 5 minutes with good stirring. After an additional 30 minutes of stirring at 0° C., the reaction mixture is diluted with ethyl acetate (2 liters) and water (1 liter) and stirred for 10 minutes. The aqueous is extracted once more with water and the combined organics washed successively with water (4×1 liter), saturated sodium bicarbonate (1×1 liter), brine (1×1 liter), dried (MgSO 4 ) and concentrated to a light brown oil (˜27 g.). The residue is chromatographed on 1.8 kg. of silica gel using benzene 15/ethyl acetate as the eluting solvent. One liter fractions are collected.
After elution of less polar impurities, fractions 16-20 are combined and evaporated to a residue which is crystallized from ether/petroleum ether to yield 5.6 g. (23.4%) of the trans-isomer of the title product. Fractions 21-27 are combined to give 7.6 g. (31.8%) of a mixture of the trans- and cis-isomers, and fractions 28-32 are combined to give 2.5 g. (10.4%) of the cis-isomer of the title product.
The trans-isomer exhibits the following characteristics:
m/e--435 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.24 (s, 5H, aromatic), 5.97 (s, 2H, meta H's), 2.28 (s, 3H, CH 3 --COO), 1.23 (d, 3H, CH 3 --CH--O--), 1.20 (d, 3H, CH 3 --CH--N), 1.3-4.5 (m, 17H, remaining protons).
M.P.--81°-83° C.
Analysis: Calc'd for C 27 H 33 O 4 N: C, 74.45; H, 7.64; N, 3.22%. Found: C, 74.15; H, 7.68; N, 3.18%.
The cis-isomer has the following characteristics:
m/e--435 (m + ).
M.P. of HCl salt--172°-176° C. (dec.) (from acetone-ether).
Analysis: Calc'd for C 27 H 33 O 4 N.HCl: C, 68.71; H, 7.26; N, 2.97%. Found: C, 68.86; H, 7.16; N, 2.97%.
EXAMPLE 38
d,l-5,6,6a,7,10,10a-Hexahydro-1-acetoxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinolin-9(8H)-one, trans- and cis-isomers
Following the procedure of Example 36, d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinolin-9(8H)-one is first reduced with lithium and ammonia and then acylated to yield the desired hexahydro isomers. Separation by column chromatography on silica gel using ether as eluant provides first d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinolin-9(8H)-one, m.p. 155°-156° C. after recrystallization from ethyl acetate/pentane (1:5).
Analysis: Calc'd for C 26 H 31 O 4 N: C, 74.08; H, 7.41; N, 3.32%. Found: C, 74.00; H, 7.47; N, 3.22%.
m/e--421 (m + ).
Further purification of later fractions by additional column chromatography on silica gel using cyclohexane-ether (1:1) as eluant yields the isomeric d,l-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinolin-9(8H)-one, m.p. 95°-96° C. after recrystallization from ethyl acetate/hexane (1:5).
m/e--421 (m + ).
Analysis: Calc'd for C 26 H 31 O 4 N: C, 74.08; H, 7.41; N, 3.32%. Found: C, 73.95; H, 7.51; N, 3.31%.
EXAMPLE 39
d,l-5,6,6aβ,7,10,10a-hexahydro-1-acetoxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one
A solution of d,l-5,6,6a,7-tetrahydro-1-hydroxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one (9.0 g.) in tetrahydrofuran (100 ml.) is added dropwise to a rapidly stirring solution of lithium (0.1 g.) in liquid ammonia (750 ml.). An additional 0.1 g. of lithium is added portionwise during the addition to insure a blue color. The mixture is stirred for 10 minutes and then the blue color discharged by addition of excess ammonium chloride. The excess ammonia is allowed to evaporate and the residue is taken up in a mixture of water and ethyl acetate. The organic layer is separated and the aqueous phase extracted twice more with ethyl acetate. The combined extracts are washed with water, brine, dried (MgSO 4 ) and evaporated to give 8.45 g. of crude product as a brown solid.
The crude product (8.0 g.) is suspended in methylene chloride (48 ml.) at 0° C. and treated with N,N-dimethyl-4-aminopyridine (3.24 g.) and triethylamine (3.72 ml.). Acetic anhydride (2.52 ml.) is then added to the mixture which is then stirred for 30 minutes at 0° C. It is diluted with methylene chloride (300 ml.) and the methylene chloride layer separated, washed with water (3×150 ml.), saturated sodium bicarbonate (1×100 ml.), brine (1×100 ml.), and dried (MgSO 4 ). Evaporation of the methylene chloride gives 13.7 g. of dark oil which is chromatographed on a silica gel (450 g.) column. The column is eluted sequentially with ether-hexane (1:1), ether-hexane (2:1) and ether. Fractions of 18 ml. each are collected. Fractions 176-224 are combined and concentrated to an oil which is crystallized from hexane to give 3.24 g. (32%) yield of the trans-isomer of the title compound as light yellow crystals; m.p. 65.5° -68° C.
m/e--373 (m + ).
IR (KBr): 5.82 (ketone C═O), 5.75 (ester C═O), 295 (NH) μ.
Fractions 246-290 are combined and concentrated to give 0.55 g. (5%) of crude cis-isomer of the title compound as an oil. It is purified further by column chromatography as described above to give the pure cis-isomer as an oil.
m/e--373 (m + ).
IR (CHCl 3 ): 5.82 (ketone C═O), 5.67 (ester C═O), 2.92 (NH) μ.
Analysis: Calc'd for C 22 H 31 O 4 N: C, 70.75; H, 8.37; N, 3.75%. Found: C, 70.90; H, 8.54; N, 3.79%.
Fractions 225-245 are combined and evaporated to give 2.69 g. (26%) of a mixture of cis- and trans-isomers which are separated by the procedure described above.
The following compounds are similarly prepared from d,l-5,6,6a,7-tetrahydro-1-hydroxy-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one;
__________________________________________________________________________ ##STR38## (°C.) m/e Calc'd FoundZW R.sub.4 R.sub.5 R.sub.9 m.p. (m.sup.+) Formula C, H, N C, H, N__________________________________________________________________________ C-69.18 C-68.89OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5 H H 125-130 449 C.sub.28 H.sub.35 O.sub.4 N . H-7.47 H-7.45 N-2.88 N-2.90 C-69.18 C-69.18OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5 H H 153-155 449 C.sub.28 H.sub.35 O.sub.4 N . H-7.47 H-7.32 N-2.88 N-2.93 C-76.00 C-75.88OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.13 H H 103-104 505 C.sub.32 H.sub.43 O.sub.4 N H-8.57 H-8.47 N-2.77 N-2.84 C-76.00 C-75.62OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.13 H H 100-101 505 C.sub.32 H.sub.43 O.sub.4 N H-8.57 H-8.39 N-2.77 N-2.63 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 ##STR39## H H 100-105 525 C.sub.34 H.sub.39 O.sub.4 N C-77.68 H-7.48 N-2.66 C-77.54 H-7.40 N-2.65 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 ##STR40## H H 118-119 525 C.sub.34 H.sub.39 O.sub.4 N C-77.68 H-7.48 N-2.66 C-77.62 H-7.61 N-2.64 C-75.73 C-75.82OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.5 H.sub.11 H H 99-100 491 C.sub.31 H.sub.41 O.sub.4 N H-8.41 H-8.31 N-2.85 N-3.12 C-75.73 C-75.68OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.5 H.sub.11 H H 129-130 491 C.sub.31 H.sub.41 O.sub.4 N H-8.41 H-8.26 N-2.85 N-2.95 C-75.44 C-75.50OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.4 H.sub.9 H H 86-88 477 C.sub.30 H.sub.39 O.sub.4 N H-8.23 H-8.12 N-2.93 N-2.91 C-75.44 C-75.76OCH(CH.sub.3)(CH.sub.2).sub. 3 C.sub.6 H.sub.5 C.sub.4 H.sub.9 H H 104-106 477 C.sub.30 H.sub.39 O.sub.4 N H-8.23 H-8.26 N-2.93 N-3.02 C-73.68 C-73.93O(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H H 132-134 407 C.sub.25 H.sub.29 O.sub.4 N H-7.17 H-7.05 N-3.44 N-3.41 C-73.68 C-73.45O(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H H 110-112 407 C.sub.25 H.sub.29 O.sub.4 N H-7.17 H-7.23 N-3.44 N-3.39 C-74.08 C-74.16OCH(CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 H H H oil 421 C.sub.26 H.sub.31 O.sub.4 N H-7.41 H-7.59 N-3.32 N-3.20 C-74.08 C-74.04OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 H H H oil 421 C.sub.26 H.sub.31 O.sub.4 N H-7.41 H-7.49 N-3.32 N-3.54 C-68.71 C-68.92OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 H CH.sub.3 H 107-110.sup.(a) 435 C.sub.27 H.sub.33 O.sub.4 N . H-7.26 H-7.17 N-2.96 N-2.86 C-68.71 C-68.71OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 H CH.sub.3 H 94-102.sup.(b) 435 C.sub.27 H.sub.33 O.sub.4 N . H-7.26 H-7.26 N-2.96 N-3.12__________________________________________________________________________ .sup.(a) and.sup.(b) : Transformed to hydrochloride salts by general procedure of salt formation. On thinlayer chromatography in benzene/ether (1:1) R.sub.f of .sup.(a) = 0.74 and R.sub.f of .sup.(b) = 0.72.
EXAMPLE 40
d,l-Trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6.beta.-methyl-3-(2-heptyloxy)benzo[c]quinoline
To a stirred suspension of 150 mg. (0.39 mmole) d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinolin-9(8H)-one in ethanol (10 ml.) at 0° C. is added 40 mg. of sodium borohydride. After 0.5 hr., the reaction mixture is poured into a mixture of ice cold 5% acetic acid (50 ml.) and ether (75 ml.). After separation of the ether layer, the aqueous phase is extracted further with ether (2×50 ml.). The combined ether extracts are washed successively with water (2×50 ml.), saturated sodium bicarbonate (1×50 ml.), brine (1×75 ml.), dried (MgSO 4 ), filtered and concentrated under reduced pressure to yield 156 mg. of a white foam containing a mixture of the axial (minor amount) and equatorial (major amount) alcohols of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline.
m/e--389 (m + ).
IR (CHCl 3 ) 5.72μ (ester carbonyl).
NMR (60 MHz, δ CDCl .sbsb.3 TMS )--showed a characteristic singlet at 2.28 ppm for the acetate methyl.
The major and minor isomers are separated in the following manner: 180 mg. of the alcohols of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinoline are charged to a column containing 15 grams of silica gel and eluted with a solvent mixture of 3 parts benzene to 1 part ether. 15 ml. Fractions are collected. Fractions 6-8 are combined and concentrated under reduced pressure to yield 13 mg. of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9α-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline.
Fractions 11-16 are combined and concentrated to yield 83 mg. of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline.
Other compounds prepared from appropriate reactants by the above procedure include the following:
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6.beta.-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline.
m/e--437 (m + )
IR (CHCl 3 )--5.70μ (ester carbonyl).
Conversion to the hydrochloride yielded a solid (m.p. 188°-190° C.). Recrystallization from acetone/methanol/ether (25:1:100) affords an analytical sample of the 9β-alcohol, m.p. 193°-194° C.
Analysis: Calc'd for C 27 H 35 O 4 N.HCl: C, 68.42; H, 7.66; N, 2.96%. Found: C, 68.48; H, 7.70; N, 2.89%.
Conversion to the methanesulfonate (with methanesulfonic acid in dichloromethane) gives a solid which is recrystallized from ethyl acetate to yield white crystals, m.p. 110°-114° C.
IR (CHCl 3 ): 2.95, 3.70, 3.95, 5.60, 6.06, 6.19 and 6.27μ.
Analysis: Calc'd for C 27 H 35 O 4 N.CH 4 O 3 S: C, 63.02; H, 7.37; N, 2.63%. Found: C, 62.90; H, 7.31; N, 2.74%.
d,l-cis-5,6,6aβ,7,8,9,10,10aβ-octahydro-1-acetoxy-9-hydroxy-6.beta.-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline.
m/e--437 (m + ).
IR (CHCl 3 )--5.71μ (ester carbonyl).
l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline; m.p. 120°-125° C. (dec.) as the hydrochloride salt.
[α] D 25 =-98.57° (c=0.351, CH 3 OH).
m/e--437 (m + ).
Analysis: Calc'd for C 27 H 35 O 4 N.HCl: C, 68.42; H, 7.66; N, 2.96%. Found: C, 68.24; H, 7.68; N, 3.00%.
d-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline; m.p. 120°-125° C. (dec.) as the hydrochloride salt.
[α] D 25 =+99.33° (c=0.30, CH 3 OH).
m/e--437 (m + ).
Analysis: Calc'd for C 27 H 35 O 4 N.HCl: C, 68.42; H, 7.66; N, 2.96%. Found: C, 68.41; H, 7.54; N, 2.95%.
In like manner, the compounds tabulated below are prepared from appropriate reactants.
__________________________________________________________________________ ##STR41## m/e Calc'd FoundZW R.sub.4 R.sub.5 R.sub.6 R.sub.8 Salt* M.P.(°C.) (M.sup.+) Formula C H N C H N__________________________________________________________________________5-phenyl-2-pentyloxy H CH.sub.3 H H HCl 110-130 437 C.sub.27 H.sub.35 O.sub.4 N . 68.42 7.66 2.96 68.45 7.60 3.085-phenyl-2-pentyloxy H CH.sub.3 H H oil 4375-phenyl-2-pentyloxy CH.sub.3 H CH.sub.3 H HCl 78-82 4515-phenyl-2-pentyloxy CH.sub.3 H CH.sub.3 H HCl 163.5-165 4514-phenylbutoxy CH.sub.3 H CH.sub.3 H 134-135 437 C.sub.27 H.sub.35 O.sub. 74.11 8.06 3.20 73.59 8.07 3.244-phenylbutoxy CH.sub.3 H H H HCl 187-188 423 C.sub.26 H.sub.33 O.sub.4 N . 67.89 7.45 3.04 67.85 7.37 2.972-heptyloxy H H H H oil 375 C.sub.21 H.sub.22 O.sub.4 N 70.37 8.86 3.73 69.85 8.87 3.632-heptyloxy H H H H oil 375 C.sub.22 H.sub.33 O.sub.4 N 70.37 8.86 3.73 70.55 8.70 3.715-phenyl-2-pentyloxy H H H H oil 4235-phenyl-2-pentyloxy C.sub.3 H.sub.7 H H H HCl 205-206 465__________________________________________________________________________ *Prepared by addition of HCl gas to ether solution of base form.
EXAMPLE 41
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
Method A
Sodium borohydride (7.57 g., 0.20 mole) is added to methanol (200 ml.) under a nitrogen atmosphere and cooled in an acetone/dry ice bath to about -75° C. The mixture is stirred for about 20 minutes to dissolve most, if not all, the sodium borohydride. A solution of d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (8.71 g., 0.02 mole) in tetrahydrofuran (88 ml.) is cooled to about -50° C. and then added dropwise over a 5-10 minute period to the sodium borohydride solution. The reaction mixture is stirred at about -70° C. for 30 minutes and is then poured onto a mixture of water (1000 ml.) containing ammonium chloride (45 g., 0.80 mole), crushed ice (250 ml.) and ethyl acetate (250 ml.). The layers are separated and the aqueous extracted with ethyl acetate (3×200 ml.). The combined extracts are washed with water (1×100 ml.) and dried (MgSO 4 ). The dried extract is cooled to about 5° C. A solution of ethyl acetate (15 ml.)/HCl, 1.5 N (0.025 mole) is then added dropwise over a 15 minute period. Upon stirring the mixture at 0°-5° C., the hydrochloride salt of the title product precipitates. The mixture is stirred for a half-hour, filtered and the salt dried at 25° C./0.055 mm. to give 6.378 g. (67.3%) of product, m.p. 195°-198° C. (dec.).
The following compounds are prepared from appropriate reactants in like manner.
__________________________________________________________________________ ##STR42## (°C.) m/e Calc'd FoundZW R.sub.4 R.sub.5 R.sub.6 m.p. (m.sup.+) Formula C, H, N C, H, N__________________________________________________________________________ C-70.23 C-70.04OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.5 H.sub.11 H H 209-210 493 C.sub.31 H.sub.43 O.sub.4 H . H-8.37 H-8.16 N-2.64 N-2.59 C-69.82 C-70.05OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.4 H.sub.9 H H 159-160 479 C.sub.30 H.sub.41 O.sub.4 N . H-8.20 H-8.44 N-2.71 N-2.66 C-67.33 C-67.60OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H H 130-138 409 C.sub.25 H.sub.31 O.sub.4 N . H-7.23 H-7.22 N-3.14 N-3.06 C-72.39 C-72.33OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 (CH.sub.2).sub.2 C.sub.6 H.sub.5 H H 199-200 527 C.sub.34 H.sub.41 O.sub.4 N . H-7.51 H-7.38 N-2.48 N-2.50 C-69.35 C-69.89OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.3 H.sub.7 H H 193-195 465 C.sub.29 H.sub.39 O.sub.4 N . H-8.03 H-8.36 N-2.79 N-3.05 C-68.88 C-68.58OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5 H H 154-157 451 C.sub.28 H.sub.37 O.sub.4 N . H-7.85 H-7.52 N-2.87 N-2.79 C-70.61 C-69.75OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.13 H H 196-199 507 C.sub.32 H.sub.45 O.sub.4 N . H-8.53 H-8.19 N-2.58 N-2.51 C-69.79 C-69.76OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 C.sub.3 H.sub.7 H CH.sub.3 154-156 479 C.sub.30 H.sub.41 O.sub.4 N . H-8.21 H-8.16 N-2.72 N-2.74 C-66.73 C-66.37O(CH.sub.2).sub.2 C.sub.6 H.sub.5 CH.sub.3 H H 210-212 395 C.sub.24 H.sub.29 O.sub.4 N . H-7.00 H-6.93 (dec.) N-3.24 N-3.18 C-74.77 C-74.47C(CH.sub.3).sub.2(CH.sub.2).sub.5 CH.sub.3 CH.sub.3 H H 114-115 401 C.sub.25 H.sub.39 O.sub.3 N H-9.79 H-9.24 N-3.49 N-3.24__________________________________________________________________________ .sup.(a) = cis 6a, 10a
Alternatively, the title compound is prepared by the following procedure (Method B).
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
A heterogeneous mixture of d,l-5,6,6a,7-tetrahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (3.0 g., 7 mmole) and palladium-on-carbon (5%, 3.0 g.) in methanol (30 ml.) is hydrogenated at room temperature in a Parr apparatus under 50 p.s.i. hydrogen for three hours. The catalyst is then filtered and the methanol filtrate evaporated under reduced pressure to give the title product.
The product is taken up in ethyl acetate (300 ml.) and the resulting solution cooled to 0° C. An excess of a saturated solution of hydrogen chloride in ethyl acetate is then added to precipitate the hydrochloride salt of the title product as a white solid. It is filtered, washed with ethyl acetate, and dried.
Similarly prepared are the following compounds:
__________________________________________________________________________ ##STR43## (°C.) m/e.sup.(b) Analysis.sup.(c)Configuration m.p. (m.sup.+) C H N [α].sub.D.sup.25(d)__________________________________________________________________________(-)2'R,6S,6aR,9R,10aR 145-154 437 68.41 7.66 2.95 -100 (dec.)(-)2'S,6S,6aR,9R,10aR 224-225 437 68.09 7.47 2.94 -118 (dec.)+2'S,6R,6aS,9S,10aS 135-140 437 67.29 7.56 3.02 +110 (dec.)+2'R,6R,6aS,9S,10aS 218-220 437 67.75 7.58 2.89 +110 (dec.)__________________________________________________________________________ .sup.(b) 100% .sup.(c) Calc'd for C.sub.27 H.sub.35 O.sub.4 N . HCl: C, 68.41; H, 7.66; N, 2.95 .sup.(d) C = 1.0, CH.sub.3 OH
The d,l-5,6,6a,7-tetrahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one is prepared as follows:
To a stirred solution of d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (4.5 g., 0.0115 mole) in pyridine (45 ml.) at room temperature is added acetic anhydride (45 ml.). The resulting solution is stirred for 3.5 hours and is then poured onto ice-water (250 ml.) and the mixture extracted with diisopropyl ether (2×250 ml.). The combined extracts are washed with water (3×200 ml.), dried (MgSO 4 ) and evaporated under reduced pressure to a yellow-brown oil which solidifies on scratching the walls of the flask containing it. Trituration of the solid with n-heptane gives 2.0 g. of the 1-acetoxy derivative (40% yield). It is purified by recrystallization from hot chloroform-n-hexane (1:4) to give the pure ester; m.p. 136°-140° C.
m/e--433 (m + ).
1 H NMR (60 MHZ) δ CDCl .sbsb.3 TMS (ppm): 7.21 (bs, 5H, aromatic), 6.62 (d, J=1.5 Hz, 1H, C═C--H), 5.97 (d, J=3 Hz, 1H, meta H), 5.86 (d, J=3 Hz, 1H, meta H9, 2.27 [s, 3H, CH 3 --C(═O)], 1.21 (d, J=7 Hz, 6H, CH 3 --C--N, CH 3 --C--O), 1.49-4.51 (m, 14H, remaining protons).
The following tetrahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-ones are similarly prepared from appropriate reactants according to the above procedures.
__________________________________________________________________________ ##STR44## (°C.) m/e Calc'd FoundZW R.sub.4 R.sub.5 R.sub.6 m.p. (m.sup.+) Formula C, H, N C, H, N__________________________________________________________________________ C-75.53 C-75.62C(CH.sub.3).sub.2 C.sub.6 H.sub.13 CH.sub.3 H H 108-112 397 C.sub.25 H.sub.35 NO.sub.3 H-8.87 H-8.73 N-3.52 N-3.52 C-74.80 C-74.96OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 H CH.sub.3 H 125-130 433 C.sub.27 H.sub.31 O.sub.4 N H-7.21 H-7.11[6R, 6aR] N-3.23 N-3.19 C-74.80 C-74.91OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H H 145-146 433 C.sub.27 H.sub.31 O.sub.4 N H-7.21 H-7.20[6S, 6aR] N-3.23 N-3.24 C-74.80 C-74.66OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H H 167-168 433 C.sub.27 H.sub.31 O.sub.4 N H-7.21 H-7.20[2'S, 6S, 6aR] N-3.23 N-3.33 C-74.80 C-74.58OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 H H 120-121 433 C.sub.27 H.sub.31 O.sub.4 N H-7.21 H-7.19[2'R, 6S, 6aR] N-3.23 N-3.27 C-73.63 C-73.38OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 H H 159-160 391 C.sub.24 H.sub.25 O.sub.4 N H-6.44 H-6.41 N-3.58 N-3.59__________________________________________________________________________
EXAMPLE 42
d,l-cis-5,6,6aβ,7,8,9,10,10aβ-octahydro-1-acetoxy-9α-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
To a solution of d,l-cis-5,6,6aβ,7,10,10aβ-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (1.0 g., 2.296 mmole) in dry tetrahydrofuran (100 ml.) at -78° C. is added, with stirring, potassium tri-sec-butyl borohydride (4.6 ml. of 0.5 M, 2.296 mmole) dropwise over a period of five minutes. The reaction mixture is stirred an additional 30 minutes at -78° C. and is then poured, with stirring, into a solution of 5% acetic acid (250 ml.) and ether (500 ml.) pre-cooled to 0° C. The layers are separated and the aqueous layer extracted with additional ether (250 ml.). The combined ether extracts are washed successively with water (2×250 ml.), saturated sodium bicarbonate solution (1×250 ml.) and brine (1×250 ml.), dried (MgSO 4 ) and concentrated in vacuo to give a yellow oil (1.4 g.). The crude oil is chromatographed on silica gel ( 100 g.) using benzene/ether (3:1) as eluant. After elution of less polar impurities, the title compound is isolated as a clear oil (700 mg.). The oil is dissolved in ether (35 ml.) and treated with ether saturated with HCl gas to give the hydrochloride salt of the title compound (448 mg.), m.p. 115°-124° C. after recrystallization from ether/chloroform.
MS (mol. ion)=437.
IR (KBr): 5.58μ (ester>C═O).
Analysis: Calc'd for C 27 H 35 O 4 N.HCl: C, 68.41; H, 7.66; N, 2.96%. Found: C, 68.52; H, 7.91; N, 2.73%.
The following compounds are prepared in like manner from appropriate reactants:
______________________________________ ##STR45## M.P. MSZW R.sub.4 R.sub.5 R.sub.6 R.sub.8 (°C.) (m.sup.+)______________________________________5-phenyl-2-pentyloxy CH.sub.3 H H H 168- 437 170*.sup.(a)5-phenyl-2-pentyloxy H CH.sub.3 H H oil5-phenyl-2-pentyloxy H CH.sub.3 H H oil 4375-phenyl-2-pentyloxy CH.sub.3 H CH.sub.3 H 159- 451 162*.sup.(b)______________________________________*HCl salt. Analysis:(a) Calc'd. for C.sub.27 H.sub.35 O.sub.4 N . HCl:C, 68.41; H, 7.66; N, 2.96%Found: C, 68.48; H, 7.57; N, 2.93%(b) Calc'd for C.sub.28 H.sub.37 O.sub.4 N . HCl: C, 68.88; H, 7.85; N, 2.87%Found: C, 68.42; H, 7.78; N, 2.75%______________________________________
EXAMPLE 43
Following the procedure of Example 40 but using the appropriate 5,6,6a,7,10,10a-hexahydro-1-acyloxy-6-R 4 -3-(Z-W)-benzo[c]quinolin-9(8H)-ones of Examples, 35, 37, 47 and 49 and the appropriate acid anhydride affords the isomeric alkanoyloxy compounds having the formula ##STR46## wherein R 4 , R 5 , R 6 , Z and W are as defined in Examples 35, 37, 47 and 49 and R 1 is acetyl, propionyl, butyryl, valeryl or benzoyl.
EXAMPLE 4
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-diacetoxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline
1.2 g. of the unchromatographed reduction product of d,l-trans-5,6,6aβ-7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline from Example 40 is stirred with excess acetic anhydride and pyridine overnight at room temperature. The mixture is poured into ice water, the aqueous mixture extracted with ether (3×100 ml.) and the combined extracts washed with water, brine, then dried (MgSO 4 ) and evaporated. The residue is subjected to column chromatography (40 g. silica gel, benzene/ether [9:1] as eluting solvent) to give 680 mg. of the desired d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-diacetoxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline, which crystallizes on addition of hexane and ethyl acetate, m.p. 86°-87° C.
m/e--431 (m + ).
IR (KBr)--5.73μ (ester carbonyls).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 5.88 (bs, H 2 , H 4 -2H), 2.28 and 2.05 [2 three-proton singlets, CH 3 --C(═O)--], and ca. 0.8-5.0 (multiplets, remaining protons).
Analysis: Calc'd for C 25 H 37 O 5 N: C, 69.57; H, 8.64; N, 3.25%. Found: C, 69.51; H, 8.54; N, 3.14%.
Similar treatment of 60 mg. d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinoline in pyridine (1 ml.) and acetic anhydride (1 ml.) for 1 hour at room temperature yields the desired d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9β-diacetoxy-6β-methyl-3-(4-phenylbutyloxy)benzo[c]quinloine, m.p. 146°-147° C. after recrystallization from ethyl acetate/hexane (1:1).
m/e--465 (m + )
Analysis: Calc'd for C 28 H 35 O 5 N: C, 72.23; H, 7.58; N, 3.01%. Found: C, 72.17; H, 7.61; N, 3.08%.
Similarly, acylation of the compounds of Examples 40, 43 and 61 with the appropriate acid anhydride affords 1,9-diacyloxy derivatives having the formula below wherein R 1 , R 4 , R 5 , R 6 , Z and W are as defined in Examples 40, 43 and 61 and R' is acetoxy, propionyloxy, butyryloxy, valeryloxy or benzoyloxy. ##STR47##
EXAMPLE 45
The 1-acyloxy derivatives of Examples 40 and 43 are acylated at the 9-position according to the procedure of Example 44 but using an acid anhydride which provides an acyl moiety different from that of the acyl moiety at the 1-position. In this manner, diacyloxy derivatives having different acyloxy groups at the 1- and 9-positions are prepared.
EXAMPLE 46
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinoline
A solution of 130 mg. d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinoline and 46 mg. potassium carbonate in 35 ml. methanol is stirred at room temperature. After 30 minutes, the reaction mixture is neutralized with acetic acid and concentrated under reduced pressure. The residue is dissolved in ether (100 ml.), washed successively with water (2×35 ml.), saturated sodium bicarbonate (1×35 ml.), brine (1×40 ml.), dried (MgSO 4 ) and concentrated under reduced pressure to give 96 mg. d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinoline as an amorphous solid, m.p. 80°-100° C. (dec.).
m/e--347 (m + ).
The NMR (CDCl 3 , αMHz) shows no absorption for the acetate methyl and the IR (CHCl 3 ) had no absorption for an ester carbonyl.
In like manner, the following compound is prepared from the corresponding 1-acetoxy derivative of Example 41.
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline.
m/e--395 (m + ).
Conversion to the hydrochloride gives a powder, m.p. 151°-156° C.
IR (KBr): 3.00, 4.00 (HN.sup.⊕ ═), 6.10 and 6.25μ.
Similarly, d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-methyl-6.beta.-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one is hydrolyzed to the corresponding 1-hydroxy compound; m.p. 157°-160° C.
m/e--359 (m + )
Analysis: Calc'd for C 22 H 33 O 3 N: C, 73.50; H, 9.25; N, 3.90%. Found: C, 73.16; H, 9.14; N, 3.85%.
Hydrolysis of the 1-acyloxy derivatives of Example 43 according to the above procedure affords compounds having the formula below wherein R 4 , R 5 , R 6 , Z and W are as defined in Example 43. ##STR48##
EXAMPLE 47
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-3-(2-heptyloxy)-5-benzoyl-6β-methylbenzo[c]quinolin-9(8H)-one
To a stirred solution of the product of Example 36, d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinolin-9(8H)-one (812 mg.) in 2.5 ml. pyridine is added 421 mg. benzoyl chloride in 5 ml. chloroform. After two hours, the reaction mixture is poured onto ice and extracted twice with ether. The combined ether extracts are washed with water, sodium bicarbonate, dried (MgSO 4 ) and filtered to yield, after concentration and crystallization from ether/petroleum ether, d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-3-(2-heptyloxy)-5-benzoyl-6β-methylbenzo[c]quinolin-9(8H)-one, m.p. 108°-110° C.
m/e--491 (m + ).
Repetition of this procedure but using an equivalent amount of acetyl chloride in place of benzoyl chloride and the appropriate benzo[c]quinoline affords the following compound:
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-3-(2-heptyloxy)-5-acetyl-6β-methylbenzo[c]quinoline-9(8H)-one.
m/e--433 (m + ).
In like manner, the remaining compounds of Example 36 and those of Example 34 are converted to their corresponding benzoyl, acetyl, propionyl, butyryl, valeryl, 2-phenylacetyl and 4-phenylbutyryl derivatives by reaction with the appropriate acyl chloride. The compounds have the formula ##STR49## wherein R 4 , R 5 , Z, W and R 1 are as defined in Examples 34 and 36 and R 6 is benzoyl, acetyl, propionyl, butyryl, valeryl, 2-phenylacetyl or 4-phenylvaleryl.
EXAMPLE 48
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-methyl-6β-methyl-3-(2-heptyloxy)-benzo[c]quinolin-9(8H)-one
To a stirred solution of 387 mg. d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(2-heptyloxy)-benzo[c]quinolin-9(8H)-one in 3 ml. acetonitrile cooled to 15° C. is added 0.5 ml. 37% aqueous formaldehyde followed by 100 mg. sodium cyanoborohydride. Acetic acid is added to maintain a neutral pH until the reaction is complete as evidenced by no remaining starting material by thin layer chromatography. The product is isolated in the following manner.
Ice water and ether is added to the reaction mixture, the ether layer separated and the aqueous extracted once more with ether. The combined ether layers are combined, dried and evaporated to yield the desired d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-methyl-6.beta.-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one as an oil.
1 H NMR (60 MHz, CDCl 3 ) shows a characteristic absorption at 2.85 ppm for >N--CH 3 .
In like manner, the following compounds are prepared from appropriate reactants:
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one, an oil.
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-diacetoxy-5-methyl-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline, an oil.
m/e--445 (m + ).
In addition, the following compounds are similarly prepared:
______________________________________ ##STR50## m/eZW R.sub.4 R.sub.5 R.sub.6 R.sub.8 M.P. (m.sup.+)______________________________________ ##STR51## CH.sub.3 H CH.sub.3 H 94°- 97° C..sup.1 449 ##STR52## CH.sub.3 H CH.sub.3 H oil.sup.2 449O(CH.sub.2).sub.4 C.sub.6 H.sub.5 CH.sub.3 H CH.sub.3 H 102°- 435 103° C..sup.3.sup.1 As the HCl salt.Analysis:Calc'd for C.sub.28 H.sub.35 O.sub.4 N . HCl: C, 69.19; H, 7.47; N, 2.88% Found: C, 68.72; H, 7.18; N, 2.74%.sup.2 Analysis:Calc'd for C.sub.28 H.sub.35 O.sub.4 N: C, 74.80; H, 7.85; N, 3.12% Found: C, 74.66; H, 8.05; N, 2.66%m.p. 69°-75° C. as the HCl salt..sup.3 Analysis:Calc'd for C.sub.27 H.sub.33 O.sub.4 N: C, 74.45; H, 7.64; N, 3.22% Found: C, 73.89; H, 7.51; N, 3.04%______________________________________
EXAMPLE 49
Repetition of the procedure of Example 48 but using the compounds of Examples 34 and 36-39 as reactants affords compounds having the formula below wherein R 4 , R 5 , R 1 , Z and W are as defined in said Examples: ##STR53##
EXAMPLE 50
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-5-ethyl-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline
To a solution of 100 mg. lithium aluminum hydride in 5 ml. dry tetrahydrofuran (cooled in an ice/water bath) is added dropwise a solution of 90 mg. d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-5-acetyl-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline in 3 ml. tetrahydrofuran. After the addition is complete, the reaction mixture is heated at reflux for one hour and is then allowed to cool to room temperature. Equivalent amounts of water, followed by 3 N potassium hydroxide are added, the resultant precipitate filtered and the filtrate concentrated in vacuo to yield the desired N-ethyl derivatives as an oil.
m/e--375 (m + ).
Similarly, the 5-acyl derivatives of Example 47 are reduced to the corresponding aralkyl or alkyl derivatives having the formula ##STR54## wherein R 4 , R 5 , Z and W are as defined in said Example and R 6 is aralkyl or alkyl.
EXAMPLE 51
d,1-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-5-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
Formaldehyde (1.1 ml. of 37% aqueous) is added to a solution of d,1-trans-5,6,6aβ,7,10,10aα-hexahydro-acetoxy-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one in acetontrile (15 ml.) at room temperature, followed by sodium cyanoborohydride (0.262 g.). The reaction mixture is stirred for one hour during which time the pH is maintained at neutral pH by addition of acetic acid as needed. Additional sodium cyanoborohydride (0.262 g.) and methanol (15 ml.) are added to the reaction mixture, which is then acidified to pH 3, stirred for two hours, and concentrated under reduced pressure to an oil. The oil is diluted with water (50 ml.), the pH then adjusted to 9-10 by means of aqueous sodium hydroxide, and the alkaline mixture extracted with ether (3×200 ml.). The combined ether extracts are washed with brine, dried (Na 2 SO 4 ) and concentrated under reduced pressure to a clear oil. The oil is then dissolved in 50% ether-hexane and charged to a silica gel column. The column is eluted first with 50% ether-hexane followed by 60%, 70% and 75% ether-hexane. The eluate is monitored by thin layer chromatography (ether-10, hexane-1). The first produced collected is d,1-trans-5,6,6a,7,10,10a-hexahydro-1-acetoxy-5-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (0.125 g.)
m/e--435 (m + ).
Analysis: Calc'd for C 27 H 33 O 4 N: C, 74.45; H, 7.64; N, 3.22%. Found: C, 74.06; H, 7.77; N, 3.31%.
The second product is the 9α-hydroxy diastereomer of the title compound (25 mg.).
m/e--437 (m 30 ).
Analysis: Cal'd for C 27 H 35 O 4 N: C, 74.11; H, 8.06; N, 3.20%. Found: C, 73.96; H, 8.34; N, 3.00%.
The third product is the 9β-hydroxy diastereomer of the title compound (0.7 g.).
m/e--437 (m + ).
Analysis: Calc'd for C 27 H 35 O 4 N: C, 74.11; H, 8.06; N, 3.20%. Found: C, 73.56; H, 7.86; N, 3.21%.
Similarly, d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)one is treated with sodium cyanoborohydride to give:
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one as an oil.
m/e--387 (m + ).
IR (CHCl 3 ): 5.80 (ketone C═O), 5.65 (ester C═O), μ.
Analysis: Calc'd for C 23 H 33 O 4 N: C, 71.29; H, 8.58; N, 3.61%. Found: C, 70.78; H, 8.71; N, 3.27%.
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-5-methyl-3-(2-heptyloxy)benzo[c]quinoline, an oil.
m/e--389 (m + ).
IR (CHCl 3 ): 2.80 (O--H); 5.70 (ester C═O), μ.
Analysis: Calc'd for C 23 H 35 O 4 N: C, 70.92; H, 9.06; N, 3.60%. Found: C, 70.56; H, 8.95; N, 3.56%.
and d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one is converted to:
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-methyl-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one;
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-5-methyl-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline, which is isolated as the hydrochloride salt; m.p. 163°-165° C.
m/e--451 (m + ).
EXAMPLE 52
d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-isobutyryl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one
A solution of isobutyryl chloride (114 mg., 1.07 mmole) in chloroform (20 ml.) is slowly added with stirring to a solution of d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (450 mg., 1.07 mmole) in dry pyridine (1.5 ml.) at 0° C. and under a nitrogen atmosphere. The reaction mixture is stirred for five hours and is then poured into ice/water (50 ml.). The chloroform layer is separated and the aqueous layer extracted with chloroform (2×20 ml.). The chloroform extracts are combined and washed with 10% hydrochloric acid (2×10 ml.), followed by brine (1×10 ml.), and then dried (MgSO 4 ). Concentration of the chloroform solution in vacuo gives a yellow oil which solidifies upon standing. Trituration of the solid with hexane affords a white crystalline solid, which is recovered by filtration and dried (400 mg.), m.p. 128°-129° C.
Concentration of the hexane filtrate gives 121 mg. of oil.
EXAMPLE 53
d,l-trans-5,6,6aβ,7,8,9,10,10α-octahydro-1-acetoxy-9β-hydroxy-5-isobutyryl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
Sodium borohydride (38 mg., 1.0 mmole) is slowly added to a solution of d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-isobutyryl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one (260 mg., 0.529 mmole) in absolute ethanol (20 ml.) 5°-10° C. under a nitrogen atmosphere. The reaction mixture is stirred for one hour and is then acidified with 10% hydrochloric acid. The ethanol is removed by concentration under reduced pressure. Water (10 ml.) is added to the remaining solution which is then extracted with ethyl acetate (2×50 ml.). The extracts are combined, washed with brine and then dried (MgSO 4 ). Concentration in vacuo affords the title compound as an amorphous solid (213 mg.) which is used without further purification.
EXAMPLE 54
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9β-diacetoxy-5-isobutyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
Under a nitrogen atmosphere, a solution of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-5-isobutyryl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline (213 mg., 0.432 mmole) in tetrahydrofuran (5 ml.) is added to a slurry of lithium aluminum hydride (100 mg., 2.6 mmole) in tetrahydrofuran (5 ml.) at room temperature. The mixture is stirred overnight and then water (0.1 ml.), 15% sodium hydroxide solution (0.1 ml.) and water (0.3 ml.) are added. It is then filtered under nitrogen and the filter cake washed with tetrahydrofuran (2×5 ml.). The combined filtrate and wash solution are concentrated to a reddish oil (0.174 g.).
The oil is dissolved under nitrogen in pyridine (1 ml.) and the solution cooled to 0° C. Acetic anhydride (1 ml.) is added, with stirring, to the pyridine solution and the reaction mixture stirred for 30 minutes at 0° C. It is then poured into water (25 ml.) and extracted with ethyl acetate (3×25 ml.). The extracts are combined, washed with brine, dried (MgSO 4 ) and concentrated to a brown oil (184 mg.). The oil is flushed with nitrogen and chromatographed on silica gel (40 g.) using benzene/ether (9:1) as eluant. Fractions of 10 ml. each are collected. Fractions 2-10 are combined and concentrated to an oil (109 mg.).
m/e--521 (m + ).
Analysis: Calc'd for C 32 H 43 O 5 N: C, 73.67; H, 8.31; N, 2.68%. Found: C, 74.33; H, 8.89; N, 2.23%.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.22 (s, 5H, aromatic), 6.05 (d, 1H, aromatic), 5.90 (d, 1H, aromatic), 4.90 (bs, 1H), 4.30 (bs, 1H), 3.10 (d, 2H, N--CH 2 ), 2.90 (d, 2H, N--CH 2 ), 2.70 (bs, 2H), 2.40 and 2.15 (s, 6H, 2--CH 3 --COO--), 1.85 (bs, 2H, H 7 and H 8 ), 1.5 (m), ##STR55## 1.0-3.0 (variable, remaining protons).
EXAMPLE 55
d,l-trans-5,6,6aβ,7,10,10aα-Hexahydro-1-hydroxy-5-acetyl-6β-methyl-9-methylene-3-(2-heptyloxy)benzo[c]quinoline
A. Triphenylmethyl phosphonium bromide (742 mg., 2.12 mmole) is added to a solution of sodium hydride (0.95 g., 2.0 mmole) in dimethyl sulfoxide (50 ml.) at 50° C. The reaction mixture is then heated at 70° C. for three hours after which d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-acetyl-6.beta.-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one (0.858 g., 2.0 mmole) in dimethyl sulfoxide (50 ml.) is added. The reaction mixture is heated at 70° C. overnight, and then cooled and poured into a mixture of ice and water containing sodium bicarbonate (12.5 g.). The aqueous mixture is extracted with benzene, dried (Na 2 SO 4 ) and evaporated under reduced pressure to give the crude product. It is purified by column chromatography over silica gel in hexanebenzene (1:1).
B. dl-trans-5,6,6aβ,7,10,10aα-hexahydro-5-acetyl-1-hydroxy-6β-methyl-9-methylene-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline.
A slurry of 0.94 g. (0.039 mole) of sodium hydride (obtained by washing 1.87 g. of 50% sodium hydride in mineral oil dispersion with dry pentane) in 57 ml. dimethylsulfoxide is heated at 50° C. for 2.5 hours. After the addition of 15.32 g. (0.043 mole) of triphenylmethylphosphonium bromide, the reaction is heated for 2 hours at 60° C. A solution of 1.86 g. (0.004 mole) of dl-trans-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-5-acetyl-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline-9(8H)-one, in 57 ml. dimethylsulfoxide is added and the reaction is heated at 60° C. for 30 minutes. The cooled reaction mixture is poured into 200 ml. ice-water containing 20 g. of sodium bicarbonate. This is extracted twice with ethylacetate (50 ml. each), the combined organic layers are washed with 50 ml. water, 50 ml. brine, dried over magnesium sulfate, filtered and evaporated the solvent to afford an orange colored oil (contains triphenylphosphine oxide by thin-layer chromatography). Purification is achieved via chromatography (Brinkman silica-gel 125 g.; solvent: cyclohexane 3, ether 1) to afford the title compound, 1.251 g. (74% yield), m.p. 174°-176° C.
Analysis: Calc'd. for C 28 H 35 O 3 N: C, 77.56; H, 8.14; N, 3.23%. Found: C, 77.29; H, 7.96; N, 3.22%.
I.R. (KBr): 2.98μ (s), 3.34μ (m), 3.38μ (m), 3.44μ (m), 6.10μ (s), 6.24μ (s), 6.58μ (s), 6.90μ (s).
m/e--433 (m + ).
1 HNMR (60 MHz) δ CDCl .sbsb.3 TMS : 8.80 (s, 1H, phenol), 7.16 (m, 5H, arom.), 6.32 (d, 1H, C -2 H), 6.09 (d, 1H, C -4 H), 4.64 (broad s, 2H, vinyl), 1.96 & 1.93 (2s, 3H, amide-CH 3 ), 1.27 & 1.25 (2d, 3H, C 6 --CH 3 ), 1.02, d, 3H (side chain CH 3 ), 0.9-4.5 (variable remaining protons).
Similarly prepared from the appropriate starting material is: dl-cis-5,6,6aβ,7,10,10aβ-hexahydro-5-acetyl-1-hydroxy-6β-methyl-9-methylene-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline.
m.p. 168-169.5, yield: 88%.
Analysis: Calc'd. for C 28 H 35 O 3 N: C, 77.56; H, 8.14; N, 3.23%. Found: C, 77.25; H, 8.14; N, 3.12%.
1 HNMr (60 MHz) δ CDCl .sbsb.3 TMS : 8.82 (s, 1H, phenol), 7.16 (m, 5H, arom.), 6.36 (d, 1H, C -2 H), 6.12 (d, 1H, C -4 H), 4.68 (s broad, 2H, vinyl), 2.08 & 2.06 (2s, 3H, amide-CH 3 ), 1.22 & 1.20 (2d, 3H, C -6 CH 3 ), 1.10 (d, 3H, side chain CH 3 ), 1.50-4.50 (variable remaining protons).
I.R. (KBr): 2.95μ (m), 3.36μ (s), 6.10μ (s), 6.33μ (s), 6.88μ (s), 7.20μ (s), 7.35μ (s), 8.50μ (s).
m/e--433 (m + ).
Similarly, the remaining keto derivatives described herein are converted to their corresponding 9-methylene derivatives.
EXAMPLE 56
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-hydroxy-5-ethyl-9-hydroxymethyl-6β-methyl-3-(2-heptyloxy)benzo[c]quinoline
To a solution of d,l-trans-5,6,6aβ,7,10,10aα-hexahydro-1-hydroxy-5-acetyl-6.beta.-methyl-9-methylene-3-(2-heptyloxy)benzo[c]quinoline (0.855 g., 2 mmole) in tetrahydrofuran (30 ml.) at 0°-5° C., is added dropwise a 1 M solution of diborane in tetrahydrofuran (borane-tetrahydrofuran complex) (6 ml.). After the addition the reaction mixture is held at room temperature for 30 minutes and then treated with water to decompose excess hydride.
The reaction mixture is then warmed to 50° C. on a water bath and 3 N sodium hydroxide (3 ml.) added followed by dropwise addition of 30% hydrogen peroxide (3 ml.). After addition, the mixture is held at room temperature for one hour, potassium carbonate (1.5 g.) added and the tetrahydrofuran layer separated. The aqueous phase is extracted with tetrahydrofuran (3×10 ml.), the extracts combined, dried (MgSO 4 ) and concentrated to give the product. Purification is achieved by column chromatography on silica gel using ether-hexane.
In like manner, the remaining 9-methylene compounds of formulae II, III and IV wherein the 1-hydroxy groups are protected by acetylation and compounds of formulae II and III wherein the 5-NH groups are protected by acetylation or alkylation are converted to their corresponding methylene derivatives. The N-acetyl groups are, of course, converted to N-ethyl groups and acetyloxy groups are converted to hydroxy groups.
EXAMPLE 57
d,l-7,10-dihydro-1-hydroxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one ethylene ketal and d,l-5,6,6a,7,10,10a-hexahydro-1-hydroxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one ethylene ketal
A suspension of d,l-trans-5,6,6aβ,7-tetrahydro-1-hydroxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one (0.50 g., 1.52 mmoles), ethylene glycol (0.43 ml., 7.70 mmoles) and p-toluenesulfonic acid monohydrate (0.28 g., 1.46 mmoles) in benzene (25 ml.) is heated at reflux for 45 minutes. The by-product water is azeotropically removed. The dark suspension thus produced is taken up in a mixture of ether and saturated sodium bicarbonate solution. The organic layer is separated, washed with saturated aqueous sodium bicarbonate solution, dried (MgSO 4 ), and concentrated to an oil which is then chromatographed on silica gel (50 g.) using ether as eluant. Fractions of 10 ml. each are collected.
Fractions 12-18 are combined and evaporated to give 203 mg. of the ethylene ketal of the hexahydro derivative.
m/e--375 (m + ).
IR (CHCl 3 ): 2.98μ (superposition of N--H and O--H stretch).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 5.7 (s, 2H, aromatic), 4.0 (s, 4H, ketal ethylene) and absorption for remaining protons.
Fractions 42-65 are combined and concentrated to afford 146 mg. of a yellow solid. Trituration of the solid in ether-pentane (1:1) gives 85 mg. of 7,10-dihydro-1-hydroxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one ethylene ketal, m.p. 171°-173° C.
m/e--371 (m + );
IR (KBr): 2.98μ (O--H).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 8.6 (s, 1H, C-6 aromatic), 6.6 and 7.0 (bd, 2H, aromatic), 4.1 (bs, 4H, ethylene ketal), 3.9 (bs, 2H, C-10 methylene), 3.1 (t, 2H, C-7 ethylene), 2.0 (bt, 2H, C-8 methylene) and other absorptions for remaining protons.
Analysis: Calc'd for C 22 H 29 O 4 N: C, 71.13; H, 7.87; N, 3.77%. Found: C, 71.19; H, 7.67; N, 3.61%.
In like manner, d,l-5,6,6a,7,10,10a-hexahydro-1-hydroxy-3-(2-heptyloxy)-6-methylbenzo[c]quinolin-9(8H)-one ethylene ketal is converted to d,l-7,10-dihydro-1-hydroxy-3-(2-heptyloxy)-6-methylbenzo[c]quinolin-9(8H)-one ethylene ketal.
m/e--385 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 6.8 and 6.4 (two 1H doublets, aromatic) 5.7 (bs, 1H, phenolic), 4.0 (bs, 4H, ethylene ketal), 3.9 (bs, 2H, C-10 --CH 2 --), 3.1 (bt, 2H, C-8 --CH 2 --), 2.5 (s, 3H, 6-CH 3 ), 2.0 (bt, 2H, C-7 --CH 2 --), and other absorptions for remaining protons.
In like manner, the compounds of Examples 29-31 are converted to compounds having the formulae: ##STR56##
EXAMPLE 58
d,l-5,6,6aβ,7,10,10aα-Hexahydro-1-hydroxy-6β-methyl-3-(2-heptylsulfinyl)benzo[c]quinolin-9(8H)-one
Equimolar amounts of m-chloroperbenzoic acid and d,l-5,6,6aβ,7,10,10aα-hexahydro-1-hydroxy-6β-methyl-3-(2-heptylthio)benzo[c]quinolin-9(8H)-one are added to a mixture of chloroform and acetic acid (2:1) and the reaction mixture stirred for one hour at room temperature. The organic phase is then separated, washed with water, dried (MgSO 4 ) and evaporated to dryness to give the title product.
In like manner, the thio ethers of Examples 31, 33, 34, 43-47, 49, and 50 are oxidized to the corresponding sulfoxides.
EXAMPLE 59
d,l-trans-5,6,6a,7,10,10a-Hexahydro-1-hydroxy-6β-methyl-3-(2-heptylsulfonyl)benzo[c]quinolin-9(8H)-one
The procedure of Example 58 is repeated but using two equivalents of m-chloroperbenzoic acid or oxidizing agent per mole of thio ether reactant to give the title compound.
Similarly, the thio ethers of Examples 31, 33, 34, 43-47, 49 and 50 are oxidized to their sulfonyl derivatives.
EXAMPLE 60
Following the procedure of Example 57 but using the appropriate ketone compound of formula II, III or IV and the appropriate alkylene glycol or alkylene dithiol having formula H-X'-alkylene-X'-H wherein X' is oxygen or sulfur and alkylene has from 2 to 4 carbon atoms affords compounds having the formulae: ##STR57##
EXAMPLE 61
(2'R,6S,6aR,9R,10aR)-(-)-1-Acetoxy-5,6,6a,7,8,9,10,10a-octahydro-9-hydroxy-5,6-dimethyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline
To a stirred solution of 1.0 g. (0.0021 moles) (2'R,6S,6aR,9R,10aR)-(-)-1-acetoxy-5,6,6a,7,8,9,10,10a-octahydro-9-hydroxy-6-methyl-3-(5-phenyl-2-pentyloxy)-benzo[c]quinoline hydrochloride in 30 ml. CHCl 3 is added 30 ml. saturated NaHCO 3 solution, and the mixture stirred 5 minutes at room temperature. The layers are separated and the aqueous layer re-extracted with 20 ml. CHCl 3 . The combined chloroform layers are dried (MgSO 4 ), filered and the solvent removed in vacuo to yield the free base as a colorless foam.
This foam is dissolved in 40 ml. tetrahydrofuran and combined with 1.0 g. 5% Pd/C, 1.05 ml (0.018 moles=8.7 equiv.) glacial acetic acid and 15.8 ml. (0.20 moles=100 equiv.) 37% aqueous formaldehyde. The mixture is placed in a Parr apparatus at 50 p.s.i. and hydrogenated for 50 minutes. The catalyst is filtered through diatomaceous earth, washing well with ethyl acetate. The filtrate is diluted to 150 ml. with ethyl acetate then washed successively 3× with 100 ml. saturated NaHCO 3 solution, 75 ml. H 2 O 3×, 75 ml. brine 1×, and dried over MgSO 4 . The solvent is filtered and removed in vacuo yielding a yellow viscous oil which is chromatographed on 50 g. silica gel (0.04-0.63 mm.) and eluted with toluene/diethyl ether (1:1). Similar fractions are combined and removed in vacuo to yield a colorless oil which is redissolved in 50 ml. diethyl ether and dry HCl bubbled in under a nitrogen atmosphere with stirring. The resulting white solid is filtered under a nitrogen atmosphere and dried in vacuo (0.1 mm.) for 24 hours at room temperature to yield 0.45 g. (44%) of the title product, m.p. 90°-95° C. (d).
NMR (CDCl 3 )--2.73 ppm, singlet, 3H (N--CH 3 ).
IR (KBr)-- ##STR58##
Calc. for C 28 H 37 O 4 N.HCl: C, 68.90; H, 7.85; N, 2.87%. Found: C, 68.60; H, 7.92; N, 2.77%.
[a] D 25 =-73° (C, 1,0, methanol).
Mass spectrum m/e=451 (m + ).
The following compounds are similarly prepared: dl-1-acetoxy-5,6,6aβ,7,8,9,10,10aα-octahydro-9β-hydroxy-5,6β-dimethyl-3-(1,1-dimethylheptyl)benzo[c]quinoline hydrochloride.
m.p. 129°-130° C. (d).
m/e=415 (m + , 100%).
IR (KBr)-- ##STR59##
and dl-1-acetoxy-5,6,6aβ,7,8,9,10,10aα-octahydro-9β-hydroxy-5-methyl-6β-n-butyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline hydrochloride.
m.p. 106°-108° C.
m/e=493.
C 31 H 43 O 4 N.HCl: Calc'd.: C, 70.21; H, 8.37; N, 2.6%. Found: C, 71.02; H, 8.43; N, 2.6%.
EXAMPLE 62
Preparation of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1-methyl-4-phenylbutoxy)benzo[c]quinoline
A stirred suspension of 47.4 g. (0.10 mol) of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1-methyl-4-phenylbutoxy)benzo[c]quinoline, hydrochloride and 500 ml. of CHCl 3 under a N 2 atmosphere is cooled to 0° C. and treated with 250 ml. pyridine followed by 58 ml. (0.50 mole) benzoyl chloride in 500 ml. chloroform. The resultant homogeneous solution is then refluxed on a steam bath for one hour. The reaction mixture is poured onto crushed ice and extracted with chloroform. The organic extracts are combined, washed successively with water (2×500 ml.), 10% hydrochloric acid, saturated sodium bicarbonate solution (500 ml.) and saturated brine solution (500 ml.), dried over MgSO 4 , filtered and concentrated to give 119 g. of a light yellow oil. Chromatography on 2000 g. silica gel (20% EtOAc-cyclohexane) affords 50.5 g. (78%) of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl- 9-benzoyloxy-6β-methyl-3-(1-methyl-4-phenylbutoxy)benzo[c]quinoline, m.p. 125°-30° C.
Anal. Calcd. for C 41 H 43 O 6 N: C, 76.24; H, 6.72; N, 2.17%. Found: C, 76.35; H, 6.92; N, 2.19%.
Separation of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1α-methyl-4-phenylbutoxy)benzo[c]quinoline and dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzyloxy-6β-methyl-3-(1α-methyl-4-phenylbutoxy)benzo[c]quinoline
Recrystallization of 50.5 g. dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1-methyl-4-phenylbutoxy)benzo[c]quinoline from 2 l. 2-propanol yielded 23.8 of white solids, m.p. 136°-8°, which are recrystallized twice more from 2-propanol and once from acetonitrile to yield 5.7 g. of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline, m.p. 148°-9° C.
The filtrate from the original 2-propanol recrystallization of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1-methyl-4-phenylbutoxy)benzo[c]quinoline is evaporated to a white foam and triturated with 500 ml. ether to yield 12.9 g. of white solids, m.p. 129°-132°. These solids are triturated twice again with ether to yield 3.8 g. of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1α-methyl-4-phenylbutoxy)benzo[c]quinoline, m.p. 139°-141° C.
Preparation of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline, hydrochloride
To a stirred solution of 2.0 g. (5.3 mmol) lithium aluminum hydride in 150 ml. tetrahydrofuran under a nitrogen atmosphere is added a solution of 5.7 g. (8.8 mmole) dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline in 112 ml. tetrahydrofuran dropwise over a five minute period. The resultant mixture is heated at reflux for 45 minutes, cooled and poured carefully onto an ice cold mixture of 1125 ml. 5% acetic acid in water and 2250 ml. ether. This biphasic mixture is stirred for ten minutes and the layers separated. The aqueous layer is extracted with an additional 500 ml. ether and the combined ether extracts are washed successively with water (3×500 ml.), saturated sodium bicarbonate solution (2×500 ml.) and saturated brine solution (1×500 ml.), dried over MgSO 4 , filtered and evaporated to yield 5.4 g. dl-5-benzyl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1,9 -dihydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline as a light purple oil.
dl-5-benzyl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)-benzo[c]quinoline is immediately taken up in 450 ml. methanol and hydrogenated at atmospheric pressure over 4.27 g. Pd/C for 3 hours to yield dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline after filtration of the catalyst and evaporation of the methanol.
dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline is immediately dissolved in 210 ml. methylene chloride, cooled to 0° C. under a nitrogen atmosphere, and treated successively with 1.35 ml. triethylamine, 1.19 g. (9.7 mmol) of 4-dimethylaminopyridine and finally with 0.834 ml. (8.8 mmol) of acetic anhydride. After stirring for 30 minutes, the reaction mixture is poured onto 250 ml. of water and the organic layer separated. The aqueous layer is extracted once more with methylene chloride and the combined methylene chloride layers washed successively with a saturated sodium bicarbonate solution (2×150 ml.), water (150 ml.) and a saturated brine solution, dried over MgSO 4 , filtered, evaporated and chromatographed on 300 g. silica gel using 33% ether-toluene as eluent to give 1.4 g. dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline, hydrochloride as the free base. Treatment of dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline, hydrochloride in ether with HCl (gas) yields 795 mg. dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1β-methyl-4-phenylbutoxy)benzo[c]quinoline, hydrochloride, m.p. 213°-215° C. after filtration and trituration in acetone, m/e=437 (m + , 100%).
Anal. Calcd. for C 27 H 35 O 4 N.HCl: C, 68.42; H, 7.66; N, 2.96. Found: C, 68.48; H, 7.63; N, 3.05.
Similarly prepared from 3.8 g. dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-5-benzoyl-9-benzoyloxy-6β-methyl-3-(1α-methyl-4-phenylbutoxy)benzo[c]quinoline is 1.1 g. dl-5,6,6aβ,7,8,9α,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(1α-methyl-4-phenylbutoxy)benzo[c]quinoline hydrochloride, m.p. 202°-205° (d.), m/e=437 (100%, m + ).
Anal. Calcd. for C 27 H 35 O 4 N.HCl: C, 68.42; H, 7.66; N, 2.96. Found: C, 68.20; H, 7.56; N, 3.04.
EXAMPLE 63
d,l-5,6,6a,7-Tetrahydro-1-(4-morpholinobutyryloxy)-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one
To a solution of d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one (0.51 g., 1.5 mmole) in dry methylene chloride (25 ml.) is added 4-morpholinobutyric acid hydrochloride (0.315 g., 1.5 mmole) and the mixture stirred at room temperature under a nitrogen atmosphere. A 0.1 M solution of dicyclohexylcarbodiimide in methylene chloride (12.5 ml., 1.5 mmole) is added dropwise and the mixture stirred for 24 hours. It is then filtered and evaporated to give the title product which is purified by column chromatography on silica gel.
Repetition of this procedure but using the appropriate reactants of formula III and the appropriate alkanoic acid or acid of formula HOOC--(CH 2 ) p --NR 2 R 3 .HCl affords the following compounds: ##STR60## wherein R 1 , R 4 , R 5 , Z and W are as defined in Examples 29, 30 and 31.
______________________________________ R.sub.1______________________________________ COCH.sub.2 CH.sub.3 CO(CH.sub.2).sub.2 CH.sub.3 CO(CH.sub.2).sub.3 CH.sub.3 COCH.sub.2 NH.sub.2 CO(CH.sub.2).sub.2 NH.sub.2 CO(CH.sub.2).sub.4 NH.sub.2 CO(CH.sub.2)N(CH.sub.3).sub.2 CO(CH.sub.2).sub.2 NH(C.sub.2 H.sub.5) CO(CH.sub.2).sub.4 NHCH.sub.3 CONH.sub.2 CON(C.sub.2 H.sub.5).sub.2 CON(C.sub.4 H.sub.9).sub.2 CO(CH.sub.2).sub.3 NH(C.sub.3 H.sub.7) CO(CH.sub.2).sub.2 N(C.sub.4 H.sub.9).sub.2 COCH.sub.2 -piperidino COCH.sub.2 -pyrrolo CO(CH.sub.2).sub.2 -morpholino CO(CH.sub.2).sub.2 -N-butylpiperazino CO(CH.sub.2).sub.3 -pyrrolidino CO-piperidino CO-morpholino CO-pyrrolo CO--N-(methyl)piperazino CO--C.sub.6 H.sub.5 COCH(CH.sub.3)(CH.sub.2).sub.2 -piperidino______________________________________
Basic esters are obtained as their hydrochloride salts. Careful neutralization with sodium hydroxide affords the free basic esters.
EXAMPLE 64
d,l-trans-5,6,6aβ,7,8,9,10,10aα-Octahydro-1-(4-N-piperidylbutyryloxy)-9-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline hydrochloride
To a 25° C. solution of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline (1.0 g., 2.53 mmoles) in methylene chloride (20 ml.) is added 4-N-piperidylbutyric acid hydrochloride (0.524 g., 2.53 mmoles) and dicyclohexylcarbodiimide (0.573 g., 2.78 mmoles). The reaction mixture is stirred at 25° C. for 6 hours and then cooled for 12 hours and filtered. Evaporation of the filtrate and trituration of the residue with ether gives 1.3 g. of solid of the monohydrochloride salt.
IR (KBr): 2.95, 3.70, 5.65 (ester C═O), 6.13 and 6.27μ.
Preparative layer chromatography of a portion of this solid on 0.5 mm. thick silica gel and elution with 10% methanol-methylene dichloride affords the free base, d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-(4-N-piperidylbutyryloxy)-9-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 1.12 (d, J=7 Hz, C-3 side-chain methyl), 1.25 (d, J=6 Hz, C-6 methyl), 5.84 (s, two ArH) and 7.16 (s, 5H).
Treatment of this free base with excess hydrogen chloride in ether yields the dihydrochloride salt as a hygroscopic powder.
EXAMPLE 65
d,l-5,6,6a,7-Tetrahydro-1-(4-N-piperidylbutyryloxy)-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one hydrochloride
To a 25° C. solution of d,l-5,6,6a,7-tetrahydro-1-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline-9(8H)-one (550 mg., 1.41 mmole) in methylene chloride (26 ml.) is added 4-N-piperidylbutyric acid hydrochloride (291 mg., 1.41 mmole) and dicyclohexylcarbodiimide (319 mg., 1.55 mmole). This reaction mixture is stirred for 18 hours and is then cooled to 0° C. and filtered. Evaporation of the filtrate and trituration of the residue with ether gives 800 mg. of d,l-5,6,6a,7-tetrahydro-1-(4-N-piperidylbutyryloxy)-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline-9(8H)-one hydrochloride as a hygroscopic yellow powder.
IR (CHCl 3 ): 2.92, 4.14 (HN.sup.⊕ ═), 5.69 (ester), 6.00, 6.20 and 6.40μ.
In like manner, d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-(4-N-morpholinobutyryloxy)-9-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline hydrochloride is prepared from 4-N-morpholinobutyric acid and d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1,9-dihydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline:
IR (KBr): 3.00, 3.75, 5.67 (ester C═O), 6.15 and 6.30μ.
Similarly, the remaining compounds of formulae I, II, III and IV described herein are converted to basic esters of the hydrocy group at the 1-position. Esters wherein the R 1 moiety has the following values are prepared:
--CON(CH 3 ) 2
--CO(CH 2 ) 2 N(C 4 H 9 ) 2
--CO(CH 2 ) 3 N(CH 3 ) 2
--CO(CH 2 ) 3 pyrrolidino
--CO(CH 2 ) 2 --N-(methyl)piperazino
--CO--CH 2 -pyrrolo
EXAMPLE 66
d,l-7,10-Dihydro-1-hydroxy-3-(2-heptyloxy)-6-methylbenzo[c]quinolin-9(8H)-one Ethylene Ketal
A solution of d,l-7,10-dihydro-1-hydroxy-3-(2-heptyloxy)benzo[c]quinolin-9(8H)-one ethylene ketal (371 mg., 1.0 mmole) in ether (50 ml.) is slowly added to an ice-cold solution of methyl-lithium (44 mg., 2.0 mmole) in ether (25 ml.) The 5-lithio-6-methyl derivative thus obtained is dissolved in dry ether and treated with dry oxygen to give, after filtration and evaporation of the solvent, the title compound.
Hydrolysis of the ketal according to standard procedures affords the 9-ketone.
Repetition of this procedure but using the compounds of Example 57 and the appropriate alkyl lithium, aralkyl lithium reactant or, when R 4 is hydrogen, lithium aluminum hydride, affords compounds having the formula ##STR61## wherein Z and W are as defined in Example 57 and R 4 is methyl, n-butyl, n-hexyl, benzyl, phenethyl, 4-phenylbutyl or hydrogen.
EXAMPLE 67
General Hydrochloride Salt Formation
Excess hydrogen chloride is passed into a solution of the appropriate benzo[c]quinoline of formulae I or II and the resulting precipitate separated and recrystallized from an appropriate solvent, e.g. methanol-ether (1:10).
In this manner the following salt is prepared:
d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9β-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline, m.p. 191°-193° C.
m/e--437 (m + )
Analysis: Calc'd for C 27 H 36 O 4 NCl: C, 68.48; H, 7.70; N, 2.89%. Found: C, 68.42; H, 7.66; N, 2.96%.
The remaining compounds of formulae I and II are converted to their hydrochlorides in like manner.
Similarly, the hydrobromide, sulfate, nitrate, phosphate, acetate, butyrate, citrate, malonate, maleate, fumarate, malate, glycolate, gluconate, lactate, salicylate, sulfosalicylate, succinate, pamoate, tartrate and embonate salts are prepared.
EXAMPLE 68
One hundred mg. of d,l-trans-5,6,6aβα,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-5-methyl-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline are intimately mixed and ground with 900 mg. of starch. The mixture is then loaded into telescoping gelatin capsules such that each capsule contains 10 mg. of drug and 90 mg. of starch.
EXAMPLE 69
A tablet base is prepared by blending the ingredients listed below:
Sucrose: 80.3 parts
Tapioca starch: 13.2 parts
Magnesium stearate: 6.5 parts
Sufficient d,l-cis-5,6,6aβ,7,10,10aα-hexahydro-1-acetoxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinolin-9(8H)-one is blended into this base to provide tablets containing 0.1, 0.5, 1, 5, 10 and 25 mg. of drug.
EXAMPLE 70
Suspensions of d,l-trans-5,6,6aβ,7,8,9,10,10aα-octahydro-1-acetoxy-9-hydroxy-6β-methyl-3-(5-phenyl-2-pentyloxy)benzo[c]quinoline are prepared by adding sufficient amounts of drug to 0.5% methylcellulose to provide suspensions having 0.05, 0.1, 0.5, 1, 5 and 10 mg. of drug per ml.
PREPARATION A
2-Bromo-5-phenylpentane
To phosphorous pentabromide, prepared by addition of bromine (9.0 g.) in methylene chloride (10 ml.) to phosphorous tribromide (15.0 g.) in methylene chloride (15 ml.) at 0° C., is added 5-phenyl-2-pentanol (812 g.) in methylene chloride at 0° C. The mixture is stirred for 2.5 hours at 0° C. and is then allowed to warm to room temperature. Water (50 ml.) is added, the mixture stirred for one hour and the methylene chloride layer separated. The extraction is repeated and the combined extracts washed with water, saturated sodium bicarbonate solution, brine and then dried over magnesium sulfate. Concentration of the dried extracts gives 12.4 g. of title product as a light yellow oil.
NMR: δ CDCl .sbsb.3 TMS 1.6 (D,3,methyl,J=7 Hz), 1.6-2.0 (M,4,ethylene), 2.3-3.0 (bd,T,2,benzylic-methylene), 3.7-4.2 (M,1,methine), 6.9-7.4 (M,5,aromatic).
PREPARATION B
2-(3,5-Dimethoxyphenyl)-5-phenylpentane
A solution of 1-bromopropylbenzene (51.7 g.) in ether (234 ml.) is added dropwise over a 2-hour period to a refluxing mixture of magnesium (7.32 g.) in ether (78 ml.). The reaction mixture is refluxed for 30 minutes longer and then a solution of 3,5-dimethoxy-acetophenone (50 g.) in ether (78 ml.) is added dropwise and heated to reflux for 1.5 hours. The reaction is quenched by addition of saturated ammonium chloride (234 ml.), the ether layer is separated and the aqueous phase extracted with ether (3×200 ml.). The combined ether extracts are dried over magnesium sulfate and concentrated under vacuum to yield 81 g. of an oil. Forty grams of the oil is hydrogenated in a mixture containing ethanol (300 ml.), concentrated hydrochloric acid (2 ml.) and 5% palladium-on-carbon (5 g.). The catalyst is filtered off and the ethanol removed under vacuum. The residue is distilled under vacuum yielding 28 g. of 2-(3,5-dimethoxyphenyl)-5-phenylpentane (b.p. 0.125 mm., 154°-159° C.)
NMR: δ CDCl .sbsb.3 TMS 1.25 (d,3,α--CH 3 ), 1.3-2.1 (M,4,ethylene), 2.2-2.9 (M,3,benzylic-methylene,methinyl), 3.45 (S,6,methoxyl), 6.2-6.7 (M,3,aromatic), 7.2 (S,5,aromatic).
PREPARATION C
2-(3,5-Dihydroxyphenyl)-5-phenylpentane
A mixture of 2-(3,5-dimethoxyphenyl)-5-phenylpentane (22 g.) and pyridine hydrochloride (94 g.) under nitrogen is heated to 190° C. for 2 hours with vigorous stirring. The reaction mixture is cooled, dissolved in 6 N hydrochloric acid (200 ml.) and diluted with water to 600 ml. The aqueous solution is extracted with ethyl acetate (4×100 ml.), the ethyl acetate extracts dried over sodium sulfate and concentrated under vacuum to yield 24 g. of crude product. The product is purified by silica gel chromatography to yield 19.2 g. of 2-(3,5-dihydroxyphenyl)-5-phenylpentane as an oil.
NMR: δ CDCl .sbsb.3 TMS 1.1 (d,3,α-methyl), 1.35-1.65 (M,4,ethylene), 2.2-2.8 (M,3,benzylic-methylene,methinyl), 6.1-6.5 (M,3,aromatic), 6.65 (bd.S,2,hydroxyl), 7-7.4 (M,5,aromatic).
Following the procedures of Preparations B and C, the compounds listed below are prepared by substituting the appropriate 1-bromoalkylbenzene for 1-bromopropylbenzene:
2-(3,5-dihydroxyphenyl)-6-phenylhexane
NMR: δ CDCl .sbsb.3 TMS 1.1 (D,3,α-methyl, J-7 cps), 1.0-1.9 [M,6,φCH 2 (CH 2 ) 3 --CH(CH 3 )--Ar], 2.2-2.8 (M,3,benzylic methylene, methinyl), 6.0 (bd.S,2,phenolic OH), 6.2-6.4 (M,3,aromatic), 7.1-7.4 (M,5,aromatic).
1-(3,5-dihydroxyphenyl)-2-phenylethane
m.p.: 76°-77° C.
2-(3,5-dihydroxyphenyl-4-phenylbutane (an oil)
NMR: δ CDCl .sbsb.3 TMS 1.1, 1.25 (d,2,methyl), 1.45-2.0 (M,2,methylene), 2.15-2.7 (M,3,benzylic-methylene,methinyl), 6.3 (S,3,aromatic), 6.85 (S,2,hydroxyl-D 2 O overlay), 7.1 (S,5,aromatic).
The following compounds are prepared in like manner from the appropriate alcohol and 3,5-dimethoxybenzaldehyde or 3,5-dimethoxyacetophenone by the methods of Preparations A, B and C:
______________________________________ ##STR62##Z W______________________________________CH(CH.sub.3)CH.sub.2 C.sub.5 H.sub.9CH(CH.sub.3) (CH.sub.2).sub.2 C.sub.5 H.sub.9CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.5CH(CH.sub.3)CH(CH.sub.3) C.sub.6 H.sub.11CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.11CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.5 H.sub.9CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 C.sub.6 H.sub.11(CH.sub.2).sub.3 C.sub.5 H.sub.9CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 C.sub.6 H.sub.5C(CH.sub.3).sub.2 C.sub.6 H.sub.5(CH.sub.2).sub.4 C.sub.6 H.sub.5(CH.sub.2).sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5CH(CH.sub.3)CH.sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5______________________________________
PREPARATION D
1-(3,5-Dihydroxyphenyl)-2-methyl-4-phenylbutane
A solution of n-butyl lithium (29 ml. of 2.2 M) is added dropwise to 3,5-dimethoxybenzyl triphenylphosphonium bromide (31.5 g.) in tetrahydrofuran (200 ml.) with stirring and the resulting deep red solution is stirred for one-half hour. Benzyl acetone (9.4 g.) is added dropwise and the reaction mixture stirred for 12 hours. It is then adjusted to pH 7 by addition of acetic acid and concentrated under reduced pressure. The residue is extracted with methylene chloride and the extract evaporated to give crude 1-(3,5-dimethoxyphenyl)-2-methyl-4-phenyl-1-butene as an oil. It is purified by chromatography on silica gel (400 g.) and elution with benzene. Yield: 10 g. as an oil.
NMR: δ CDCl .sbsb.3 TMS 1.95 (S,3), 2.3-3.1 (M,4), 3.8 (S,6), 6.15-6.6 (M,3), 7.1-7.5 δ(M,6).
The 1-(3,5-dimethoxyphenyl)-2-methyl-4-phenyl-1-butene (9.4 g.) thus prepared is dissolved in ethanol (250 ml.) and catalytically hydrogenated at 45 p.s.i. in the presence of palladium-on-charcoal (1 g. of 10%) and concentrated hydrochloric acid (1 ml.). Yield: 9.4 g. of 1-(3,5-dimethoxyphenyl)-2-methyl-4-phenylbutane as an oil.
NMR: δ CDCl .sbsb.3 TMS 0.9 (d,3), 1.35-1.95 (M,3), 2.2-2.9 (M,4), 3.75 (S,6), 6.35 (S,3), 7.25 δ(S,5).
It is demethylated according to the procedure of Preparation C to give 1-(3,5-dihydroxyphenyl)-2-methyl-4-phenylbutane.
The 3,5-dimethoxybenzyl triphenylphosphonium bromide is prepared by refluxing a mixture of 3,5-dimethoxybenzyl bromide (12 g.) and triphenylphosphine (14.2 g.) in acetonitrile (200 ml.) for one hour. The reaction mixture is then cooled and the crystalline product recovered by filtration, washed with ether and dried (20 g.); m.p. 269°-270° C.
PREPARATION E
2-Methyl-2-(3,5-dihydroxyphenyl)-5-phenylpentane
To a solution of the Grignard reagent prepared from 2-phenylbromoethane (5.5 g.), magnesium (0.8 g.) and dry ether (60 ml.) is added a solution of 2-methyl-2-(3,5-dimethoxyphenyl)propionitrile (2.75 g.) in dry ether (20 ml.). The ether is distilled off and replaced by dry benzene (50 ml.) and the mixture refluxed for 48 hours. It is then decomposed by careful treatment with dilute sulfuric acid and heated on a steam bath for one hour. The mixture is then extracted with ether, the extract dried (MgSO 4 ) and concentrated to an oil. Distillation of the oil in vacuo affords 2-methyl-2-(3,5-dimethoxyphenyl)-5-phenyl-3-pentanone; b.p. 168° C./0.2 mm. (Yield: 2.32 g., 60%)
The thus-produced pentanone (58 g.) is dissolved in ethanol (400 ml.) and treated with sodium borohydride (10 g.) at room temperature. The reaction mixture is stirred for 12 hours and is then cooled and neutralized with 6 N hydrochloric acid. The ethanol is removed under reduced pressure and the residue extracted with ether. The extract is dried (MgSO 4 ) and concentrated to give 2-methyl-2-(3,5-dimethoxyphenyl)-5-phenyl-3-pentanol as an oil (52 g., 88% yield).
The pentanol (16 g.) is taken up in ether (100 ml.) and reacted with powdered potassium (2.5 g.) in ether (200 ml.). Carbon disulfide (equimolar to the potassium) is added and the mixture stirred for a half-hour. Methyl iodide (9.0 g.) is then added and the reaction mixture stirred for 6 hours. The resulting suspension is filtered and the filtrate concentrated under reduced pressure. The residue is taken up in ethanol (150 ml.), Raney nickel added (25 g.) and the mixture refluxed for 18 hours. Evaporation of the alcohol and distillation of the residue gives 2-methyl-2-(3,5-dimethoxyphenyl)-5-phenyl-3-pentene.
The pentene derivative is catalytically hydrogenated according to the procedure of Preparation D and the resulting 2-methyl-2-(3,5-dimethoxyphenyl)-5-phenyl-3-pentane demethylated via the procedure of Preparation C to give the product.
PREPARATION F
3,5-Dibenzyloxyacetophenone
Over a period of 1.5 hours, methyl lithium (531 ml. of a 2 molar solution, 1.06 M) is added under a nitrogen atmosphere to a rapidly stirring solution of 3,5-dibenzyloxybenzoic acid (175 g., 0.532 M) in ether (250 ml.)tetrahydrofuran (1400 ml.) maintained at 15°-20° C. After stirring an additional 0.75 hour at 10°-15° C., water (600 ml.) is slowly added keeping the reaction temperature below 20° C. The aqueous layer is separated and extracted with ether (3×250 ml.). The organic phases are combined, washed with saturated sodium chloride solution (4×300 ml.), dried over sodium sulfate, and concentrated under vacuum to give an oil which slowly crystallized from isopropyl ether. The crude product is recrystallized from ether-hexane to yield 104.7 g. (59%) of product; m.p. 59°-61° C.
PREPARATION G
Ethyl 3-(3,5-dibenzyloxyphenyl)crotonate (Wittig Reaction)
A mixture of 3,5-dibenzyloxyacetophenone (43.2 g., 0.13 mole) and carbethoxymethylenetriphenylphosphorane (90.5 g., 0.26 mole) is heated under a nitrogen atmosphere at 170° C. for 4 hours. The clear melt is cooled to room temperature, triturated with ether and the precipitate of triphenyl phosphine oxide removed by filtration. The filtrate is concentrated under vacuum to an oily residue which is chromatographed over silica gel (1500 g.) and eluted with benzene:hexane solutions of increasing benzene concentration beginning with 40:60 and ending with 100% benzene. Concentration of appropriate fractions gives an oily residue which is crystallized from hexane. Yield: 40.2 g. (77%); m.p. 73°-75° C.
Analysis: Calc'd for C 26 H 26 O 4 : C, 77.58; H, 6.51%. Found: C, 77.72; H, 6.60%.
In like manner, ethyl 3-(3,5-dimethoxyphenyl)crotonate is prepared from 3,5-dimethoxyacetophenone (51.7 g.) and carbethoxymethylene triphenylphosphorane (200 g.). Yield=61.8 g., 86%, b.p. 146°-162° C. at 0.3 mm.
PREPARATION H
3-(3,5-Dibenzyloxyphenyl)-1-butanol
A solution of ethyl 3-(3,5-dibenzyloxyphenyl)crotonate (24.1 g., 60 mM) in ether (250 ml.) is added to a mixture of lithium aluminum hydride (3.42 g., 90 mM) and ether (250 ml.). Aluminum chloride (0.18 g., 1.35 mM) is added and the mixture refluxed for 12 hours and then cooled. Water (3.4 ml.), sodium hydroxide (3.4 ml. of 6 N) and water (10 ml.) are then added successively to the reaction mixture. The inorganic salts which precipitate are filtered off and the filtrate is then concentrated in vacuo to give the desired alcohol as an oil--2.4 g. (98%).
R f =0.25 [silica gel:benzene(18):ethyl acetate(1)].
m/e--362 (m + )
Analysis: Calc'd for C 24 H 26 O 3 : C, 79.53; H, 7.23%. Found: C, 79.37; H, 7.11%.
In like manner, ethyl 3-(3,5-dimethoxyphenyl)crotonate (60.4 g.) is reduced to 3-(3,5-dimethoxyphenyl)butanol (48.0 g., 90%).
PREPARATION I
3-(3,5-Dibenzyloxyphenyl)butyl Tosylate
Tosyl chloride (11.1 g., 58.1 mM) is added to a solution of 3-(3,5-dibenzyloxyphenyl)-1-butanol (20.7 g., 57 mM) in pyridine (90 ml.) at -45° C. The reaction mixture is held at -35° C. for 18 hours and is then diluted with cold 2 N hydrochloric acid (1500 ml.) and extracted with ether (5×250 ml.). The combined extracts are washed with saturated sodium chloride solution (4×250 ml.) and then dried (Na 2 SO 4 ). Concentration of the dried extract affords the product as an oil. It is crystallized by treatment with ether-hexane. Yield: 24.63 g. (84%).
Analysis: Calc'd for C 31 H 32 O 5 S: C, 72.06; H, 6.24%. Found: C, 72.05; H, 6.29%.
PREPARATION J
3-(3,5-Dibenzyloxyphenyl)-1-phenoxybutane
A solution of phenol (4.56 g., 48.6 mM) in dimethylformamide (40 ml.) is added under a nitrogen atmosphere to a suspension of sodium hydride (2.32 g., 48.6 mM of 50% previously washed with pentane) in dimethylformamide (70 ml.) at 60° C. The reaction mixture is stirred for one hour at 60°-70° C., after which a solution of 3-(3,5-dibenzyloxyphenyl)butyl tosylate (23.93 g., 46.3 mM) in dimethylformamide (80 ml.) is added. The reaction mixture is stirred at 80° C. for a half-hour and is then cooled to room temperature, diluted with cold water (2500 ml.) and extracted with ether (4×400 ml.). The combined extracts are washed successively with cold 2 N hydrochloric acid (2×300 ml.) and saturated sodium chloride solution (3×300 ml.) and then dried (Na 2 SO 4 ). Removal of the solvent under reduced pressure affords the product as an oil. The oily residue is dissolved in benzene and filtered through silica gel (100 g.). Concentration of the filtrate under reduced pressure gives the product as an oil. Yield: 14.86 g. (73%).
R f =0.7 (silica gel, benzene).
m/e--438 (m + )
Analysis: Calc'd for C 30 H 30 O 3 : C, 82.16; H, 6.89%. Found: C, 82.07; H, 6.84%.
Repetition of Procedures G through J, but using the 3,5-dibenzyloxy derivatives of benzaldehyde, acetophenone or propiophenone, the appropriate carbethoxy (or carbomethoxy) alkylidene triphenyl phosphorane; and the appropriate alcohol, phenol, thiophenol, hydroxypyridine or hydroxypiperidine as reactants affords the following compounds: ##STR63##
For convenience, the various values of W for given values of --(alk 1 )--X--(alk 2 ) n -- are collectively tabulated.
__________________________________________________________________________ alk.sub.1 X alk.sub.2 n W__________________________________________________________________________(CH.sub.2).sub.3 0 -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, C.sub.4 H.sub.7, 4-ClC.sub.6 H.sub.4, C.sub.6 H.sub.11, 4-pyridyl, 3-pyridyl, 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10, 4-piperidyl, CH.sub.3, 4-(4-FC.sub.6 H.sub.4)C.sub.6 H.sub.10.(CH.sub.2).sub.3 0 CH.sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, C.sub.6 H.sub.11, 4-piperidyl, CH.sub.3.(CH.sub.2).sub.3 0 (CH.sub.2).sub.2 1 C.sub.6 H.sub.5, CH.sub.3, 4-ClC.sub.6 H.sub.4, 4-pyridyl.(CH.sub.2).sub.3 0 CH(CH.sub.3) 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, CH.sub.3, 4-piperidyl, 2-pyridyl.(CH.sub.2).sub.3 0 CH(CH.sub.3)(CH.sub.2).sub.2 1 C.sub.6 H.sub.5, 4-pyridyl, CH.sub.3.CH(CH.sub.3)(CH.sub.2).sub.2 0 -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub. 4, C.sub.6 H.sub.11, C.sub.3 H.sub.5, 4-pyridyl, C.sub.7 H.sub.13, 3-piperidyl, CH.sub.3, 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10, 2-(4-ClC.sub.6 H.sub.4)C.sub.4 H.sub.6.CH(CH.sub.3)(CH.sub.2).sub.2 0 CH.sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-pyridyl, 2-piperidyl, CH.sub.3.CH(CH.sub.3)(CH.sub.2).sub.2 0 (CH.sub.2).sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-pyridyl, 4-piperidyl, CH.sub.3, C.sub.5 H.sub.9.CH(CH.sub.3)(CH.sub.2).sub.2 0 (CH.sub.2).sub.4 1 C.sub.6 H.sub.5, 4-pyridyl, 2-piperidyl, CH.sub.3, 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10.CH(CH.sub.3)(CH.sub.2).sub.2 0 (CH.sub.2).sub.2 CH(CH.sub.3) 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, CH.sub.3, C.sub.3 H.sub.5.CH(CH.sub.3)(CH.sub.2).sub.2 0 CH(CH.sub.3) C.sub.6 H.sub.5, 4-ClC.sub.6 H.sub.4, CH.sub.3, 3-piperidyl, C.sub.7 H.sub.13.CH(CH.sub.3)(CH.sub.2).sub. 2 0 CH.sub.2 CH(C.sub.2 H.sub.5) 1 C.sub.6 H.sub.5, CH.sub.3, C.sub.6 H.sub.11.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 0 -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 2-pyridyl, CH.sub.3, 4-piperidyl, C.sub.3 H.sub.5, 2-(4-FC.sub.6 H.sub.4)C.sub.7 H.sub.12.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 0 (CH.sub.2).sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-pyridyl, C.sub.6 H.sub.11 2-piperidyl, CH.sub.3.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 0 (CH.sub.2).sub.4 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-pyridyl, C.sub.3 H.sub.5, C.sub.5 H.sub.9.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 0 CH(CH.sub.3) 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, CH.sub.3, 2-pyridyl, 4-piperidyl, C.sub.6 H.sub.11.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 0 (CH.sub.2).sub.2 CH(CH.sub.3) 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, C.sub.7 H.sub.13.(CH.sub.2 ).sub.4 0 -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-ClC.sub.6 H.sub.4, 4-pyridyl, C.sub.4 H.sub.7, 2-piperidyl, CH.sub.3.(CH.sub.2).sub.4 0 CH.sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-pyridyl, 3-pyridyl, 4-piperidyl, CH.sub.3, C.sub.6 H.sub.11.(CH.sub.2).sub.4 0 CH.sub.2 CH(CH.sub.3) 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10.(CH.sub.2).sub.4 0 CH(CH.sub.3)CH.sub.2 1 C.sub.6 H.sub.5, CH.sub.3, 2-pyridyl, 3-piperidyl, 4-piperidyl, 4-FC.sub.6 H.sub.4.(CH.sub.2).sub.4 0 (CH.sub.2).sub.5 1 C.sub.6 H.sub.5, 4-pyridyl, 3-piperidyl, 4-ClC.sub.6 H.sub.4.(CH.sub.2).sub.3 S -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-ClC.sub.6 H.sub.4, 4-pyridyl, 2-pyridyl, 2-piperidyl, 4-piperidyl, CH.sub.3, C.sub.3 H.sub.5, C.sub.5 H.sub.9, C.sub.6 H.sub.11, 4-(ClC.sub.6 H.sub.4)C.su b.6 H.sub.10.(CH.sub.2).sub.3 S CH.sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, CH.sub.3, 2-pyridyl, 4-pyridyl, 3-piperidyl, C.sub.5 H.sub.9.(CH.sub.2).sub.3 S (CH.sub.2).sub.2 1 C.sub.6 H.sub.5, 4-ClC.sub.6 H.sub.4, 4-pyridyl, CH.sub.3, C.sub.3 H.sub.5.(CH.sub.2).sub.3 S (CH.sub.2).sub.4 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-pyridyl, CH.sub.3, 4-piperidyl, C.sub.6 H.sub.11.CH(CH.sub.3)(CH.sub.2).sub.2 S -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, C.sub.6 H.sub.11, CH.sub.3, 4-pyridyl, 3-pyridyl, 4-piperidyl, C.sub.3 H.sub.7, 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10.CH(CH.sub.3)(CH.sub.2).sub.2 S CH.sub.2 1 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, CH.sub.3, 2-pyridyl.CH(CH.sub.3)(CH.sub.2).sub.2 S (CH.sub.2).sub.2 1 C.sub.6 H.sub.5, 4-ClC.sub.6 H.sub.4, CH.sub.3, 4-pyridyl, 3-piperidyl.CH(CH.sub.3)(CH.sub.2).sub.2 S (CH.sub.2).sub.4 1 C.sub.6 H.sub.5 , CH.sub.3, 4-pyridyl.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 S -- 0 C.sub.6 H.sub.5, 4-FC.sub.6 H.sub.4, 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10, 4-pyridyl, 3-pyridyl, 2-piperidyl, C.sub.6 H.sub.11.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 S CH( CH.sub.3) 1 C.sub.6 H.sub.5, 4-ClC.sub.6 H.sub.4, CH.sub.3, 4-piperidyl.CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 S (CH.sub.2).sub.2 CH(CH.sub.3) 1 C.sub.6 H.sub.5, CH.sub.3, 4-pyridyl.CH(CH.sub.3)(CH.sub.2).sub.3 0 -- 0 C.sub.6 H.sub.5, CH.sub.3, 4-FC.sub.6 H.sub.4, 4-pyridyl, C.sub.3 H.sub.5, C.sub.7 H.sub.13, 2-(4-FC.sub.6 H.sub.4)C.sub.5 H.sub.8.CH(CH.sub.3)(CH.sub.2).sub.3 0 (CH.sub.2).sub.2 1 C.sub.6 H.sub.5, CH.sub.3, 3-pyridyl, C.sub.6 H.sub.11.CH(CH.sub.3)(CH.sub.2).sub.3 S -- 0 C.sub.6 H.sub.5, CH.sub.3, 4-ClC.sub.6 H.sub.4, 2-pyridyl, C.sub.6 H.sub.11, 3-(4-ClC.sub.6 H.sub.4)C.sub.6 H.sub.10.CH(CH.sub.3)(CH.sub.2).sub.3 S (CH.sub.2).sub.4 1 CH.sub.3, C.sub.6 H.sub.5, 4-F.sub.6 C.sub.4, 4-pyridyl.__________________________________________________________________________
PREPARATION K
3-(3,5-Dihydroxyphenyl)-1-phenoxybutane
A solution of 3-(3,5-benzyloxyphenyl)-1-phenoxybutane (14.7 g., 133.5 mM) in a mixture of ethyl acetate (110 ml.), ethanol (110 ml.) and concentrated hydrochloric acid (0.7 ml.) is hydrogenated for 2 hours under 60 p.s.i. hydrogen in the presence of 10% palladium-on-carbon (1.5 g.). Removal of the catalyst by filtration and concentration of the filtrate gives an oil. The oil is purified by chromatography on silica gel (100 g.) and eluting with benzene-ethyl acetate consisting of 0-10% ethyl acetate. The middle fractions are combined and concentrated to give the title product: 7.8 g. (80%), as an oil.
R f =0.25 [silica gel, benzene(4), methanol(1)].
m/e--258 (m + ).
Analysis: Calc'd for C 16 H 18 O 3 : C, 74.39; H, 7.02%. Found: C, 74.13; H, 7.00%.
In like manner, the remaining ethers (X=O) of Preparation J are debenzylated to afford the corresponding 3,5-dihydroxy derivatives.
The thio ethers are debenzylated by treatment with trifluoroacetic acid. The procedure comprises stirring a solution of the dibenzyl ether (X=S) in trifluoroacetic acid at room temperature for two hours. The reaction mixture is evaporated to dryness and the residue taken up in ether. The ether solution is washed with water, dried (MgSO 4 ) and evaporated to give the debenzylated compound.
PREPARATION L
1-Bromo-3-(3,5-dimethoxyphenyl)butane
A solution of phosphorous tribromide (5.7 ml., 0.06 mole) in ether (30 ml.) is added to a solution of 3-(3,5-dimethoxyphenyl)-1-butanol (30.0 g., 0.143 mole) in ether (20 ml.) at -5° C. to -10° C. and the reaction mixture stirred at -5° C. to -10° C. for 2.5 hours. It is then warmed to room temperature and stirred for an additional 30 minutes. The mixture is poured over ice (200 g.) and the resulting mixture extracted with ether (3×50 ml.). The combined extracts are washed with 5% sodium hydroxide solution (3×50 ml.), saturated sodium chloride solution (1×50 ml.) and dried (Na 2 SO 4 ). Removal of the ether and vacuum distillation of the residue affords the title product; 25 g. (55% yield); b.p. 125°-132° C. at 0.4 mm.
The following compounds are prepared from 3,5-dimethoxybenzaldehyde, 3,5-dimethoxyacetophenone and 3,5-dimethoxypropiophenone and the appropriate carbethoxyalkylidene triphenylphosphorane by the procedures of Preparations G, H and L.
______________________________________ ##STR64## Z______________________________________ (CH.sub.2).sub.3 (CH.sub.2).sub.4 C(C.sub.2 H.sub.5)CH.sub.2______________________________________
PREPARATION M
4-(3,5-Dihydroxyphenyl)-1-(4-pyridyl)pentane
A mixture of 3-(3,5-dimethoxyphenyl)butyl triphenylphosphonium bromide (19.0 g., 35.4 mmoles) in dimethylsulfoxide (50 ml.) is added to 4-pyridinecarboxaldehyde (3.79 g., 35.4 mmoles) in tetrahydrofuran (40 ml.). The resulting mixture is then added dropwise to a slurry of 50% sodium hydride (1.87 g., 39 mmoles) in tetrahydrofuran (20 ml.) under a nitrogen atmosphere at 0°-5° C. Following completion of addition, the mixture is stirred for one hour at 0°-5° C. and then concentrated under reduced pressure. The concentrate is diluted with water (200 ml.) and then acidified with 6 N HCl. The aqueous acid solution is extracted with benzene (4×50 ml.). It is then made basic and extracted with ethyl acetate (3×50 ml.). Evaporation of the combined extracts after drying (MgSO 4 ) affords 4-(3,5-dimethoxyphenyl)-1-(4-pyridyl)-1-pentene (7.1 g., 70%) as an oil.
Catalytic hydrogenation of the thus-produced pentene derivative according to the procedure given in Preparation D gives 4-(3,5-dimethoxyphenyl)-1-(4-pyridyl)pentane in quantitative yield; m.p. 131°-133° C.
The pentane derivative thus obtained is demethylated by heating a mixture of the compound (7.15 g., 25 mmoles) and pyridine hydrochloride ( 35 g.) under a nitrogen atmosphere at 210° C. for 8 hours. The hot mixture is poured into water (40 ml.) and the resulting solution made basic with 6 N sodium hydroxide. Water and pyridine are removed by distillation in vacuo. Ethanol (50 ml.) is added to the residue and the inorganic salts which precipitate are filtered off. The filtrate is concentrated in vacuo and the residue chromatographed on silica gel (150 g.) using as eluting agents 5% ethanol/benzene (4 liters), 10% ethanol/benzene (1 liter), 13% ethanol/benzene (1 liter) and 16% ethanol/benzene (5 liters). The product is isolated as a glassy solid by concentration of appropriate fractions of the eluate. Yield=5.0 g (78%).
The 3-(3,5-dimethoxyphenyl)butyltriphenylphosphonium bromide is prepared by refluxing a mixture of 1-bromo-3-(3,5-dimethoxyphenyl)butane (21.5 g., 78.5 mmoles) and triphenyl phosphine (20.5 g., 78.5 mmoles) in xylene (60 ml.) for 18 hours. The reaction mixture is then cooled to room temperature and filtered. The filter cake is washed with ether and dried in a vacuum desicator to give 36.4 g. (86%) yield of product; m.p. 190°-200° C.
Repetition of this procedure but using the appropriate bromo-(3,5-dimethoxyphenyl)alkane and the appropriate aldehyde or ketone affords the following compounds.
______________________________________ ##STR65##Z W______________________________________(CH.sub.2).sub.3 2-pyridyl(CH.sub.2).sub.3 3-pyridyl(CH.sub.2).sub.3 4-pyridyl(CH.sub.2).sub.3 2-piperidyl(CH.sub.2).sub.3 4-piperidyl(CH.sub.2).sub.4 2-pyridyl(CH.sub.2).sub.4 4-pyridyl(CH.sub.2).sub.4 3-piperidyl(CH.sub.2).sub.4 4-piperidylCH.sub.2 CH(CH.sub.3)CH.sub.2 2-pyridylCH.sub.2 CH(CH.sub.3)CH.sub.2 4-piperidylCH(CH.sub.3)CH(CH.sub.3)CH.sub. 2 3-pyridylCH(CH.sub.3)CH(CH.sub.3)CH.sub.2 4-pyridylCH(CH.sub.3)CH(CH.sub.3)CH.sub.2 3-piperidylCH(CH.sub.3 )(CH.sub. 2).sub.2 2-pyridylCH(CH.sub.3)(CH.sub.2).sub.2 3-pyridylCH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylCH(CH.sub.3)(CH.sub.2).sub.3 3-pyridylCH(CH.sub.3)(CH.sub.2).sub.3 4-piperidylCH(CH.sub.3)CH(C.sub.2 H.sub.5 )CH.sub.2 4-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 2-piperidylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-piperidylCH.sub.2 CH(C.sub.2 H.sub.5)CH.sub.2 3-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2 ).sub.3 3-pyridylCH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 4-piperidylCH(C.sub.2 H.sub.5)CH(CH.sub.3)CH.sub.2 2-pyridylCH(C.sub.2 H.sub.5)CH(C.sub.2 H.sub.5)CH.sub.2 4-pyridylCH(C.sub.2 H.sub.5)CH(C.sub.2 H.sub.5)CH.sub.2 2-piperidyl(CH.sub.2).sub.3 C.sub.6 H.sub.11CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.11(CH.sub.2).sub.4 C.sub.3 H.sub.5(CH.sub.2).sub.2 C.sub.4 H.sub.7CH.sub.2 CH(CH.sub.3)CH.sub.2 C.sub.5 H.sub.9CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13CH(CH.sub.3)CH(CH.sub. 3)CH.sub.2 C.sub.6 H.sub.11(CH.sub.2).sub.6 C.sub.6 H.sub.5(CH.sub.2).sub.7 C.sub.6 H.sub.5(CH.sub.2).sub.8 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.6 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4C(CH.sub.3).sub.2 (CH.sub.2).sub.3 C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.3 4-ClC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2).sub.4 4-ClC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2) 4-ClC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2) 4-FC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4(CH.sub.2).sub.3 CH(CH.sub.3) C.sub.6 H.sub.11CH(CH.sub.3 )(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.5CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.11CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) 4-piperidylCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.11CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.11(CH.sub.2).sub.3 C.sub.6 H.sub.11(CH.sub.2).sub.4 C.sub.6 H.sub.11(CH.sub.2).sub.8 C.sub.6 H.sub.11______________________________________
PREPARATION N
3,5-Dimethoxy-α-methylstyrene Oxide
To a solution of dimethylsulfoxonium methylide (69.4 mM) in dimethyl sulfoxide (65 ml.) at room temperature is added solid 3,5-dimethoxyacetophenone (10 g., 55.5 mM). The reaction mixture is stirred for one hour at 25° C., for one-half hour at 50° C. and is then cooled. The mixture is diluted with water (50 ml.) and added to a mixture of ice water (200 ml.)--ether (250 ml.)--low boiling petroleum ether (25 ml.). The organic extract is washed twice with water (250 ml.), dried (MgSO 4 ) and evaporated to an oil. Fractional distillation of the oil yields 8.0 g. (75%) of 3,5-dimethoxy-α-methylstyrene oxide, b.p. 93°-97° C., 0.2 mm.
IR (CCl 4 ): 2780, 1595, 1196, 1151, 1058 cm -1 .
UV (95% ethanol): λ max =279 nm (ε=2068).
m/e--194 (m + ).
PMR (CDCl 3 ) (60 MHz): δ 1.70 (S,CH 3 --), ##STR66## 3.81 (S,CH 3 O--), 6.41 (t,J=2 Hz, ArH) and 6.58 (d,J=2 Hz, ArH).
Analysis: Calc'd for C 11 H 14 O 3 : C, 68.02; H, 7.27%. Found: C, 67.96; H, 7.28%.
PREPARATION O
2-(3,5-Dimethoxyphenyl)-2-hydroxypropyl-2-phenylethyl Ether
A mixture of dry 2-phenylethanol (30 ml., 251 mM) and sodium metal (690 mg., 30 mM) is heated at 110° C. for 30 minutes. The resulting 1 M solution of sodium 2-phenylethoxide is cooled to 60° C., 3,5-dimethoxy-α-methylstyrene oxide ( 2 g., 10.3 mM) added and the reaction heated 15 hours at 60° C. The reaction mixture is cooled and added to a mixture of ether and water. The ether extract is dried over magnesium sulfate and evaporated. Excess 2-phenylethanol is removed by vacuum distillation (b.p. -65° C., 0.1 mm.) leaving a 3.5 g. residue. The residue is purified via column chromatography on Merck silica gel 60 (300 g.) and eluted in 15 ml. fractions with 60% ether-pentane. Fractions 52-88 yielded 2.9 g. (89%) of 2-(3,5-dimethoxyphenyl)-2-hydroxypropyl 2-phenylethyl ether.
IR (CCl 4 ): 3534, 1595, 1202, 1153 cm -1 .
UV (95% ethanol): λ max =278 (ε=1830), 273 (ε=1860).
m/e--316 (m + ).
PMR (CDCl 3 , 60 MHz): δ 1.46 (S,CH 3 --), 2.86 (S,OH), 2.86 (t,J=7 Hz, --CH 2 --Ph), 3.53 (S,--CH 2 O), 3.71 (t,J=7 Hz,--CH 2 O), 3.80 (S,OCH 3 ), 6.38 (t,J=2 Hz, ArH), 6.61 (d,J=2 Hz, ArH) and 7.23 (S,PhH).
Analysis: Calc'd for C 19 H 24 O 4 : C, 72.12; H, 7.65%. Found: C, 71.92; H, 7.63%.
PREPARATION P
2-(3,5-Dimethoxyphenyl)propyl 2-Phenylethyl Ether
To a 0° C. solution of 2-(3,5-dimethoxyphenyl)-2-hydroxypropyl 2-phenylethyl ether (550 mg., 1.74 mM) in pyridine (2 ml.) is added dropwise phosphorus oxychloride (477 ml., 5.22 mM). The reaction is allowed to warm to 20° C. over a 1.5 hour period. It is then stirred for 1.5 hours at 20° C. and then added to ether (150 ml.) and 15% sodium carbonate (100 ml.). The organic phase is separated and washed with 15% sodium carbonate (3×50 ml.), dried over magnesium sulfate and evaporated to an oil. The oil is dissolved in absolute ethanol (15 ml.), 10% palladium-on-carbon (100 mg.) added and the mixture stirred under one atmosphere of hydrogen gas. When hydrogen uptake ceases (26.5 ml., 20 min.), the reaction is filtered through diatomaceous earth and the filtrate evaporated to an oil. The oil is purified via preparative layer chromatography on silica gel plates, eluted twice with 6:1 pentane:ether to yield 211 mg. (40%) of 2-(3,5-dimethoxyphenyl)propyl 2-phenylethyl ether.
IR (CCl 4 ): 1600, 1205, 1155, 1109 cm -1 .
m/e--300 (m + ).
PMR (CDCl 3 , 60 MHz) δ 1.22 (d,J=7 Hz, CH 3 --), 2.82 (t,J=7 Hz, CH 2 Ph), -2.8 (H--C--Me), -3.6 (--CH 2 --O--CH 2 --), 3.75 (S,OCH 3 ), 6.35 (m,ArH) and 7.18 (S,PhH).
PREPARATION Q
2-(3,5-Dihydroxyphenyl)propyl 2-Phenylethyl Ether
A mixture of 2-(3,5-dimethoxyphenyl)propyl 2-phenylethyl ether (195 mg., 0.65 mM), pyridine (0.4 ml., 4.96 mM) and dry pyridine hydrochloride (4 g., 34.6 mM) is heated at 190° C. for 6 hours. The reaction mixture is cooled and added to a mixture of water (100 ml.) and ether (150 ml.). The ether extract is washed once with water (50 ml.) and, along with a second ether extract (50 ml.) of the aqueous phase, is dried over magnesium sulfate and evaporated to an oil. The oil is purified via preparative layer chromatography on silica gel plates, eluted six times with 30% ether-pentane to yield 65.8 mg. (37%) of 2-(3,5-dihydroxyphenyl)propyl 2-phenylethyl ether.
IR (CHCl 3 ): 3559, 3279, 1605, 1147, 1105 cm -1 .
m/e--272 (m + ).
PMR (CDCl 3 , 60 MHz) δ 1.18 (d,J=7 Hz, CH 3 --), 2.80 (t,J=7 Hz, --CH 2 Ph), 2.80 (H--C--Me), 3.4-3.8 (--CH 2 OCH 2 --), 6.08 (t,J=2 Hz, ArH), 6.21 (d,J=2 Hz, ArH) and 7.16 (S,PhH).
The following compounds are prepared from appropriate alkanols by the methods of Procedures O and P.
______________________________________ ##STR67##(alk.sub.2) W______________________________________(CH.sub.2).sub.6 CH.sub.3(CH.sub.2).sub.6 C.sub.6 H.sub.5(CH.sub.2).sub.4 CH.sub.3CH(CH.sub.3)CH.sub.2 CH.sub.3CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3(CH.sub.2) 4-FC.sub.6 H.sub.4(CH.sub.2).sub.2 4-pyridyl(CH.sub.2).sub.2 2-piperidylCH(CH.sub.3)CH.sub.2 4-piperidyl(CH.sub.2).sub.2 CH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3CH(CH.sub.3) CH.sub.3C(CH.sub.3).sub.2 CH.sub.3______________________________________
PREPARATION R
4-(3,5-Dihydroxyphenyl)-1-phenoxypentane
Under a nitrogen atmosphere a mixture of 3,5-dibenzyloxyacetophenone (50.0 g., 0.15 M) in tetrahydrofuran (175 ml.) and 3-phenoxypropyltriphenylphosphonium bromide (7.18 g., 0.15 M) in dimethylsulfoxide (450 ml.) is added dropwise over 1.75 hours to a suspension of 50% sodium hydride (7.89 g., 0.165 M) (previously washed with pentane) in tetrahydrofuran (75 ml.) maintained at 0°-5° C. After stirring for 4 hours at 0°-5° C. the reaction is allowed to warm to room temperature and is then carefully stirred into ice water (2000 ml.), acidified with concentrated hydrochloric acid, and extracted with ethyl acetate (5×400 ml.). The combined organic phases are washed with saturated sodium chloride solution (3×300 ml.), dried over sodium sulfate and concentrated under vacuum to yield an oil which is triturated with ether to precipitate triphenylphosphine oxide. Filtration, followed by concentration of the filtrate, gives an oily residue which is chromatographed over silica gel (1300 g.) eluting with benzene-hexane consisting of 30% to 100% benzene. From the middle fractions 51 g. (75%) of 4-(3,5-dibenzyloxyphenyl)-1-phenoxypent-3-ene is isolated as an oil; R f =0.8 (silica gel, 2-benzene:1-hexane); m/e--450 (m + ).
Analysis: Calc'd for C 31 H 30 O 3 : C, 82.63; H, 6.71%. Found: C, 82.90; H, 6.69%.
A solution of 4-(3,5-dibenzyloxyphenyl)-1-phenoxypent-3-ene (51 g., 0.113 M) in a mixture of absolute ethanol (160 ml.), ethyl acetate (160 ml.) and concentrated hydrochloric acid (0.2 ml.) is hydrogenated for 12 hours under 55 lbs. hydrogen in the presence of 10% Pd/C. Removal of the catalyst by filtration and concentration of the filtrate under vacuum yields 30.8 g. (100%) of product as a viscous oil.
Analysis: Calc'd for C 17 H 20 O 3 : C, 74.97; H, 7.40%. Found: C, 74.54; H, 7.45%.
PREPARATION S
3,5-Dimethoxy-β-methylstyrene oxide
To a -78° C. solution of diphenylsulfonium ethylide (1.0 mole) in tetrahydrofuran (one liter) is slowly added 3,5-dimethoxybenzaldehyde (1.0 mole). The reaction mixture is stirred at -78° C. for 3 hours and then allowed to warm to room temperature. It is then added to ether-water and the ether phase separated. The ether phase is washed with water, dried (MgSO 4 ) and evaporated. Fractional distillation of the residue gives the title product.
PREPARATION T
3-(3,5-Dihydroxyphenyl)-2-propylbutyl Ether
To a solution of sodium butoxide in butanol (0.5 liters of 1 M) is added 3,5-dimethoxy-β-methylstyrene oxide (6.33 M). The mixture is heated for 18 hours at 70° C. and is then cooled and added to a mixture of ether-water. The ether solution is separated, dried (MgSO 4 ) and evaporated to give 3-(3,5-dimethoxyphenyl)-3-hydroxy-2-propylbutyl ether. It is purified by column chromatography on silica gel with ether-pentane elution.
By means of the procedure of Preparation P the title product is produced.
Similarly, the following are prepared from appropriate alcohols:
______________________________________ ##STR68##(alk.sub.2) W______________________________________CH.sub.2 CH.sub.3(CH.sub.2).sub.6 CH.sub.3(CH.sub.2).sub.3 C.sub.6 H.sub.5(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4(CH.sub.2).sub.2 4-pyridylCH(CH.sub.3)CH.sub.2 CH.sub.3CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 CH.sub.3CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5______________________________________
PREPARATION U
Alkylation of 3,5-Dihydroxyphenylmercaptan
A solution of 3,5-dihydroxyphenylmercaptan (3.5 g., 0.01 mole) in absolute ethanol (50 ml.) is made just alkaline with sodium ethoxide. The appropriate bromide of formula Br--(alk 2 ) n --W (0.01 mole) is added and the mixture refluxed for 3 hours. It is the concentrated under reduced pressure and the residue extracted with ether. Evaporation of the ether affords the product.
The following compounds are thus prepared:
______________________________________ ##STR69##n (alk.sub.2) W______________________________________1 CH(CH.sub.3)(CH.sub.2).sub.5 CH.sub.31 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.31 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.31 (CH.sub.2).sub.8 CH.sub.31 (CH.sub.2).sub.4 CH.sub.31 CH.sub.2 C.sub.6 H.sub.51 (CH.sub.2).sub.2 C.sub.6 H.sub.51 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.51 CH.sub.2 C.sub.3 H.sub.51 CH.sub.2 C.sub.5 H.sub.91 CH.sub.2 C.sub.6 H.sub.111 (CH.sub.2).sub.2 C.sub.5 H.sub.91 (CH.sub.2).sub.3 C.sub.5 H.sub.91 (CH.sub.2).sub.5 C.sub.6 H.sub.111 (CH.sub.2).sub.4 C.sub.5 H.sub.91 (CH.sub.2 ).sub.3 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.111 (CH.sub.2).sub.7 C.sub.5 H.sub.91 (CH.sub.2).sub.4 C.sub.7 H.sub.131 (CH.sub.2).sub.2 C.sub.7 H.sub.131 (CH.sub.2).sub.5 C.sub.4 H.sub.71 (CH.sub.2).sub.5 C.sub.3 H.sub.51 (CH.sub.2) 2-piperidyl1 (CH.sub.2).sub.3 4-piperidyl1 (CH.sub.2) 2-pyridyl1 (CH.sub.2).sub.3 3-pyridyl1 (CH.sub.2).sub.4 2-pyridyl1 CH(CH.sub.3)(CH.sub.2).sub.2 2-pyridyl1 CH(CH.sub.3)(CH.sub.2).sub.3 4-pyridyl1 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-piperidyl1 (CH.sub.2).sub.4 4-FC.sub.6 H.sub.41 CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.41 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.40 -- C.sub.6 H.sub.50 -- 4-FC.sub.6 H.sub.40 -- 4-ClC.sub.6 H.sub.40 -- C.sub.3 H.sub. 50 -- C.sub.5 H.sub.90 -- C.sub.6 H.sub.110 -- C.sub.7 H.sub.130 -- 4-pyridyl0 -- 2-piperidyl0 -- 2-pyridyl0 -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.40 -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.100 -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.120 -- CH.sub.3______________________________________
PREPARATION V
3-Hydroxy-5-pentylaniline
Olivetol (1.8 g., 0.01 M), ammonium chloride (2.65 g., 0.05 M), sodium bisulfite (5.2 g., 0.05 M) and ammonium hydroxide (12.5 ml.) are combined and heated in a steel bomb at 230° C. for a half-hour. The bomb is then cooled, the contents dissolved in ethyl acetate (350 ml.). Hydrochloric acid (300 ml. of 10%) is added, the mixture stirred and then the organic layer separated. The extraction is repeated two more times. The aqueous acid solution is neutralized with 6 N sodium hydroxide and then extracted with chloroform (3×300 ml.). The combined chloroform extracts are dried and concentrated. The residue is taken up in ethyl acetate, decolorized with charcoal and concentrated. The addition of hexane to the residue causes it to crystallize: 270 mg.; m.p. 88°-91° C. When recrystallized from hot ethyl acetate-hexane (1-1) it melts at 95°-96° C.
Analysis: Calc'd for C 11 H 17 ON: C, 73.70: H, 9.56; N, 7.81%. Found: C, 73.64; H, 9.62; N, 7.91%.
In like manner, the compounds of Preparations C, D, E, K, M, Q, R, T, U and CC are converted to the corresponding aniline derivatives having the formula ##STR70## wherein Z and W are as defined in said Preparations.
PREPARATION W
d,l -N-Acetyl-3-hydroxy-5-(5-phenyl-2-pentyl)aniline
A solution of 2.4 g. (9.5 mmole) d,l-3-hydroxy-5-(5-phenyl-2-pentyl)aniline in 24 ml. pyridine and 24 ml. acetic anhydride is stirred at room temperature for 45 minutes. The reaction mixture is poured onto 200 ml. each of water and ethyl acetate. After stirring for 10 minutes, the organic layer is separated and washed successively with water (4×100 ml.), brine (1×100 ml.), dried (MgSO 4 ), filtered and concentrated to yield 3.5 g. of crude d,l-N-acetyl-3-acetoxy-5-(5-phenyl-2-pentyl)aniline. A solution of d,l-N-acetyl-3-acetoxy-5-(5-phenyl-2-pentyl)aniline and 1 g. potassium carbonate in 100 ml. methanol is stirred at room temperature for one hour, filtered, concentrated and dissolved in ethyl acetate. The organic solution is washed with water, dried (MgSO 4 ) and concentrated to an oil which is crystallized from hexane to yield 1.5 g. d,l-N-acetyl-3-hydroxy-5-(5-phenyl-2-pentyl)aniline, m.p. 128°-130° C.
m/e--297 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 8.64 (bs, 1H, --NH), 7.12, 6.58 and 6.45 (bs. 1H variable, ArOH), 2.19-2.78 (m, 3H, Ar--CH and Ar--CH 2 ), 2.05 (s, 3H, CH 3 --C(═O)--), 1.3-1.78 (m, 4H, (CH 2 ) 2 ), 1.12 (d, 3H, --C--CH 3 ).
PREPARATION X
d,l-3-Benzyloxy-5-(5-phenyl-2-pentyl)aniline
To a stirred solution of 1.2 g. d,l-N-acetyl-3-hydroxy-5-(5-phenyl-2-pentyl)aniline (4.03 mmole) in 50 ml. tetrahydrofuran is added 193 mg. of 50% sodium hydride (4.03 mmole). After 30 minutes of stirring, 1.38 g. (8.06 mmole) of α-bromotoluene is added and stirring continued for 16 hours. The reaction mixture is then filtered, 1 ml. of acetic acid added to the filtrate which is then concentrated and chromatographed (silica gel, benzene/ether [2:1] as eluent) to yield 1.43 g. d,l-N-acetyl-3-benzyloxy-5-(5-phenyl-2-phentyl)aniline as an oil.
m/e--387 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.88 (bs, 1H, N--H), 7.38, 7.20, 6.84, 6.59 (bs, 5H, 6H, 1H, 1H, aromatic), 5.0 (s, 2H, --O--CH 2 Ar), 2.21-2.98 (m, 3H, Ar--CH and Ar--CH 2 ), 2.07 (s, 3H, CH 3 --C(═O)--N), 1.30-1.69 (m, 4H, --(CH 2 ) 2 ), 1.15 (d, 3H, CH 3 --C--Ar).
A solution of 1.4 g. d,l-N-acetyl-3-benzyloxy-5-(5-phenyl-2-pentyl)aniline, 14 ml. 20% potassium hydroxide, 14 ml. methanol and 10 ml. 2-propanol is heated at reflux on a steam bath for 4 days. After cooling, water and ethyl acetate are added and the mixture stirred for 10 minutes. The organic phase is separated and the aqueous phase extracted again with ethyl acetate. The organic solutions are combined, dried (MgSO 4 ), concentrated in vacuo and chromatographed (35 g. silica gel, benzene/ether [3:1] as eluent) to yield d,l-3-benzyloxy-5-(5-phenyl-2-pentyl)aniline as an oil.
m/e--345 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.32 (bs, 5H, aromatic), 7.13 (bs, 5H, aromatic), 6.01-6.33 (m, 3H, aromatic), 4.95 (s, 2H, ArCH 2 O), 3.48 (bs, 2H variable, NH 2 ), 2.17-2.88 (m, 3H, Ar--CH and Ar--CH 2 ), 1.32-1.76 (m, 4H, (CH 2 ) 2 ), 1.14 (d, 3H, --C--CH 3 ).
Following the procedures of Preparations W and X, the 3-hydroxy-5-(Z-W)-anilines of Preparation V are converted to 3-benzyloxy-5-(Z-W)anilines wherein X and W are as defined in Preparation V.
PREPARATION Y
d,l-3-Methoxy-5-(5-phenyl-2-pentyl)aniline
The procedures of Preparations W and X are repeated but using methyl bromide in place of α-bromotoluene to give the title product.
Similarly, the compounds of Preparation V are reacted with methyl bromide or ethyl bromide to give compounds having the formula ##STR71## wherein Z and W are as defined in Preparation V and Y 1 is methyl or ethyl.
PREPARATION Z
3,5-Diethoxyaniline
A mixture of 3-ethoxy-5-hydroxynitrobenzene (8.7 g.), diethyl sulfate (9.1 g.), potassium carbonate (7.4 g.) and toluene (200 ml.) is heated at reflux for four hours. The toluene is removed by steam distillation and the residue cooled. The solid product 3,5-diethoxy nitrobenzene is recovered by filtration and dried.
The solid (11 g.) is dissolved in glacial acetic acid (100 ml.) and water (100 ml.). Tin (1 g.) is added, followed by a solution of stannous chloride (7 g.) in concentrated hydrochloric acid (70 ml.). The mixture is stirred vigorously and held at 40° C. for six hours. It is then made alkaline with sodium hydroxide and extracted with ether (3×100 ml.). The combined extracts are dried (Na 2 SO 4 ) and evaporated to give the product. It is purified by vacuum distillation.
PREPARATION AA
(2-Halophenyl)cycloalkanols
The procedure of Huitric et al., J. Org. Chem., 23, 715-9 (1962) is employed but using the appropriate cycloalkylene oxide and p-halo (Cl or F) phenyl lithium reactants to produce the following compounds.
______________________________________ ##STR72##a X a X______________________________________2 Cl 2 F3 Cl 3 F5 Cl 5 F______________________________________
PREPARATION BB
(4-Halophenyl)cyclohexanols
A. 3- and 4-(4-Fluorophenyl)cyclohexanols
A benzene solution containing equimolar amounts of 4-fluorostyrene and 2-methoxybutadiene and hydroquinone (1% by weight based on diene) is heated in a sealed tube at 150° C. for 10 hours. The reaction vessel is cooled, the contents removed and concentrated to give 1-methoxy-4(and 5)-4-(fluorophenyl)cycloheptene which are separated by distillation in vacuo. Hydrolysis of the ether with 3% hydrochloric acid affords 3- and 4-(4-fluorophenyl)cyclohexanones.
Sodium borohydride reduction of the ketones according to the procedure of Example 31 affords the hydroxy compounds.
In like manner, the corresponding 3- and 4-(4-chlorophenyl)cyclohexanols are prepared from 4-chlorostyrene.
B. 2-(4-Fluorophenyl)cyclohexanol
This compound is prepared from cyclohexane oxide and p-fluorophenyl lithium according to the procedure of Huitric et al., J. Org. Chem., 27, 715-9 (1962), for preparing 2-(4-chlorophenyl)cyclohexanol.
PREPARATION CC
Alkylation of 3,5-Dihydroxyphenylmercaptan
A solution of 3,5-dihydroxyphenylmercaptan (3.5 g., 0.01 mole) in absolute ethanol (50 ml.) is made just alkaline with sodium ethoxide. The appropriate bromide of formula Br--(alk 2 ) n --W (0.01 mole) is added and the mixture refluxed for 3 hours. It is then concentrated under reduced pressure and the residue extracted with ether. Evaporation of the ether affords the product.
The following compounds are thus prepared:
______________________________________ ##STR73##n (alk.sub.2) W______________________________________1 CH(CH.sub.3)(CH.sub.2).sub.6 H1 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.31 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.31 (CH.sub.2).sub.8 CH.sub.31 (CH.sub.2).sub.4 CH.sub.31 CH.sub.2 C.sub.6 H.sub.51 (CH.sub.2).sub.2 C.sub.6 H.sub.51 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.51 CH.sub.2 C.sub.3 H.sub.51 CH.sub.2 C.sub.5 H.sub.91 CH.sub.2 C.sub.6 H.sub.111 (CH.sub.2).sub.2 C.sub.5 H.sub.91 (CH.sub.2).sub.5 C.sub.6 H.sub.111 (CH.sub.2).sub.4 C.sub.5 H.sub.91 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.111 (CH.sub.2).sub.7 C.sub.5 H.sub.91 (CH.sub.2).sub.4 C.sub.7 H.sub.131 (CH.sub.2).sub.2 C.sub.7 H.sub.131 (CH.sub.2).sub.5 C.sub.4 H.sub.71 (CH.sub.2).sub.5 C.sub.3 H.sub.51 (CH.sub.2) 2-piperidyl1 (CH.sub.2).sub.3 4-piperidyl1 (CH.sub.2) 2-pyridyl1 (CH.sub.2).sub.3 3-pyridyl1 (CH.sub.2).sub.4 2-pyridyl1 CH(CH.sub.3)(CH.sub.2).sub.2 2-pyridyl1 CH(CH.sub.3)(CH.sub.2).sub.3 4-pyridyl1 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-piperidyl1 (CH.sub.2).sub.4 4-FC.sub.6 H.sub.41 CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.41 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.40 -- C.sub.6 H.sub.50 -- 4-FC.sub.6 H.sub.40 -- 4-ClC.sub.6 H.sub.40 -- C.sub.3 H.sub.50 -- C.sub.5 H.sub.90 -- C.sub. 6 H.sub.110 -- C.sub.7 H.sub.130 -- 4-pyridyl0 -- 2-piperidyl0 -- 2-pyridyl0 -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.40 -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.100 -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.120 -- CH.sub.3______________________________________
PREPARATION DD
d,l-5-Phenyl-2-Pentanol Mesylate
To a stirred solution of 5-phenyl-2-pentanol (482 g.; 2.94 moles) in tetrahydrofuran (2250 ml.) at 0° C. is added methanesulfonyl chloride (300 ml.) at such a rate that the internal temperature does not rise above 10° C. (total addition time 4.5 hours). After addition is complete, the reaction mixture is allowed to warm to room temperature and stirring is continued for an additional hour. The reaction mixture is filtered and the supernate concentrated to a light yellow oil (2800 g.) which is dissolved in chloroform (2 l.) and washed with water (4×1 l.), brine (1×1 l.), charcoal treated (50 g.) dried (MgSO 4 ), filtered through diatomaceous earth and concentrated to a light orange oil (687 g., 95% yield). This material is suitable for use without further purification.
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.23 (s, 5H, aromatic), 4.53-5.13 (m, 1H, --CH--O--), 2.93 (s, 3H, O--SO 2 --CH 3 ), 2.42-2.93 (m, 2H, --CH 2 C 6 H 5 ), 1.50-1.92 (m, 4H, --(CH 2 ) 2 --), 1.23 (s, 3H, O--CH--CH 3 ).
Similarly, the following mesylates are prepared from appropriate alcohols:
4-phenylbutanol mesylate, a yellow oil.
m/e--228 (m + ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 7.22 (bs, 5H, aromatic), 4.08-4.24 (m, 2H, --CH 2 --O--), 3.93 (s, 3H, SO 2 CH 3 ), 2.40-2.82 (m, 2H, --CH 2 C 6 H 5 ), 1.51-1.93 (m, 4H, --(CH 2 ) 2 --).
1-2-octanol mesylate, a colorless oil.
[α] D 25 =-9.l695° (C--2.6, CHCl 3 ).
1 H NMR (60 MHz) δ CDCl .sbsb.3 TMS (ppm): 4.79 (bg, 1H, --CH--O--), 2.97 (s, 3H, S--CH 3 ), 1.40 (d, 3H, CH 3 --CH), 0.87 (t, 3H, CH 3 --CH 2 ), 1.0-2.0 (m, 10 H, --(CH 2 ) 5 --). d-2-octanol mesylate.
[α] D 25 =+9.238° (C=2.8, CHCl 3 ).
1 H NMR, identical to the 1-form. | 1,9-Dihydroxyoctahydrobenzo[c]quinolines (I), 1-hydroxyhexahydrobenzo[c]quinoline-9(8H)-ones (II), and 1-hydroxy-tetrahydrobenzo[c]quinolines (IV) useful as CNS agents, especially as analgesics and tranquilizers, as hypotensives, as agents for the treatment of glaucoma and as diuretics; intermediates therefor (III) and derivatives thereof having the formulae ##STR1## wherein R is hydroxy, alkanoyloxy having from one to five carbon atoms and hydroxymethyl;
R 1 is hydrogen, benzyl, benzoyl, alkanoyl having from one to five carbon atoms or --CO--(CH 2 ) p --NR 2 R 3 wherein p is 0 or an integer from 1 to 4; each of R 2 and R 3 when taken individually is hydrogen or alkyl having from one to four carbon atoms; R 2 and R 3 when taken together with the nitrogen to which they are attached form a 5- or 6-membered heterocyclic ring (piperidino, pyrrolo, pyrrolidino, morpholino and N-alkylpiperazino having from one to four carbon atoms in the alkyl group); R 4 is hydrogen, alkyl having from 1 to 6 carbon atoms and --(CH 2 ) z --C 6 H 5 wherein z is an integer from 1 to 4; R 5 is hydrogen, methyl or ethyl; R 6 is hydrogen, --(CH 2 ) y -carbalkoxy having from 1 to 4 carbon atoms in the alkoxy group wherein y is 0 or an integer from 1 to 4; carbobenzyloxy, formyl, alkanoyl having from two to five carbon atoms, alkyl having from one to six carbon atoms; --(CH 2 ) x --C 6 H 5 wherein x is an integer from 1 to 4; and --CO(CH 2 ) x-1 --C 6 H 5 ;
R 0 is oxo, methylene or alkylenedioxy having from two to four carbon atoms;
R' is R or R 0 ;
Z is (a) alkylene having from one to nine carbon atoms; (b)--(alk 1 ) m --X--(alk 2 ) n -- wherein each of (alk 1 ) and (alk 2 ) is alkylene having from one to nine carbon atoms, with the proviso that the summation of carbon atoms in (alk 1 ) plus (alk 2 ) is not greater than 9; each of m and n is 0 or 1; X is 0, S, SO or SO 2 ; and
W is hydrogen, methyl, ##STR2## wherein W 1 is hydrogen, chloro or fluoro, pyridyl, piperidyl, cycloalkyl having from 3 to 7 carbon atoms, or monosubstituted cycloalkyl wherein the substituent is ##STR3## wherein W 2 is hydrogen, chloro or fluoro; and pharmaceutically-acceptable acid addition salts of compounds of formulae I, II and IV and the ketals of compounds of formulae II, III and IV wherein the ketal moiety has from two to four carbon atoms. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to a door or window with a lighting device. The invention also relates to a lighting section capable of being used with or inserted in said door or window.
DESCRIPTION OF THE PRIOR ART
[0002] The lighting of particular environments can become problematical on account of the fact that, either for aesthetic reasons or lack of an appropriate space, it is not possible to make use of the traditional light sources. This is the case, for example, of rooms of particular artistic or architectural interest and of halls and rooms in museums. On the other hand, there may also be needs deriving from pure design considerations or from the arrangement of the interiors that make it unfeasible the installation of light sources in a conventional manner.
[0003] In many cases, moreover, even the natural lighting provided by an adequate number of windows can be utilized only to a very limited extent, because the windows may be screened to a more or less substantial extent by, for example, the employment of special glasses or reflection curtains, due to a wide variety of reasons, including—for example—reasons of security or privacy or to prevent damage to precious materials or objects that may prove sensitive to direct exposure to sunlight.
OBJECTS AND SUMMARY OF THE INVENTION
[0004] The object of the present invention is to provide a door or window, capable of satisfying the need discussed above.
[0005] Another purpose of the present invention is to provide a lighting section capable of being used with or incorporated in a door or window in order to render it suitable for illuminating environments in which it is not possible to install conventional light sources.
[0006] These aims are attained by means of the door or window and the associated lighting section in accordance with the present invention, the feature of which are set out, respectively, in claim 1 and claim 6. Further important characteristics of the invention are set out in the dependent claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The characteristics and the advantages of the door or window and the associated lighting section in accordance with the present invention will be apparent from the following description of embodiments thereof, which is given purely by way of example and is not to be considered limitative in any way, said description making reference to the attached drawings, of which:
[0008] [0008]FIG. 1 shows a partial cross section of a first embodiment of the invention;
[0009] [0009]FIG. 2 shows a partial cross section of a second embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Referring to FIG. 1, the reference number 1 has been used to schematically indicate a portion of a window frame, while 2 indicates a glass panel supported in a conventional manner within said frame. On one face of the glass panel there extends a layer 3 of material capable of reflecting at least a part of the light radiation arriving from outside, schematically indicated by the arrow R, for example, a sunscreen tissue. The edges of the glass panel 2 are engaged in a continuous groove 4 provided in an intermediate position along the inner side 1 a of the frame 1 . The latter, of course, may be either of the type that can move, slide or swivel with respect to a window opening within which it is mounted or may be installed in a fixed position in that same opening.
[0011] The continuous groove 4 divides the inner side 1 a of the frame 1 into two parts and on the part that is situated on the same side as the layer 3 there is provided a continuous and substantially C-shaped section 5 of which the open side is turned towards the centre of the window. The section may be made of metal, plastic material, wood or any other substantially rigid material. Inside the section 5 there is accommodated one or more light sources 6 , advantageously of the tubular or fluorescent type, aligned within the seating formed by the section 5 , or made up of a plurality of punctiform light sources placed at such a distance from each other as to give rise to a substantially continuous illumination. The section 5 may extend for the entire length of the inside faces of the frame 1 or merely along some parts thereof, for example, only along the longitudinal sides and any longitudinal crosspieces.
[0012] Advantageously, the section 5 may be provided with feet or small ribs 5 a that extend from its base and delimit—between the base and the inner side 1 a of the frame 1 —a space 7 within which there may pass the cables 9 providing the electricity supply.
[0013] A finishing frame 8 is provided on the outside of the section 5 on the side opposite the glass panel 2 in order to hide the section from view. The frame 8 may be fixed in any known manner to the corresponding side face of the frame 1 .
[0014] A substantial part of the light emitted by the light source 6 will be reflected into the interior of the environment by the reflecting layer provided on the glass panel 2 , while only a small fraction, not greater than 30%, will be transmitted to the outside.
[0015] The solution described above makes it possible to apply the invention to existing windows. The embodiment of the invention shown in FIG. 2, on the other hand, makes it possible to produce windows that are already predisposed for containing a light source. In fact, FIG. 2 shows a section through a metal section, made of aluminum for example, that permits the production by means of known techniques of a metal frame 10 for a window to be fixed—typically by means of hinges—to a counterframe 11 integral to the wall structure 20 . On the inside face 10 a of the frame 10 there are provided two continuous grooved seatings 12 and 13 . The first seating 12 is intended to engage in a conventional manner with the perimetral edges of a glass panel 14 , while the second seating 13 accommodates a light source 15 of the previously specified type. Advantageously, the light source may be anchored by means of elastic counteracting members to the walls of the seating 13 , which may be configured in such a way as to enable it to accommodate also at least one power supply unit 17 for the light source or the light sources contained therein. On the inner face 10 a of the frame 10 between the two seatings 12 and 13 there is also provided a continuous groove 18 intended to accommodate the edges of a movable reflecting curtain 19 . As an alternative, of course, the reflecting element in this case may once again be applied directly to the glass panel or use may be made of reflecting glasses of equivalent functionality.
[0016] The shape of the section used to obtain the frame 10 may vary with respect to the one here illustrated in accordance with the specific technical and aesthetic requirements. | A door or window comprising a frame ( 1 ) for supporting at least one glass panel ( 2 ) and, applied to one face of said panel, a layer ( 3 ) for filtering the light radiations. Along said frame, in a position corresponding to the periphery of said panel, there extends a seating ( 5 ) in which there is accommodated a tubular light source ( 6 ) or a light source distributed along the seating. | 5 |
BACKGROUND OF THE INVENTION
It is old to supply fluff to a converting machine through a fluff batt forming and feeding machine having a single screen. See, for example, Joa U.S. Pat. Nos. 3,086,253 and 3,666,611. It is also old to utilize such a machine to reclaim waste pulp and fluff and to mix the output of said reclaiming machine with fluff generated from a virgin source of fluff for joint delivery to a converting machine. However, in such prior devices, each converting machine required its own waste reclaiming fluff feeder. In a converting plant having several converting machines with each requiring its own feeder for reclaimed fluff, the high cost of the machinery, the large floor spaced required and the power demands of the several reclaimers have militated against the utilization of reclaimed fluff.
SUMMARY OF THE INVENTION
In accordance with the present invention, a single reclaimed fluff feeder is provided with multiple, separately driven screens, each one serving its own converting machine. Accordingly, a single reclaimed fluff feeder can service a plurality of converting machines, thus greatly reducing the capital investment, floor space and energy which would otherwise be required for utilizing and recycling waste pulp and fluff.
In accordance with the present invention, a fluff distributor is provided and which comprises a fluff chamber with a plurality of vacuum screens onto which screens reclaimed fluff is laid in batts. There are separately controllable drive mechanisms for each screen whereby each screen can be independently driven at a desired rate of speed whereby the volume of fluff output from said chamber for each screen is similarly separately controllable. Each screen furnishes reclaimed fluff to its own converting machine which is also supplied with fluff from a virgin source. Proportioning and distribution control mechanism is provided whereby the screen speed and hence the quantity of reclaimed fluff for each converting machine is varied in response to the demand of said converting machine for fluff. The control mechanism proportions the fluff supplied to each converting machine from a virgin source at a predetermined ratio to the quantity of reclaimed fluff supplied by the fluff distributor.
Mechanism is also provided to sense a deficiency of fluff on the screens in the fluff distributor, whereupon the fluff distributor will be disconnected from the system and the ratio selector will function to supply the converting machines with 100% virgin fluff. Reclaimed fluff will then be bypassed from the output of the fluff distributor to its input. When the sensing mechanism in the fluff distributor senses an adequate supply of reclaimed fluff, the fluff distributor will be reconnected to the converting machines and the ratio selector will reduce the amount of virgin fluff to the desired ratio of virgin fluff and reclaimed fluff.
Otherobjects, features and advantages of the invention will appear from the disclosure hereof.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view, partly in elevation and partly in vertical cross section, through a fluff distributor and its hopper feeder and embodying the invention.
FIG. 2 is a view partly in top plan and horizontal cross section through the apparatus of FIG. 1.
FIG. 3 is a fragmentary diagrammatic perspective view of the fluff distributor of FIGS. 1 and 2 with portions cut away to expose internal details.
FIG. 4 is a schematic view illustrating the utilization of the fluff distributor of FIGS. 1 and 2 with two converting machines, each having its own supply of virgin fluff.
FIG. 5 is a schematic circuit diagram for the control mechanism of apparatus embodying the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Although the disclosure hereof is detailed and exact to enable those skilled in the art to practice the invention, the physical embodiments herein disclosed merely exemplify the invention which may be embodied in other specific structure. The scope of the invention is defined in the claims appended hereto.
The fluff generated and utilized by the apparatus herein illustrated is typically fluff used for the absorbent fillers of sanitary pads, such as sanitary napkins, diapers, hospital pads, bandages, etc. Joa U.S. Pat. No. 3,666,611 illustrates a converting machine incorporating disposable diaper fabricating apparatus of the type above referred to. Two such disposable diaper fabricating machines 10, 11 are illustrated diagrammatically in FIG. 4.
Virgin fluff is supplied to the converting machines 10, 11 from any conventional pulp source thereof, for example, rolled stock 12, 13 of pulpboard which are defiberized in the fluff generators 14, 15. These can incorporate the structures of Joa U.S. Pat. Nos. 3,268,954 and 3,538,551. The fluff output from the generators 14, 15 is supplied in batt form to the converting machines 10, 11 through volumetric feeders 16, 17. These desirably incorporate the structures of the several Joa U.S. patents hereinbefore mentioned.
As hereinbefore indicated, it is frequently desired from an engineering and materials and energy conservation standpoint to utilize waste fluff, pulp, etc., which is generated in converting plants, as for example from clean reject products, for mixture with the virgin fluff supplied by the generators 14, 15. The prior art has utilized this technique by employing apparatus fabricated by applicant in which the waste fluff, pulp stock, cellulose wadding, plastic film, etc., is comminuted and mixed with the virgin fluff output of the generators 14, 15. However, in the prior art, a separate waste reclaimer is required for each converting machine, with the disadvantages hereinbefore mentioned.
In accordance with the present invention, a single waste reclaimer will serve a plurality of converting machines such as is typified by the two converting machines 10, 11 of the instant drawings.
As shown in the drawings, waste fluff, pulp, etc. 27 is deposited in the hopper 20 and is fed by endless belt 21 into an intake hood 22 of a hammer mill or similar fluff generator 23. Generator 23 has a rotor 24 driven by motor 26. Reclaimed fluff thus generated is pneumatically conveyed through the pipe 30 to the inlet eye of blower 31 which blows the fluff through the distribution manifold 32 into the chamber 33 of the fluff distributor 34. Fluff distributor 34 has elements similar to those of the volumetric feeder shown in Joa U.S. Pat. No. 3,086,253, except for important differences which adapt the apparatus to service a plurality of converting machines at rates of supply based upon the demand of said converting machines for reclaimed fluff.
Feeder 34 is provided with as many vacuum screens as there are converting machines 10, 11. In the embodiment disclosed herein to exemplify the invention, there are two such screens 35, 36. The respective screens 35, 36 travel over vacuum boxes 37, 38 so that the runs of the screens 35, 36 which are exposed to the chamber 33 will provide a surface upon which reclaimed fluff 41 will be drawn to form a relatively thick batt or mat of fluff, as shown in FIG. 1.
Each screen 35, 36 is trained about a top end roller 42 and a bottom end roller 43 and the screen is tightened by idler rollers 44, 45. The bottom rollers 43 for the respective screens 35, 36 are driven by separately controlled electric motors 46, 47. Accordingly, the speed of each screen 35, 36 can be varied in accordance with the speed of the motors 46, 47.
The thickness of the batts 50 on the screens 35, 36 is established by rotating paddle reels 51, 52 so that batts 50 of uniform thickness can be stripped off of the ends of the screens 35, 36 as they bend around the top rollers 42. With a uniform batt thickness, the volume or quantity of fluff delivered by each screen 35, 36 varies directly with screen speed.
The batt 50 from screen 35 is fed into a pneumatic discharge pipe 53. Batt 50 from screen 36 is fed into pneumatic discharge pipe 54. The respective pipes 53, 54 feed reclaimed fluff into the eyes of blowers 55, one at each side of the feeder 34 and only one of which is shown in FIG. 3, the other one being concealed in this figure behind the feeder. The output of the respective blowers 55 is selectively fed into pneumatic conveyor ducts 56, 57 which extend respectively to the volumetric feeder chambers 16, 17 of the converting machines 10, 11, or alternatively, to the bypass pneumatic ducts 60, 61 which return the fluff to the fluff chamber 33 of feeder 34.
In order to alternatively direct the fluff as between the pneumatic conveyor ducts 56, 57 and the bypass ducts 60, 61, the outlet of each blower 55 is provided with one of the gate valves 62, 63. These are best shown in FIG. 2 of the drawings. In FIG. 2, valve 63 is shown in its position in which the reclaimed fluff output of screen 36 is recycled through bypass duct 61 back to the chamber 33. Gate valve 62 is shown in its position in which the output from screen 35 is delivered through the pneumatic duct 56 to the volumetric feeder 16 of converting machine 10.
The respective gate valves 62, 63 are operated by conventional apparatus such as the air cylinders 64, 65. Cylinders 64, 65 are controlled by air valves 66, 67 (FIG. 4) in a manner hereinafter described.
As hereinbefore indicated, the volumetric feeders 16, 17 of the converting machines 10, 11 are provided with virgin fluff from the respective fluff generators 14, 15. The rate of feed of pulpboard stock 12, 13 to the generators 14, 15 is controlled by drive mechanism including paired feed rollers 68 for generator 14 and paired feed rollers 71 for generator 15. Drive rollers 68 are driven by a belt drive unit 72 and the drive rollers 71 for fiberizer 15 are driven by a belt drive unit 73. The respective drive units 72, 73 are provided with speed controllers 74, 75 as hereinafter explained.
The control circuitry is illustrated schematically in FIGS. 4 and 5. Converting machines 10, 11 typically comprise belts 76, 77. The speed of these belts 76, 77 will vary from one converting machine to another, depending upon various conditions of production. Accordingly, the demand of the respective converting machines 10, 11 for fluff will vary from one machine to the other. This demand is sensed by tachometers 80, 81 which signal speed sensing apparatus 82, 83. The speed sensors 82, 83 signal ratio selectors 84, 85, one for each converting machine 10, 11. The ratio selectors function to regulate the supply of fluff to the volumetric feeders 16, 17 for each converting machine 10, 11 in a desired proportion between virgin fluff generated by the generators 14, 15 and reclaimed fluff supplied by the respective screens 35, 36 of the waste reclaimer 34.
Typically, the desired ratio is 80% virgin fluff and 20% reclaimed fluff, although other ratios appropriate for the ultimate product of the converting machines 10, 11 can be selected. Accordingly, the ratio selectors 84, 85 signal the speed controllers 74, 75 of the pulp drive rollers 68, 71 to maintain a ratio of 80% virgin pulp to 20% reclaimed fluff, or any other desired ratio. If, for example, the speed of belt 76 of converting machine 10 drops because of a temporary slowdown of this particular machine, its tachometer 80 and speed sensor 82 will signal the ratio selector 84 which will, in turn, signal the controller 74 for pulp sheet drive 68 to reduce the quantity of pulp fed into the generator 14 and will also signal the controller for motor 46 which drives the screen 35, thus to reduce the speed of screen 35 in the same proportion as the speed of the pulp drive rollers 68 is reduced, thus to maintain the 80:20 per cent ratio between virgin fluff and reclaimed fluff.
When the speed of the belt 76 of converting machine 10 increases, thus reflecting a greater demand for fluff, corresponding signals will be sent by the speed sensor 80 to the ratio selector 84 and the screen drive controller for motor 46 to concurrently increase the speed of the pulp drive rollers 68 and the screens 35.
There may be conditions in the fabricating plant pursuant to which there is a shortage of waste product 27 so that the desired 80:20 ratio between virgin fluff and reclaimed fluff cannot be maintained. In this circumstance, the control circuitry herein disclosed will discontinue supply of reclaimed fluff from the waste reclaimer 34 and the ratio selectors 84, 85 will signal the virgin fluff generators 14, 15 to supply 100% virgin fluff to the volumetric feeders 16, 17. For this purpose the waste reclaimer 34 is provided with level sensing mechanism which senses the thickness of the batts 50 on the screens 35, 36.
In the disclosed embodiment, this sensing apparatus comprises paired light sources 87 and photocells 86, as shown in FIGS. 1, 2 and 3. The light beams therebetween are arranged at a predetermined spacing from the screens 35, 36, for example, 1 inch. So long as the supply of reclaimed fluff 41 to the screens 35, 36 is sufficient to maintain batts 50 at the 1 inch thickness, reclaimer 34 will continue to function to supply all of the reclaimed fluff demands of the converting machines 10, 11, at the 80:20% ratio. However, if the supply of reclaimed fluff is insufficient to maintain a 1 inch depth of batt 50 on one or the other or both of screens 35, 36 or for any other reason the thickness of batt 50 drops below 1 inch on one or the other or both of screens 35, 36, the photocell 86 for the screen deficient in fluff will sense the reduction in batt thickness and will send a signal to its ratio selector 84 or 85 to change the ratio of 80:20 to 100% virgin fluff for the converting machine serviced by the screen 35, 36 which has a deficiency of reclaimed fluff. At the same time, said photocell 86 will signal its air valve 66 or 67 to actuate the appropriate air cylinder 64 or 65 to swing the appropriate gate valve 62 or 63 to its position which will block the appropriate pneumatic duct 56 or 57 and bypass fluff from the appropriate output or discharge duct 53 or 54 back through the appropriate bypass ducts 60 or 61 to the inlet of the chamber 33 of the waste distributor 34.
As soon as the supply of reclaimed fluff 41 builds up to an adequate level to restore the thickness of deficient batt 50 to a point where the batt breaks the light beam from light source 87 to its photocell 86, the photocell will again signal the appropriate air valve 66 or 67 to swing appropriate gate 62 or 63 to its opposite position to discontinue bypassing waste fluff and to transmit this fluff to the appropriate volumetric feeder 16 or 17 and also will signal the appropriate ratio selector 84 or 85 to reduce the speed of the appropriate pulp drive unit 68 or 71 and restore the ratio of virgin fluff to reclaimed fluff to the 80:20 ratio. Accordingly, both screens 35, 36 can be feeding reclaimed fluff to the converting machines 10, 11, both can be bypassing fluff, or one can be feeding and the other can be bypassing, depending upon conditions.
The disclosed apparatus will function when all converting machines are operating, even though at different demand levels. When one converting machine stops entirely, its screen in the waste reclaimer 34 will operate at minimum speed and the output of said screen will bypass or recycle back to the chamber 33, in readiness to resume delivery to the idle converting machine when it resumes operation.
In order to prevent overloading the input to the distributor 34 during low demand periods, the drive mechanism 90 (FIGS. 4 and 5) for its feed belt 21 is controlled by a speed controller including summation circuit 91 which responds to the speed of the distributor screens 35, 36. Photocell 92 receives light from light source 93. Light source 93 and photocell 92 are mounted across the screens 35, 36 at a spacing therefrom beyond which the screens will be overloaded. Summation circuit adds the speeds of the two screens 35, 36 and signals the drive mechanism 90 in proportion to said sum. Accordingly, if the demand is low, with corresponding low speed of one or both screens 35, 36, this summation circuit will slow down the hopper drive mechanism 90, thus to prevent overloading the distributor 34. If the amount of fluff 41 becomes excessive in the distributor 34, the photocell 92 signals the drive control 90 for feed belt 21 to stop. When the fluff 41 reduces in volume, the photocell 92 signals the drive control 90 for feed belt 21 to start feeding. | A fluff distributor comprises a fluff chamber, two or more vacuum screens in said chamber and onto which screens fluff is laid in batts. The screens have separately controllable drive mechanism whereby each screen can be independently driven at a desired rate of speed. Accordingly, the volume of fluff output from said chamber for each screen is similarly separately controllable. Each screen supplies fluff to one of several converting machines. The converting machines can operate at different rates of speed requiring different volumes of fluff and by reason of the separate control for each distributor screen, the same fluff distributor can supply fluff to different converting machines operating at different demand levels for fluff. | 3 |
This is a continuation of application Ser. No. 827,064, filed Aug. 23, 1977, now abandoned.
BACKGROUND AND FIELD OF THE INVENTION
Briefly, the invention relates to energy conservation in general, to reduction of heat loss from a building in particular, and specifically to apparatus for such reduction occurring through the window area of a building.
Humanity's battle to conserve and most efficiently utilize the energy generated to heat buildings is ancient. Aesthetics, perhaps a need to feel unconfined, no matter what the reason, ever since building materials and techniques have permitted, a significant amount of the wall area, and even of the roof area in some instances, of a building has been windows. Much effort has been expended towards minimizing heat loss at a window area, symbolized by the universal acceptance, for decades, of storm windows. Less conspicuous but of even greater antiquity are various chinking, weatherstripping, and calking means for sealing a window frame to building interface. Some concessions have been made in the crusade against heat loss in the case of storm windows for the sake of user convenience. Lightweight windows having aluminum frames which are completely and totally useable and operable, including removal for cleaning, from inside a building, but which have a greater heat loss than wood frame windows, have been in widespread use for many years.
A general object of the invention is an article which reduces heat losses from a window area.
A specific object of the invention is a window cap which reduces heat loss both through the window glass and from the window frame to building interface portions of a window area.
Another object of the invention is a window cap which is modular.
An additional object of the invention is a window cap which provides a seal even against irregular building siding such as stucco, brick, and conventional lapped siding.
Yet another object of the invention is a window cap which fully encompasses even a window frame the top of which abuts a building soffit.
A further object of the invention is a window cap which can be stacked in a nesting relationship with another window cap.
BRIEF DESCRIPTION OF THE INVENTION
Briefly, the invention comprises a window cap which encompasses an entire window area, including the window frame to building interface.
According to a preferred embodiment of the invention, the vertical sides of the invention include a resilient seal slit crossways at regular intervals. In this way a tight seal is provided against a building, including all along the vertical sides even for an overlapped, stucco, or brick siding building.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view, including an enlarged view of one corner, of a window cap according to the present invention;
FIG. 2 is a bottom plan view of the window cap of FIG. 1;
FIG. 3 is a sectional view taken along line 3 of FIG. 2;
FIG. 4 is a fragmentary vertical sectional side view of a window cap of FIG. 1 attached to a building;
FIG. 5 is a fragmentary vertical sectional side view of a window cap according to FIG. 1 attached to a building having a window the top frame of which abuts the building soffit; and,
FIG. 6 is a fragmentary horizontal sectional view of two window caps according to FIG. 1 modified and joined together as an integral unit and attached to a building.
DETAILED DESCRIPTION OF THE INVENTION
A perspective view of a window cap according to a preferred embodiment of the invention is shown generally as 10 in FIG. 1, and comprises a window panel 12, top horizontal side 14, vertical sides 16 and 18, and horizontal bottom side 20. All of said sides combine to form a spacer element to position the panel 12 in outwardly spaced relation to the window and frame unit as shown in FIGS. 4, 5, and 6. Means for attachment of the window cap 10 to a building, apertures 22, are included in each of sides 14, 16, 18, and 20. FIG. 1 includes an enlarged view in which it can more easily be seen that side 14 includes a score 24 and that the corner seam between sides 14 and 16 similarly includes a crease 26 which extends part way up the corner. Score 24 extends the full width of side 14 and an identical score 24 extends across side 20 although it is hidden from view in FIG. 1. Each corner seam includes a crease 26.
A bottom plan view of the window cap 10 of FIG. 1 is shown in FIG. 2, and illustrates that a resilient seal 28 having crossways slits 30 is included in each of vertical sides 16 and 18.
FIG. 3 is a cross section taken along line 3 of FIG. 2 which shows that seal 28 sits in a channel formed by an outer wall 32, bottom surface 34, and inner wall 36. Vertical side 18 (as does the vertical side 16, not shown) includes a barb 38 between peripheral edge 40 of window pane 12 and the side 18 outer edge 42, the latter of which comprises the ends of the channel walls 32 and 36 and of the end of seal 28. A separation line 44 is included between each barb 38 and outer edge 42 to facilitate removal of seal 28 and its channel for joinder of one window cap with another which has also had a seal 28 and its channel removed. By definition, each peripheral edge 40 of a window pane 12 is located midway between the ends of the radius joining or, as the case may be, the juncture of the side (side 18 in the case of FIG. 3) and window pane 12. In FIG. 3 it can be seen that the included angle designated as 50 between side 14 and pane 12 is an obtuse angle selected, together with the thickness of the cap sides, to provide nesting of one cap within another.
FIG. 4 is a fragmentary side view of a window cap 10 attached to a building having lap siding shown generally as 46 by means of conventional wood screws 48 inserted through apertures 22. Slits 30 permit an abrupt and marked change in the degree of compression of resilient seal 28 to provide a highly efficient seal of a vertical edge to the side of a building, even at the point of overlap of a bottom 52 with a face 54 of the lap siding 46, and for all similarly irregular siding buildings. In FIG. 4 it can also be seen that score 24 is a double score, i.e. a score on both the inside and the outside.
FIG. 5 is a fragmentary vertical cross-sectional view of a window cap 10 attached to a building which includes a conventional eave shown generally as 60 which has a soffit 62 and a window the top frame 64 of which abuts soffit 62. Total encompassment of such a window is accomplished by wedging a compression strip 66 between the outer face 68 of top side 14 and soffit 62, after removal of the side 14 attachment flange 70 by fracturing side 14 along score 24 and up each of the creases 26 in the seams between side 14 and each of sides 16 and 18.
FIG. 6, a fragmentary, horizontal, sectional view, illustrates the modularity of the present invention. A pair of window caps 10 are formed into a double window cap by severing a channel and its seal 28 from a vertical side along separation line 44 of each of the window caps 10. The two so shortened sides are secured together with a barbed sleeve 80 which includes internal barbs 82 and 84 spaced for mating engagement with the barbs 38 of each of the vertical sides.
In the foregoing drawings, the glass of a window in each instance is designated as 86, the window sill as 88, and sides of the window frame as 90 and 92. According to the present invention, a window cap is provided which totally encompases an entire window area. A window cap is provided which extends beyond the entire window frame to building interface. Attachment beyond the window frame top 64 is illustrated in FIGS. 4 and 5; beyond the sides 90 and 92 is illustrated in FIG. 6; and, beyond the bottom or window sill 88 is illustrated in FIG. 5.
A window cap according to the present invention can be manufactured or fabricated from any of a variety of well known, readily available materials by well known processes. It is believed a clear plastic material vacuum formed or cold pressed would be the best mode for carrying out the invention.
The foregoing is given by way of illustration and not limitation and modifications and variations thereof deemed obvious to one of ordinary skill in the art are considered encompassed within the invention. For example, again by way of illustration and not limitation, window cap 10 could be provided with a seal 28 on each of its four sides. The true scope of the invention is set forth in the following claims. | A pan shaped window cap having a window pane with a peripheral edge and at least one side extending around the edge of and generally perpendicularly to said window pane, and wherein each side includes means for attachment of the window cap to the siding of a building beyond a window frame to completely encompass a window and its frame. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a data storing unit for a camera which operates to store film count data and data necessary for operating the camera.
2. Description of the Background Art
A microcomputer is generally used to control a variety of operations of a camera. In this connection, it is necessary to use a memory for storage and renewal of the various data required for control of the microcomputer. The memory is generally a RAM (random access memory) integral with the microcomputer. The RAM is volatile and therefore lose its contents when the power supply is cut off. Accordingly a non-volatile memory which does not lose its contents even if the power supply is turned off (hereinafter referred to as "an E 2 PROM," when applicable) is employed together with the microcomputer. Film count data generated as corresponding to every film winding operation and various data necessary for the operations of the camera, such as data representing the shutter's exposure operation and data indicating the fact that the film is being wound or rewound, are stored within the non-volatile memory.
The E 2 PROM retains its contents as they are even when the power is cut off. Therefore, in general, no backup power source (capacitor) is provided for the E 2 PROM. If, however, while data are being written in the E 2 PROM, the power supply is cut off, for instance by removal of the battery, data can no longer be written into the E 2 PROM and the data stored therein may be lost.
A first method of overcoming the above-noted difficulties is set forth in U.S. Pat. No. 4,733,265 and is disclosed as follows: A switch is provided in the battery chamber which detects intended removal of the battery before it is actually removed, so that abrupt cut off of the power is prevented whereby power supply time necessary for writing data in the E 2 PROM is secured. In addition, a second method is disclosed in Japanese Patent Application (OPI) No. 61731/1985 (the term "OPI" as used herein means an "unexamined published application") in which abnormal battery voltage is detected and the contents of the RAM are thereafter written into E 2 PROM before the power is cut off.
In the above-described first prior art method, the film count data and the data necessary for the operations of the camera are stored in the RAM in the microcomputer, and the switch detects cut off of power in advance so that the data are transferred from the RAM into the E 2 PROM. The detecting switch operates much earlier than actual cut off of the power; for instance, in operates at the start of the removal of the battery. Thus, a power supply time period long enough to ensure writing of the data in the E 2 PROM can be obtained.
However, the first prior art method is disadvantageous in that, since it is necessary to provide a mechanism such as a switch for detecting the removal of the battery from the battery chamber prior to the actual removal of the battery, it is necessary to provide space for the mechanism which results in increased manufacturing cost.
In the second prior art method, upon detection of the abnormal voltage of the battery, the data are written in the E 2 PROM. However, it is considered that, at the instant of detection, it is rather difficult to obtain a power supply time period long enough to write the data. In addition, with respect to the second prior art method, in order to eliminate the use of the backup power source, in a manner similar to the first prior art method, it is necessary to provide a mechanism for detecting cut off of the power before such cut off actually occurs.
Therefore, as described above with respect to the prior art, in order to prevent cut off of power during the period in which being written in the E 2 PROM, it is necessary to provide means for detecting cut off of power prior to actual cut off or to provide a backup power source. As a result, the camera is accordingly more intricate in construction and of increased manufacturing cost.
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide a data storing unit for a camera which, even if power is cut off while data are being written in a non-volatile memory, correct data can be written in the non-volatile memory after restoration of the power, and even if the power is cut off unexpectedly, the camera is operated smoothly after restoration of power. The above-noted camera of the present invention is of simple construction which eliminates the need of a mechanism for detecting cut off of power prior to actual cut off and a backup power source.
The above-noted object of the invention has been achieved by the provision of a data storing unit for a camera, which is adapted to store film count data and data necessary for the operation of the camera, which, according to the invention, comprises: a non-volatile memory; data writing means for writing the film count data in at least three addresses in the non-volatile memory successively, and for storing the data necessary for the operation of the camera together with the inverted data thereof in addresses present therefore; comparison means for subjecting the film count data written in the addresses by the data writing means to comparison and for determining whether or not the data necessary for the operation of the camera is in a correct inversion relation with the inverted data; and data rewriting means for obtaining, when a difference is present between the film count data in the addresses, a correct count value with reference to the address of the data which is determined to be different and the data necessary for the operation of the camera, and for rewriting the correct count value in the addresses, and for rewriting, when the correct inversion relation is not realized with respect to the data necessary for the operation of the camera and the inverted data thereof, correct data according to other data which has been written in the correct inversion relation.
In the data storing unit of the invention, the film count data, in the addresses, which are intended to be the same, are subjected to comparison and it is also detected whether or not the data necessary for the operation of the camera has been stored in a correct inversion relation with respect to the inverted data. Therefore, even if the power is cut off abruptly while data is being written in the non-volatile memory with the result that the data thus written is erroneous, the correct data can be rewritten. That is, when the power is restored, the erroneous data can be detected, and the data in the other addresses can be referred to in order to rewrite the correct data. Thus, after the power supply is restored, the camera can be operated smoothly. Furthermore, in the data storage unit of the invention, it is unnecessary to provide the power cut off detect mechanism or the backup power source. Hence, the data storing unit is simple in construction and low in manufacturing cost.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWING
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus, are not limitative of the present invention, and wherein:
FIG. 1 is a block diagram of a data storage unit for a camera according to an embodiment of the invention;
FIGS. 2 and 3 are flow charts descriptive of the operation of the data storing unit according to the invention; and
FIG. 4 is an explanatory diagram illustrating the arrangement of a non-volatile memory in the data storing unit according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
One preferred embodiment of this invention will be described with reference to the accompanying drawings. In FIG. 1, reference numeral 11 designates a microcomputer. The microcomputer 11, incorporating a RAM 12, functions as data writing means, comparison means and rewriting means, and performs predetermined operations according to a predetermined program to control instructions supplied to a shutter 13, a motor drive circuit 14 and an E 2 PROM 17, as will be described subsequently. Further, in FIG. 1, reference character SW1 designates a main switch; SW2, a first release switch; and SW3, a second release switch. The main switch SW1 is turned on before the operation of the camera to apply a signal to the microcomputer 11 to allow the latter to control the camera in its entirety. The first release switch SW2 is turned on to apply a signal to the microcomputer 11 so as to cause a range finder (not shown) to perform an automatic focusing (AF) operation and to cause a photometer (not shown) to carry out a photometric operation. The second release switch SW3 is used to apply a signal to the microcomputer 11 to cause the shutter 13 to perform an exposure operation.
The first release switch SW2 is turned on by depressing a release button (not shown) halfway; and the second release switch SW3 is turned on by depressing the release button fully.
The shutter 13 is operated in response to an exposure instruction which the microcomputer 11 outputs when the second release switch is turned on. The motor drive circuit 14 operates in response to a film winding instruction provided by the microcomputer 11, to operate a film winding motor 15. Further in FIG. 1, reference numeral 16 designates a battery which is a power source for the microcomputer 11, the shutter 13, the motor drive circuit 14 and a non-volatile memory 17, or E 2 PROM.
Under the control of the microcomputer 11, film count data and a variety of data necessary for the operation of the camera (data for the shutter's exposure operation and the film winding operation) are written in the E 2 PROM 17. The data can be read from the E 2 PROM 17 when the microcomputer issues a read request. The data written in the E 2 PROM 17 are also written in the RAM 12.
When, in the above-described circuit, the battery 16 is connected, and the main switch SW1 is turned on, the microcomputer 11 operates according to the flow chart shown in FIG. 2.
First, the contents stored in the E 2 PROM 17 are read out (Step 201). That is, the data written in the E 2 PROM 17 before power was cut off, are read out when the power is restored. Next, the data thus read are compared with one another and are subjected to a determination, as described later, and when unacceptable data is detected, correct data is rewritten in the E 2 PROM 17 (Step 202). In regard to the above step, if the power is cut off while data is being written in the E 2 PROM 17, then the data thus stored is partially erroneous, thus causing operational malfunctions regarding the operation of the camera. Therefore, it is necessary to determine whether or not the data stored in the E 2 PROM 17 is correct. When it is determined that part of the data is incorrect, then correct data is rewritten into the E 2 PROM. This operation in Step 202 will be described in more detail forthcoming with reference to FIG. 3.
The data in the E 2 PROM 17 which have been corrected in the above-described manner are transferred into the RAM 12 by the microcomputer 11 (Step 203).
Under these conditions, it is thereafter determined whether or not the first release switch SW2 has been turned on (Step 204). When it is determined that the first release switch SW2 has been turned on, the operating instructions are issued to perform the corresponding operations; i.e., to operate the above-described range finder and photometer (Step 205).
Next, it is determined whether or not the second release switch SW3 has been turned on (Step 206). When it is determined that the second release switch SW3 has been turned on, then it is necessary to cause the shutter 13 to perform the exposure operation as was described above. However, before the exposure operation is carried out, the following operations are carried out. In order to store the operating instruction of the shutter 13 in the memory, data "SHSTFLG=1" is set, and written both in the RAM 12 and in the E 2 PROM 17. As for the E 2 PROM, as shown in FIG. 4, data "SHSTFLG=1" is written in bit 7 of address 5 and the inverted data "SHSTFLG=0" is written in bit 6 of the same address 5 (Step 207). Thereafter, the exposure instruction is issued for the shutter 13, so that the shutter 13 performs the exposure operation (Step 208).
Upon completion of the exposure operation of the shutter 13, in order to store the film winding instruction, data "WDFLG=1" is set, and written both in the RAM 12 and in the E 2 PROM 17. As for the E 2 PROM, as shown in FIG. 4, the data "WDFLG=1" is written in bit 7 of address 4, and its inverted data "WDFLG=0" is written in bit 6 of the same address 4 (Step 209). At this time instant, the exposure operation of the shutter 13 has been accomplished. Therefore, the above-described data concerning the exposure operation are reset to "SHSTFLG=0" and "SHSTFLG=1" and the data are written in bits 7 and 6 of address 5 of the E 2 PROM 17 (Step 210).
Thereafter, the film winding instruction is applied to the motor drive circuit 14 to perform the film winding operation (Step 211). Upon completion of the film winding operation (Y in Step 212), the film count value in the RAM 12 is increased by +1, the resultant value (film count data) is written in the E 2 PROM 17 (Step 213). At this time instant, the film winding operation has been accomplished. Therefore, the above-described data are reset to "WDFLG=0" and "WDFLG=1," which are written in address 4 of the E 2 PROM 17 (Step 214). Thereafter, Step 204 is effected gain for the next photographing operation.
Writing of the film count data in the E 2 PROM 17 in Step 213 is carried out as follows: The film count value in the RAM 12 is written, as film count data, in a plurality of addresses, for instance three addresses 1, 2 and 3 in FIG. 4, successively.
If, while data is being written in the E 2 PROM 17, the power is abruptly cut off, for instance, by removal of the battery 16, then the data written in the E 2 PROM 17 becomes erroneous. For instance, when the power is cut off while the film count data is being written into one of the successive addresses of the E 2 PROM, the data written at this time instant in erroneous and thus is different from those written in the other of the successive addresses.
The data necessary for the operation of the camera which are to be written in addresses 4 and 5 must be in an inversion relation of the like "WDFLG=1" and "WDFLG=0." However, if the power is cut off during the data writing operation, the inversion relation is not established, as a result of which the data are written incorrectly such as, for instance, "WDFLG=1" and "WDFLG=1."
In order to eliminate this occurrence, Steps 201 and 202 (FIG. 2) are carried out. After restoration of the power, the contents of the E 2 PROM 17 are read out, and the film count data in the addresses are subjected to comparison and it is determined whether or not the data necessary for the operation of the camera are in the predetermined inversion relation to thereby detect unacceptable data. When such unacceptable data is detected, with reference to the remaining data, correct data is obtained and is rewritten in the E 2 PROM 17. This operation will be described with reference to the flow chart of FIG. 3 in more detail.
First, the film count data of the addresses are subjected to comparison (Step 301). It is assumed here for purpose of discussion, that the power was cut off while film count data was being written in address 2 of the E 2 PROM 17, as a result of which the data in address 2 is erroneous.
In this case, the data in addresses 1, 2 and 3 are not equal to one another, with "WDFLG=1." Therefore, the determination in Step 301 results in "N (No)," the determination in Step 302 results in "Y (Yes)," the determination in Step 303 results in "N," and the determination in Step 304 results in "N." Therefore, Step 307 is effected. In Step 307, the film count data correctly written in the address 1 before the cutting off of the power is rewritten in addresses 2 and 3. In this case, the film winding operation has been accomplished, and therefore data "WDFLG=0" and "WDFLG=1" are rewritten in address 4.
In the case where the power was cut off while film count data was being written in address 1, the data in the address 1 is erroneous. Therefore, the determination in Step 301 results in "N," the determination in Step 302 results in "Y," and the determination in Step 303 results in "Y." Hence, Step 305 is effected. In Step 305, the film count data in address 2 is increased by the resultant data is rewritten in addresses 1, 2 and 3. In addition, the data "WDFLG=0" and "WDFLG=1" are rewritten in address 4.
In the case where the power was cut off while film count data was being written in address 3, the data in the address 3 is erroneous. Therefore, the determination in Step 301 results in "N," the determination in Step 302 results in "Y," the determination in Step 303 results in "N," and the determination in Step 304 results in "Y." Therefore, Step 306 is effected. In Step 306, the film count data in address 2 is rewritten in address 3. In addition, the data "WDFLG=0" and "WDFLG=1" are rewritten in address 4.
Thus, even if the power is cut off while film count data is being written, after restoration of the power, correct film count data can be restored. The data necessary for the operation of the camera; that is, the film winding data WDFLG can be stored correctly as if the power was not cut off. Thus, the operation of the camera will not be affected.
Now, the case will be described in which, the exposure operation of the shutter 13 has been accomplished, and data "WDFLG=1" has been set, and the power is cut off while the data thus set is being written in address 4 of the E 2 PROM 17.
In this case, the film count data is not written yet, and the data in addresses 1, 2 and 3 are equal to one another. Accordingly, the determination in Step 301 results in "Y." The data in address 4, being erroneous, is not in the predetermined inversion relation. Hence, it is determined that the data in address 4 is erroneous and the determination is Step 308 results in "Y." On the other hand, the data in address 5 remains in the predetermined inversion relations as "SHSTFLG= 1" and "SHSTFLG=0". Hence, the determination in Steps 309 and 310 result in "N" and "Y," respectively, and Step 311 is effected. In Step 311, the data "WDFLG=1" and "SHSTFLG=0," and their inversion data are rewritten in the respective addresses in the E 2 PROM 17.
When the determination in Step 310 results in "N"; that is, when "SHSTFLG=0," then this is the case where, in Step 214 of FIG. 2 "WDFLT=0" is reset, and the power is cut off while the data thus reset is being written in the E 2 PROM 17. Therefore, in Step 312, the data "WDFLG=0" and its inversion data are written in address 4 of the E 2 PROM 17.
In the case there the data in address 4 is not erroneous ("N" in Step 308) whereas the data in address 5 is erroneous ("Y" in Step 313), Step 314 is effected, so that "SHSTELG=0" and "SHSTFLG=1" are rewritten in address 5 of the E 2 PROM 17.
In the case where the data in address 4 is erroneous ("Y" in Step 308) and the data in address 5 also has been destroyed ("Y" in Step 309), Step 315 is effected, so that "WDFLG=0" and "WDFLG=1," and "SHSTFLG=0" and "SHSTFLG=1" are rewritten in addresses 4 and 5 of the E 2 PROM 17, respectively.
Thus, even if the power is cut off while the data necessary for the operation of the camera; i.e., the data "WDFLG" concerning the film winding operation and the data "SHSTFLG" concerning the exposure operation of the shutter 13 is being written, correct data can be stored after restoration of the power, so that the operation of the camera will not be affected at all.
As was described above, with the data storing unit of the invention, even if the power is cut off abruptly while data is being written in the non-volatile memory, correct data can be rewritten therein after restoration of the power. Therefore, the camera can be operated satisfactorily after the power supply is restored. Furthermore, in the invention, unlike the prior art, it is unnecessary to provide a mechanism for detecting the cut off of the power supply prior to such an occurrence or a backup power source. Thus, the data storing unit of the invention is simple in construction, which effectively prevents increases in manufacturing cost.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | The invention relates to a data storage unit of a camera which includes a power failure protection system which ensures that data written into the data storage unit, during the occurrence of power failure, is not lost. Film count data is stored successively in three memory address locations and comparison of the correspondence of the film count data is utilized to generate and rewrite corrected film count data. In regard to shutter exposure and film wind commands, both commands and inverted forms therein are stored and comparison of inversion relationships are used to determine if the data is correct. Thereafter, the correctly determined data is utilized to generate and rewrite corrected data. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a sewing data forming device for a sewing machine equipped with a cloth presser device which is to drive a material to be sewed (hereinafter referred to as "a sewing material", when applicable) according to predetermined sewing data.
An industrial sewing machine has been put in practical use which is so designed that, according to sewing data programmed and stored in a memory unit, a sewing material (work) such as a cloth is moved in a predetermined plane while being held, to automatically form a desired sewing pattern on it. The sewing data are stored in a memory medium in the memory unit, to form a variety of sewing patterns on the sewing materials. The memory medium is, for instance, a semiconductor memory, magnetic card, or floppy disk. Data for controlling the operation of the sewing machine are stored in the memory medium in the order of sewing operations.
The control data includes control instructions for controlling an amount of relative displacement of a needle and a cloth, and a sewing speed for every stitch by the sewing machine forming a sewing pattern, and those for controlling the operations of the sewing machine and an electric motor adapted to drive the sewing machine. Control data for one sewing pattern is the assembly of control instructions for a number of stitches. Hence, in order to form a desired sewing pattern on a sewing material with the sewing machine, it is necessary to form sewing data for the sewing pattern in advance and to store them in the memory medium.
FIG. 1 is a perspective view showing a conventional sewing data forming device for a sewing machine which is disclosed by Published Unexamined Japanese Paten Application No. 148582/1985. The device comprises a tablet digitizer 10 including inputting means having a menu section 11, a pattern input section 13, a cursor means 12 such as a mouse to select a desired item from the menu section 11 and to obtain coordinate data from the pattern input section 13. Further in FIG. 1, reference numeral 20 designates an LED (light emitting diode) display panel in the sewing data forming device which comprises a variety of switches and LEDs; 26, a CRT (cathode ray tube) for displaying pattern data; 18, a PROM (programmable read-only memory) section for writing sewing data in a memory medium such as a PROM and for reading the sewing data from the PROM; and 8, an eraser for erasing the sewing data from the PROM.
FIG. 2 shows the menu section 11 in more detail, and the cursor means 12 comprising a reading section 12a and a switch 12b.
The operation of the conventional sewing data forming device will be described with reference to FIG. 3 which is an explanatory diagram showing the arrangement of the device.
A desired sewing pattern is drawn on the tablet digitizer with the mouse 12. In compliance with the sewing pattern thus drawn, sewing data is formed mainly under the control of a CPU 14 and then stored in a RAM 24 temporarily. Then, a PROM writer 16 is operated to write the sewing data thus stored in the RAM 24 to the PROM 18 contained in a PROM cassette 42 through a gate 44. The PROM cassette 42 is loaded in the a sewing machine control device 40 to drive the sewing machine 38. The settings of modes and the procedure of operations in the formation of sewing data are applied, as I/O data, through the gate 44 to the LED display panel 20 to be displayed thereon. The program for writing the input data from the tablet digitizer 10 through the gate 44 in the PROM 18, according to which the CPU 14 operates, has been stored in a system program ROM 22. X and Y coordinate data, which are input data from the table digitizer 10, are stored temporarily in the RAM 24. By operating the input data, sewing data, namely, X and Y coordinate data are obtained. The amounts of variation of the X and Y coordinate data; that is, relative value data thereof are also stored in the RAM 24. The pattern display CRT 26 is provided to monitor the pattern data inputted from the tablet digitizer 10. With the aid of the CPU 14, the sewing data stored in the RAM 24 are converted into image displaying data, which are applied through a gate 33 to an image data RAM 28 so as to be stored therein. Thus, the sewing pattern is displayed on the CRT 26 by a CRT control circuit 46, which facilitates the data inputting operation of the operator.
FIG. 4(a) shows one example of a sewing pattern. Now, a concrete data inputting method will be described. First, a drawing on which the sewing pattern as shown in FIG. 4(a) has been drawn is stuck on the pattern inputting section 13 of the tablet digitizer 10. Thereafter, with the reading section 12a of the mouse 12 set at the "Pattern Input" of the menu section 11, the switch 12b is operated so as to input the sewing pattern. Similarly, in the menu section 11, "Scale", "1", "0", "0", "Stitch length", "3", ".", "0", "Low speed", "Point input" and "Start" are selected successively, to set input conditions. In this case, the scale is set to 100%; that is, the data in the drawing are equal in scale to data inputted, and when two points are inputted, sewing data of 3.0 mm is produced. Further, the sewing speed is made low and an input condition is set to point input.
Thereafter, with the reading section 12a of the mouse 12 set at the origin 0 of the sewing pattern 10a, the switch 12b is operated to input the origin's position. Under this condition, the items in the menu section 11 and the points of the sewing pattern are inputted with the mouse 12 in the following order: "Idle feed", point A→point B→"Straight line input", "High speed", point C→"Point input", "Middle speed 1", point D→point E→"Straight line input", "High speed", point F→"Pause", point G→"Point input", "Middle speed 1", point H→point I→Straight line input", "High speed", point J→"Idle feed", origin 0→"End".
FIG. 4(b) shows another example of the circular sewing pattern. The sewing pattern can be inputted by the same method as the sewing pattern of FIG. 4(a). However, the inputting of the sewing pattern shown in FIG. 4(b) is troublesome when compared with the inputting of the one shown in FIG. 4(a), because the sewing pattern is a free curve, and therefore after point A is inputted, point A 1 , the remaining points--point A 2 , point A 3 . . . point A 41 , point A 42 , point A 43 , point A 44 and point J forming the circular sewing pattern--must be all inputted correctly.
Thus, the inputting of the sewing pattern shown in FIGS. 4(a) and 4(b) has been accomplished. During the inputting operation, the scale value, stitch length, speed instruction values, and inputting method are displayed on the LED display panel 20 whereas the sewing pattern is displayed on the CRT 26.
FIG. 5 is a flow chart showing a data processing operation corresponding to the above-described data inputting operation. When the switch 12b of the mouse 12 is operated in Step S1, the coordinate data are read in Step S2. In Step S3, it is determined whether the data thus read in Step S2 is the one selected from the menu section 11 or whether it is of the sewing pattern. When it is determined that the data is selected from the menu section 1, Step S5 is effected. In Step S5, it is determined which of the items in the menu section 11 has been selected. And, in Step, S6, a process corresponding to the item selected from the menu is carried out. When, on the other hand, the data read in Step S2 is of the sewing pattern in Step S3, the coordinate data read in Step S4 are subjected to arithmetic operation. In Step S7, sewing data is formed, and an operation for displaying the sewing data together with the result of process in Step S6 on the LED display panel is carried out. Thereafter, in Step S8, an operation for displaying the sewing data thus formed on the CRT 26 or writing in the PROM 18 is carried out.
Being designed as described above, the conventional sewing data forming device is difficult to convert a sewing pattern made up of free curves into sewing data high in quality (promising fine seams) with specified stitch length.
SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to eliminate the above-described difficulty accompanying a conventional sewing data forming device. More specifically, an object of the invention is to provide a sewing data forming device with which sewing data providing fine seams can be formed merely by inputting the coordinate data of a plurality of points on a free curve which includes the start and end points thereof.
The above, and other objects of the present invention are accomplished by the provision of a sewing data forming device for a sewing machine comprising: data input means for inputting coordinate data of a plurality of points along a sewing pattern, the data input means designating an input condition among point input, linear input and curve input; data storage means for storing data inputted by the data input means successively; and data processing means for applying inclination data to each of said coordinate data so as to form the sewing data between the points adjacent to each other according to a stitch length specified for an interval therebetween.
In the sewing data forming device, the sewing data for the interval between the points adjacent to each other are formed on a curve approximated by a cubic expression.
In the sewing data forming device, the input coordinate data of (N-1)th point, N-th point and (N+l)th point are subjected to arithmetic operation, to apply inclination data representing an inclination to the input coordinate data of the N-th point, the N being a positive integer.
In the sewing data forming device, the inclination data of the N-th point is obtained by an average of the inclination of a straight line bridging the (N-1)th and N-th points and the inclination of a straight line bridging the N-th and (N+1)th points.
In the sewing data forming device, an inclination of a straight line bridging the first and second points is applied as the inclination data of the first point whereas an inclination of a straight line bridging the last point and the last but one point is applied as the inclination data of the last point.
In the sewing data folding device, the same inclination data is applied to the first and last points in the case where the coordinate data of the last point is coincident with or close to the coordinate data of the first point.
In the sewing data forming device, the same inclination data is obtained by the average of the inclination of a straight line bridging the first and second points and the inclination of a straight line bridging the last and the last but one points.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a perspective view showing a conventional sewing data forming device in a sewing machine;
FIG. 2 is an explanatory diagram showing a tablet digitizer and a mouse in the conventional sewing data forming device;
FIG. 3 is an explanatory diagram, partly as a block diagram, showing the arrangement of the conventional sewing data forming device;
FIGS. 4(a) and 4(b) are explanatory diagrams showing examples of a sewing pattern;
FIG. 5 is a flow chart for a description of the operation of the conventional sewing data forming device;
FIG. 6 is an explanatory diagram showing a tablet digitizer and a mouse in an example of a sewing data forming device in a sewing machine which constitutes one embodiment of this invention;
FIGS. 7(a) and 7(b) is an explanatory diagrams showing the arrangement of sewing data;
FIG. 8 is a flow chart for a description of the operation of the sewing data forming device according to the invention; and
FIGS. 9, 10 and 11 are explanatory diagrams for complement of the description of a calculating method which is made with reference to the flow chart shown in FIG. 8.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of this invention will be described. FIG. 6 shows a tablet digitizer 10 and a menu section 11a according to the invention. As shown in FIG. 6, the menu section 11a includes a menu key "Curve Input " which, when sewing data are formed for a free curve, is selected with the reading section 12a of a mouse 12. More specifically, the menu key "Curve Input " is selected at the start of a sewing data forming operation or during the sewing data forming operation, and data on a plurality of coordinates including those of the start and end points of a given free curve are inputted to form the sewing data along the free curve.
Now, the data inputting method will be described concretely according to the sewing pattern shown in FIG. 4(b). The data inputting method is substantially equal to that which has been described with reference to the conventional sewing data forming device.
First, a drawing on which the sewing pattern as shown in FIG. 4(b) has been drawn is stuck on the pattern inputting section 13 of the tablet digitizer 10. Thereafter, with the reading section 12a of the mouse 12 set at the "Pattern Input " of the menu section 11a, the switch 12b is operated so as to input the sewing pattern. Similarly, in the menu section 11, "Scale", "1", "0", "0", "Stitch Length", "3", ".", "0", "Low speed", "Curve Input " and "Start" are selected successively, to set input conditions. In this case, the scale is set to 100%; that is, the data shown in the drawing are equal in scale to the data inputted, and the speed instruction inputted is of low speed, and the inputting method is for curves.
Thereafter, with the reading section 12a of the mouse 12 set on the origin 0 of the sewing pattern shown in FIG. 4(b), the switch 12b is operated to input the origin's position. Under this condition, the relevant items of the menu section 11a and the positions of the relevant points on the sewing patterns are inputted with the mouse 12 in the following order: "Idle Feed", point A→"Curve Input", "High Speed", point A 5 →point A 10 →point A 15 →point A 20 →point A 25 →point A 30 →point A 35 →point A 40 →point J→"Curve Input"→"Idle Feed", origin point 0→"End". For convenience in description, the points A 5 , A 10 , . . . A 40 and J are selected as the input points; however, in practice, any points on the curve can be employed.
The inputs of the points from the point immediately before the menu key "Curve Input " is operated; i.e., the point A to the point immediately after the menu key "Curve Input " is operated next; i.e., the point. J are subjected to arithmetic operation by arithmetic means (described later), to obtain points A, A 1 , A 2 , A 3 , A 4 . . . A 44 and J which form the aimed sewing pattern.
Thus, the operation of inputting the sewing pattern shown in FIG. 4(b) has been accomplished. In this operation, the scale value, stitch length, speed instruction value, and input method are displayed on the LED display panel 20. In the above-described pattern inputting operation, by operating the switch 12b of the mouse 12, sewing data are successively formed and stored in the RAM 24, and in order to display positions, the absolute values of the sewing data with the position of the input origin point as a reference are stored in the RAM 28.
FIGS. 7(a) and 7(b) show the arrangement of the sewing data stored in the RAM 24. FIG. 7(a) shows one unit of sewing data of a stitch. That is, the first byte stores the above-described control instruction, the second byte stores stitch data or the amount of X-axis feed of the idle feed data, and the third byte stores stitch data or the amount of Y-axis feed of the idle feed data. The one unit of sewing data, as shown in FIG. 7(b), are stored in predetermined addresses in the inputting order beginning from the first stitch to the end data which is one of the control instructions of sewing data.
FIG. 8 is a flow chart for a description of the operation of the sewing data forming device according to the invention.
When the menu key "Curve Input " is selected with the switch 12b of the mouse 12, a sewing data forming mode by curve inputting is established in Step S10 of FIG. 8. In Step S11, coordinate data (points A, A 5 , A 10 , A 15 . . . A 40 and J) inputted are read and stored in the RAM 24 shown in FIG. 3 successively.
When the menu key "Curve Input " is operated again in Step S12, Step S13 is effected. In Step S13, inclination data (G, G 5 , G 10 , G 15 , . . . G 40 and GJ) are applied to the coordinate data (of the points A, A 5 , A 10 , A 15 , . . . A 40 and J) respectively.
The inclination data G determines the inclination of the straight line connecting the points A and A 5 . That is, assuming that the coordinates of the point A is represented by (X a , Y a ) and the coordinates of the point A 5 by (X a5 , Y a5 ), the data G can be calculated from the following equation:
G=(Y.sub.a5 -Ya)/(X.sub.a5 -X.sub.a)
At any one of the points G 5 through G 40 , the inclination is determined as the average of the inclination of the straight line connecting the point and the preceding point and the straight line connecting the point and the following point. That is, the average is calculated from the following equation. In this case, the inclination of a point A n is G n , and the coordinates of the preceding point A n-1 , the point A n and the following point A n+1 are (X an-1 , Y an-1 ), (X an , Y an ) and (X an+1 , Y an+1 ), respectively.
Gn=1/2[{(Y.sub.an -Y.sub.an-1)/(X.sub.an -X.sub.an-1)}+{(Y.sub.an+1 -Y.sub.an)/(X.sub.an-1 -X.sub.an)}]
The last inclination data GJ determines the inclination of the straight line connecting the points A 40 and J. That is, it can be calculated from the following equation. In this case, the coordinates of the point A 40 is (X a40 , Y a40 ), and the coordinates of the point J is (X j , Y j ).
GJ=(Y.sub.j -Y.sub.a40)/(X.sub.j -X.sub.a40)
The inclination data (G, G 5 , G 10 , G 15 , . . . G 40 and GJ) for all the inputted points are calculated, so that they are stored in the RAM 24 shown in FIG. 3.
In the case where the start point (the point A) and the end point (or the point J) of the pattern are one and the same point as in the case of a circle shown in FIG. 11, or close to each other, the inclinations of all the points are calculated, and the inclinations (G and GJ) of the start and end points are calculated again from the following equation. That is, as for the start and end points, the inclinations thus calculated are employed. This method is advantageous in that the start and end points are connected smoothly.
G=GJ=(G+GJ)/2
Next, in Step S14 , a curve approximated by a cubic expression is calculated to connect the points (FIG. 9), the cubic expression being as follows:
Y=LX.sup.3 +MX.sup.2 +NX+P.
A curve C 5 approximated by the cubic expression to connect the points A and A 5 can be obtained by arithmetic operation on the coordinates of the points A and A 5 and the inclinations G A and G 5 of the points A and A 5 which have been obtained before. In this case, assuming that the coordinates of the point A and A 5 are (0, 0) and (X a5 , Y a5 ), respectively, and the inclinations thereof are G A and G 5 , constants in the cubic expression can be determined as follows:
P=0;
N=G A ;
M=3(Y a5 )/(X a5 ) 2 -(G 5 +2G A )/(X a5 ); and
L={G 5 -G A -2M(X a5 )}/3(X a5 ) 2 .
In the same manner, curves C 10 , C 15 , C 20 , . . . C 40 and CJ can be obtained to connect the points A 5 and A 10 , the point A 10 and A 15 , the points A 15 and A 20 , . . . the points A 40 and J, respectively. FIG. 9 is a diagram for a description of the above-described operations . The curve in FIG. 9 is substantially similar to the one shown in FIG. 4(b).
Thereafter, in Step S15, the curves C 5 , C 10 , . . . and CJ are divided into a number of stitch lengths slen. This curve dividing method will be described with reference to FIG. 10 under the following conditions:
______________________________________Equation of the curve C5 Y = f(x)Given stitch length slenIncreasing x by unit length (1) x.sub.iIncrement of Y with X increment dyPoints on C5 with increase of xi p1, p2, p3, . . .Minute length on C5 dlSum of the minute lengths on C5 sdl______________________________________
First, a point is marked on the X-axis at the distance x i from the point A. In this case, the increment of Y is dy which is calculated from the following equation. The value x i and the value dy thus calculated are employed as the coordinates of the point p1.
dy=f(x.sub.i)
The minute length between the points A and p1 on the curve C 5 is calculated from the following equation, in which "sqrt " is intended to mean taking the square root of the value in the parentheses {}.
dl=sqrt{(xi).sup.2 +(dy).sup.2 }
The above-described operations are carried out for the points p1, p2, p3, . . . to determine the coordinates of them, and the sum sdl is obtained by adding the values dl of them. The point pn which is immediately before the point where the sum sdl exceeds the stitch length slen is determined as the first stitch point from the point A. The point pn is the point A 1 in FIG. 4(b) .
Upon determination of the first stitch point, the sum sdl is cleared to zero, and new minute lengths dl are added up to determine the next stitch point.
The above-described operations are carried out on the curve C 5 to determined stitch points corresponding to the points A 1 , A 3 , A 4 and A 5 in FIG. 4(b). In the same way, the points A 10 , A 11 , A 12 , A 13 , . . . A 43 , A 44 and J on the curves C 10 , C 15 , C 20 , . . . C 40 and CJ can be obtained.
In Step S16, it is determined whether or not the operations for all the points up to the point J have been accomplished. When it is determined that the operations for all the points have been done, Steps S14 and S15 are effected to perform the operations for the next curve C 10 . Upon completion of the operations for the last curve CJ, the routine is ended leaving Step S16. Thus, the curve inputting operation has been accomplished.
In the above-described case, the inputted point A 5 of the curve C 5 coincides with the stitch point A 5 . However, as is seen from the contents of the above description, in general the two points do not coincide with each other. In the case where the inputted point A 5 does not come out as a stitch point, the sum slen of minutes lengths is smaller than the specified stitch length. However, this shortage is complemented by summing the minute lengths on the next curve C 10 , so that the last stitch point on the curve C 5 is connected expertly to the first stitch point on the next curve C 10 .
As was described above, in the sewing data forming device of the invention, the menu section of the table digitizer has the menu key "Curve Input". Therefore, sewing data to give a fine seam can be formed merely by inputting the coordinate data of a plurality of points on a free curve including its start and end points with the menu key "Curve Input " selected at the start of a sewing data forming operation or during it. Accordingly, the time and labor required for the data inputting operation is reduced to one-fifth to one-tenth of that with the conventional sewing data forming device. In addition, the sewing data formed with the device of the invention is much higher in quality (accuracy and smoothness) than with the conventional device resulting in making the curve connecting the points most natural and smooth.
With the sewing data forming device according to the invention, coordinate data and curve inclination data are provided for two points, to determine a cubic curve connecting the two points. Hence, an amount of calculation to obtain the sewing data is relatively small.
Further, according to the invention, the inclination data of the middle of three points which are inputted successively is automatically calculated from their coordinate values inputted. Hence, it is unnecessary to provide means for applying the inclination data to it.
Furthermore, according to the invention, the inclination data of the first and third points, are automatically calculated from their coordinate values inputted. Hence, similarly as in the case of the device of claim 3, it is unnecessary to provide means for applying the inclination data to them.
In addition, with the sewing data forming device according to the present invention, in the case where a given pattern is of a closed loop (as in the case of a circle or ellipse) the inclination data of the first point is made equal to that of the last point inputted (which is coincident with the first point or close to the latter). Thus, the smooth sewing pattern can be obtained. | A sewing data forming device which forms sewing data to form a fine seam merely by inputting the coordinate data of a plurality of points on a free curve which includes the start and end points. The sewing data forming device for a sewing machine comprises data input unit for inputting coordinate data of a plurality of points along a sewing pattern, the data input unit designating an input condition among point input, linear input and curve input, data storage unit for storing data inputted by the data input unit successively, and data processing unit for applying inclination data to each of the coordinate data so as to form the sewing data between the points adjacent to each other according to a stitch length specified for an interval therebetween. | 3 |
FIELD OF THE INVENTION
[0001] This present invention relates to undergarments in general, and more specifically to women's disposable undergarments having a fluid repellent region and an absorbent layer to be used with a woman's normal feminine care protection during her menstrual period.
BACKGROUND OF THE INVENTION
[0002] Regular undergarments in current use are made of cotton and/or synthetic materials. The cotton and synthetic panties typically do not offer barrier protection. Often the synthetic panties have a cotton lined crotch to absorb vaginal discharges or perspiration. The absorbent/barrier properties of regular undergarments are minimal such that any vaginal, discharge and/or heavy perspiration may strike through onto outer clothing (i.e., penetration of liquid from the interior to the exterior of the panty.)
[0003] Panty liners and feminine care sanitary napkins or pads used with regular undergarments have polyethylene backings that provide some barrier properties needed to prevent liquid strike through. However, if the vaginal discharge extends to the sides or the ends of the pads it can leak onto the undergarment. This leakage can stain the undergarment. Depending upon the amount of leakage, liquid may strike through or go around the undergarment to stain outer clothing and or bedding. Women with heavy periods often use one or more maxi pads, double pads and/or tampons alone, or in combination, and change these pads and tampons frequently to prevent embarrassing, messy, leakage and/or staining of outer clothing. In some cases, during their heaviest flow days, women will restrict their activities and stay home.
[0004] A majority of women experience some leakage of menses from their pads to their undergarments. This varies from being limited to a small number of pads leaking onto only the undergarment during light flow to leakage onto the wearer's outer clothing on almost half the pads worn during heavy flow. Normally this leakage occurs at the side of the product, although end leakage is also a problem. Placement of maxi pads and overnight pads in the crotch of regular undergarments shows that, at best, the pads lay on the leg elastic and, at worst, overhang the leg elastics. This causes side leakage onto the undergarment and possibly onto outer clothing. Typical leakage from the pads is caused by poor fit of the pad to the body, improper positioning of the pad by the user and lack of absorbency. Leakage from the undergarment onto the outer clothing is due to incompatibility between the pad width and the panty crotch width and lack of barrier properties, in the panty material around the edge portion of the pad.
SUMMARY OF THE INVENTION
[0005] Briefly, this invention describes a three dimensional, disposable, discrete panty with fully elasticized leg and waist openings that is circumferentially stretchable about the hip and stomach regions and which provides back-up leakage protection to feminine care products. It is particularly useful during the wearer's menstrual period, normally occurring in non-pregnant women about every four weeks, from menarche to menopause.
[0006] The protection benefit is obtained by providing a flexible secondary absorbent associated with the crotch of the undergarment which holds the primary absorbent in proper location for vaginal discharge (menses). The secondary absorbent extends from the crotch into the body of the undergarment front and back and may extend over the leg elastics. This provides an undergarment which is capable of trapping and absorbing the leakage from the pad and preventing liquid strike through onto outer clothing and bed linen.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The present invention will be more fully understood and further advantages will become apparent when reference is made to the following detailed description of the invention and the drawings, in which:
[0008] [0008]FIG. 1 is a top plan view of a panty article of the present invention in a preassembled flat configuration;
[0009] [0009]FIG. 2 is a perspective view of a full-sized, disposable menstrual panty of the present invention.
[0010] [0010]FIG. 3 is a sectioned view taken along view lines 3 - 3 of FIG. 1 and illustrating the outer cover, liner and elastics.
[0011] [0011]FIG. 4 is a sectioned view taken along view lines 4 - 4 of FIG. 1 and illustrating the absorbent layer, barrier and outer cover.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0012] The following detailed description is made in the context of an article including a disposable panty for holding a sanitary pad in place during use. It is readily apparent, however, that the present invention can be employed with other disposable articles, such as feminine tampons, incontinent garments and the like.
[0013] The disposable panty of FIG. 1 illustrates the preferred embodiment of the present invention in a flat configuration prior to assembly. In FIG. 1, a panty 12 is shown having an outer cover 13 which includes a front body portion 14 , a back body portion 15 , a front waist portion 16 , a back waist portion 17 , a crotch portion 18 , waist liner 26 (not shown), leg liner 38 (not shown) and body liner 80 (not shown).
[0014] The outer cover 13 is compliant and soft feeling to the wearer. The outer cover 13 may be liquid pervious, permitting liquids to readily penetrate into its thickness, or impervious, resistent to the penetration of liquids into its thickness. A suitable outer cover 13 may be manufactured from a wide range of materials, such as natural fibers (e.g., wood or cotton fibers), synthetic fibers (e.g., polyester or polypropylene fibers) or from a combination of natural and synthetic fibers or reticulated foams and apertured plastic films.
[0015] There are a number of manufacturing techniques which may be used to manufacture the outer cover 13 . For example, the outer cover 13 may be woven, nonwoven, such as spunbonded, carded, or the like. A suitable outer cover 13 is carded, and thermally bonded by means well known to those skilled in the fabric art. Alternatively, the outer cover is a spunbond. Ideally, the outer cover is a spunbond polypropylene nonwoven with a wireweave bond pattern having a grab tensile of 19 pounds as measured by ASTM D1682 and D1776, a Taber 40 cycle abrasion rating of 3.0 as measured by ASTM D1175 and Handle-O-Meter MD value of 6.6 grams and CD value of 4.4 grams using TAPPI method T402. Suitably, the spunbond material is available from Kimberly-Clark Corporation, located in Roswell, Ga. The outer cover 13 has a weight from about 0.3 oz. per square yard (osy) to about 2.0 osy and alternatively about 0.7 osy. Preferably, the outer cover of the undergarment has a printed pattern, is colored or is decoratively embossed.
[0016] Referring to FIGS. 1, 2 and 3 , an edge 60 of front body portion 14 is assembled with an edge 62 of the back body portion 15 to form a seal 64 . Similarly, an edge 66 of the front body portion 14 is assembled with an edge 68 of the back body portion 15 to form a seal 70 . The waist portions 16 and 17 , when assembled form a waist opening 20 for putting on and taking off the panty 12 . The waist opening 20 is surrounded at least in part by a waist elastic 22 . The waist elastic 22 is stretched and attached to the waist portion 16 . The waist elastic 22 is released after attachment to produce waist folds or pleats 24 to allow expansion of the waist opening 20 so that the panty 12 can fit various sized women. Because users of this invention generally prefer a brief style panty, the waist portion 16 of the panty 12 preferably comes to the navel and is even around the wearer's waist. Having the panty 12 at this height and then drawing in the waist portion 16 with the waist elastic 22 provides a snug fit. Alternative panty styles include bikini (e.g. regular leg cut and french leg cut) and hipster (e.g. regular leg cut or french leg cut).
[0017] Referring again to FIGS. 1 and 2, the front body portion 14 and the back body portion 15 together with the crotch portion 18 forms leg openings 28 and 30 , respectively, which are generally circular or oval in shape. The leg openings 28 and 30 are each surrounded at least in part by leg elastics 32 and 34 , respectively. The leg elastics 32 and 34 are stretched and attached to the front and back body portions 14 and 15 and the crotch portion 18 . The elastics are released after attachment to produce leg folds or pleats 36 to allow expansion of the leg openings 28 and 30 to fit various sized legs.
[0018] The front body portion 14 is usually divided into a front upper portion 40 and a front lower portion 42 . Similarly, the back body portion 15 is divided into a back upper portion 41 and a back lower portion 43 . The upper portions 40 and 41 are preferably designed to include body elastics 44 which are capable of stretching to allow the wearer to put on the panty 12 and then readily resume the body elastic's normal contracted form. This ensures a close or snug fit to different body and size forms. A number of body elastics 44 are positioned on both the front and the back portions 40 and 41 , respectively, at positions between the waist opening 20 and the leg openings 28 and 30 , so that the panty 12 fits the wearer better, particularly around the body. The lower body portions 42 and 43 do not necessarily require elastics. If the outer cover incorporates the body elastic, the basis weight of the outer cover and body elastic laminate may be as high as 5 osy.
[0019] In reference to the crotch portion 18 of FIG. 1, the functional total capacity of normal pads worn during the menstrual cycle ranges from about 12 grams to about 63 grams. More typically, the capacity of the pads is above 20 grams. The marketing names associated with such pads include “thin maxi”, “maxi”, “thick maxi” and “super maxi”. These will be referred to as maxi pads. The entire absorbent core normally contained in a maxi pad and which is used during medium to high menstrual flow periods in the panty 12 is the “primary” absorbent 45 . The absorbent which is associated with the crotch portion of the current invention is the “secondary” absorbent.
[0020] The crotch portion 18 of the panty 12 consists of an absorbent barrier composite 46 . The absorbent barrier composite 46 further consists of a liquid barrier 48 and a secondary absorbent 50 . Preferably, the thickness of the crotch portion 18 is less than about 4 mm. The thickness is measured on a 4 inch (102 mm) square sample (leg elastics removed) with a Mitutoyo Digamatic Indicator using a 3 inch (76 mm) diameter acrylic platen and assembly to produce a pressure of 0.05 psi. The liquid barrier 48 is needed to prevent liquid strike through onto the outer clothing when leakage occurs on. the panty 12 . The liquid barrier 48 is located on the inside of the crotch portion 18 and consists of a liquid impervious film such as polyethylene. Use of only the film would be hot and uncomfortable, would not be durable enough to withstand changing of pads and would smear any menses which leaked off of the primary absorbent 45 . Any film crotch material in the prior art that is elastic is nominally undesirable for the attachment of a pad since the stretch could detach the pad. Therefore, it is desirable to associate the secondary absorbent 50 with a liquid barrier 48 which is nonelastic.
[0021] The secondary absorbent 50 should have a liquid capacity great enough to absorb leakage of menses from the primary absorbent 45 . The secondary absorbent 50 should preferably have a capacity (described below) and a thickness substantially less than that of the primary absorbent 45 , thus providing a nonbulky and flexible fit. The capacity of the secondary absorbent 50 should have a total capacity of about one-half of the primary absorbent 45 . Preferably, the secondary absorbent 50 should have a total capacity of at least about 3 grams and not more than 6 grams. More preferably, the total capacity of the secondary absorbent 50 should be from about 4 grams to about 6 grams. However, the basis weight of or the type of secondary absorbent 50 should be adjusted to provide resistance to flexibility of less than around 400 grams.
[0022] The absorbent barrier composite of the present invention has a low stiffness. The low stiffness allows the absorbent and barrier to remain attached to the conformable outer cover which conforms to a wide range of body sizes and shapes. Preferably the absorbent barrier composite has a stiffness of less than 400 grams along any axis tested, more preferably less than 300 grams along any axis and less than 100 grams along the axis parallel to the waist opening in the invention.
[0023] The secondary absorbent alone will have a stiffness of less than 250 grams and preferably less than 100 grams along any axis and more preferably less than 75 grams along the axis parallel to the waist opening in the invention.
[0024] The stiffness of the absorbent barrier composite is measured by peak bending stiffness. Peak bending stiffness is measured by INDA Standard Test method IST 90.3-92-Standard Test Method for Handle-O-Meter Stiffness of Nonwoven Fabrics. The nonwoven to be tested is deformed through a restricted slot opening by a blade, and the required force is measured. This force is a measure of both flexibility and surface friction of the absorbent.
Apparatus
[0025] The test apparatus is an Electronic Digital Read-Out Handle-O-Meter, Model #211-5 equipped with flat plates. The apparatus is available from Thwing-Albert Instrument Company in Philadelphia, Pa.;
Number and Preparation of Samples
[0026] For each procedure for this test, five samples should be prepared according to the method described in IST 90.3-92. For tests involving the absorbent barrier composite, the specimen should include all structural components of the absorbent barrier composite including any materials or methods used to bond that composite together. For tests of the secondary absorbent only, the specimens should be all structural components of the secondary absorbent including materials or methods for bonding that secondary absorbent together.
Procedure
[0027] The procedure should be conducted as described in IST 90.3-92. The procedure makes provisions for altering specimen dimensions if resultant grams readout exceeds the 100 gram capacity of the instrument. Reduction in sample size to result in a read-out within the range of the instrument may be necessary for materials falling in the range of the above description. Conduct all such modifications as described in IST 90.3-92 and use the test unit conversion described in section 7.1 of IST 90.3-92. The gap should be set at 0.25 inches (6 mm) as described in section 10.1 of the IST 90.3-92. The absorbent barrier composite should be tested along an axis parallel to the direction in which the absorbent composite was manufactured (so-called machine direction) as well as the axis perpendicular to the direction of the absorbent composite's manufacture (so-called cross direction). In addition each side should be tested along each axis. These steps are detailed in sections 10.1 through 10.10 inclusive in IST 90.3-92.
Calculations
[0028] The maximum reading for each specimen is recorded per IST 90.3-92 section 10.3. The five values are averaged for each axis and side condition tested. The results are reported as maximum grams reading for each specimen. This differs from the millinewtons called for in IST 90.3-92 sections 11 and 12. The average of all five values for each condition is calculated.
[0029] The total capacity of the primary absorbent 45 and the secondary absorbent 50 are determined as follows. Any panty adhesive release paper is removed from the pad to be tested. The total capacity of the primary absorbent 45 is determined using the entire napkin minus any release paper. The total capacity of the secondary absorbent 50 is determined using the absorbent barrier composite 46 of the panty 12 and the outer cover 13 . The specimen is weighed to the nearest 0.1 gram and acclimated at standard relative humidity and temperature for two hours. The specimen is then submerged in a beaker of sterile saline (0.9% sodium chloride solution obtainable from the Baxter Travenol Company of Deerfield, Ill.), such that the specimen is totally submerged and is not bent or otherwise twisted or folded. The specimen is submerged for 10 minutes. The specimen is removed from the saline and suspended for two minutes in a vertical position to allow the saline to drain out of the specimen. The specimen is then placed body facing surface down onto an absorbent blotter, such as filter paper #631 available from the Filtration Science Corp, Eaton-Dikmena Division of Mount Holly Springs, Pa. A uniform 17.6 grams per square centimeter load is placed over the specimen to squeeze excess liquid out of the specimen. The absorbent blotter is replaced every 30 seconds until the amount of liquid transferred to the absorbent blotter is less than 0.5 grams in a 30 second period. The specimen is then weighed to the nearest 0.1 gram and the dry weight of the specimen is subtracted from the final wet weight. The difference in grams is the total capacity of the specimen.
[0030] In construction of the absorbent barrier composite 46 , the liquid barrier 48 should retard the movement of the liquid through the absorbent barrier composite 46 by making the barrier liquid resistant to penetration normally encountered under wearing conditions. The composite may be rendered liquid impermeable by any method well known in the art such as coating the secondary absorbent 50 or by securing a separate liquid impermeable material to the secondary absorbent 50 . Alternatively the liquid barrier 48 consists of a liquid impervious film or foam which is pervious to water vapor under normal wearing conditions. More preferred, the liquid barrier 48 has a water vapor transmission rate of at least about 3500 grams/m 2 /day measured by ASTM E96-92. One example of a suitable film is a 39.4 grams per square meter microporous film produced by Mitsui and sold by Consolidated Thermoplastics (CT) under the tradename of ESPOIR® N-TAF-CT.
[0031] The secondary absorbent 50 may be any construction which is generally compressible, conformable, non-irritating to the wearer's skin, capable of absorbing and retaining menstrual fluid. Optionally, the secondary absorbent 50 has first and second opposed faces and includes an absorbent rich layer 51 and a support layer 53 . The absorbent rich layer 51 may be manufactured in a wide variety of sizes and shapes (e.g., rectangular, hour-glass, etc. ) and from a wide variety of liquid absorbent materials, such as fiberized wood pulp. Examples of other suitable absorbent materials include creped cellulose wadding, absorbent foams, absorbent sponges, superabsorbent polymers, or any equivalent material or combination materials. The support layer 53 may be any construction which is generally resistent to deterioration by liquids while being conformable, non-noisy and capable of holding the absorbent rich layer 51 in place.
[0032] Alternatively, the absorbent rich layer 51 can range from 30 to 80 gsm 1:1 blend of northern hardwood pulp and southern softwood pulp. The support layer 53 can be a 12-15 gsm spunbond. The pulp layer is hydroentangled through the spunbond. Alternatively, the combined layers may then be microcreped. The liquid barrier 48 and the secondary absorbent 50 are bonded together using an adhesive 72 add-on of 3 to 7 gsm. Optionally, the absorbent rich layer 51 is bonded to the barrier of the absorbent barrier composite 46 . This arrangement permits improved attachment, removal and reattachment of the primary absorbent 45 to the panty 12 . The liquid barrier 48 is bonded to the outer cover 13 on the inside of the panty with an adhesive 74 add-on of 5 to 10 gsm. The liquid barrier 48 may be an adhesive film which bonds the secondary absorbent 50 to the outer cover 13 . A suitable adhesive for both applications includes, for example, National Starch NS 34-5561 hot melt adhesive which is available from National Starch and Chemical Company located in Bridgewater, N.J.
[0033] The width of the crotch portion 18 between the leg elastics 32 and 34 should be wide enough to lay the primary absorbent 45 between the edges without having the primary absorbent 45 obstruct the leg elastics. This allows the leg elastics 32 and 34 to contract and draw up the sides of the crotch to accommodate the depth of the primary absorbent 45 being used and give surface area within the crotch portion 18 to contain leakage from the primary absorbent 45 .
[0034] The minimum width of the crotch portion 18 should not be so wide as to seem bulky or uncomfortable, but a suitable width is at least about 2.75 inches (70 mm) between the leg elastics. The minimum width is advantageous from about 3 inches (76 mm) to about 3.5 inches (89 mm). Optionally, the width is about 3 inches (76 mm). Preferably, the leg elastics 32 and 34 are from about 0.375 inch (10 mm) to about 0.625 inch (16 mm) wide. More preferably, the width is about 0.5 inch (13 mm). Preferably, ruffle material on the edge of the leg openings 28 and 30 outside the leg elastics 32 and 34 is less than about 0.25 inch (6 mm). More preferably, the ruffle material is less than about 0.125 inch (3 mm). It is most desirable to eliminate the ruffle material from the edge of the leg openings 28 and 30 . The overall width of the crotch portion 18 includes the width between the leg elastics 32 and 34 , the width of the leg elastics 32 and 34 and the ruffle material outside the leg elastics 32 and 34 to the edge of the leg openings 28 and 30 . Preferably, the overall width of the crotch portion 18 should be at least about 4 inches. (102 mm). The width of the absorbent barrier composite 46 is sized in relation to the width of the crotch portion 18 . Preferably, the width of the composite 46 is at least the width of the crotch portion 18 between the leg elastics 32 and 34 . More preferably, the width is equivalent to the width of the crotch portion 18 .
[0035] The overall length of the absorbent barrier composite 46 should be adequate to extend beyond the ends of the primary absorbent 45 to help prevent liquid strike through at these points when sleeping or sitting. This overall length is at least about 15 inches (382 mm) thus extending beyond the crotch portion 18 along the longitudinal centerline A-A of the panty 12 . Alternatively, the length should be in the range of about 15 inches (382 mm) to about 19 inches (484 mm). Optionally, the length of the composite 46 is about 17 inches (433 mm).
[0036] The width of the absorbent barrier composite 46 beyond the crotch portion 18 should be at least as wide as the width of the crotch portion 18 . The width of the absorbent barrier composite 46 could be narrowed beyond the crotch portion 18 but may compromise the leakage containment. More preferably, the width is from about 5 inches (127 mm) to about 12 inches (306 mm), alternatively from about 5.5 inches (140 mm) to about 7.5 inches (191 mm). Optionally, the width is about 6.5 inches (165 mm).
[0037] The present invention contemplates various shapes of the composite 46 . One preferred composite has a non-rectangular shape with rounded ends which provides extensive coverage in the seat of the finished panty 12 . Another preferred absorbent barrier composite 46 embodiment is rectangular in shape with rounded ends. The essentially rectangular-shaped absorbent barrier composite 46 is more preferred since it can be squared off at the ends to provide a smoother appearance in the back of the panty 12 . Line 76 may be embossed or printed on the inner surface of the crotch portion 18 to aid in placement of the primary absorbent 45 by the wearer.
[0038] Referring to FIG. 3, the waist elastic 22 is shown covered with a waist liner 26 . Referring to FIGS. 3 and 4, the leg elastics 32 and 34 are shown covered by the absorbent barrier composite 46 and a leg liner 38 . Referring to FIG. 3, the body elastic 44 is shown covered with a body liner 80 . The liner consists of a nonwoven or other soft material for contacting the wearer's skin.
[0039] The position and the shape of the leg openings 28 and 30 are important to avoid tightness in the crotch and groin area of the wearer, to obtain adequate buttocks coverage, and to prevent the panty 12 from tilting forward, i.e. tilting such that the front waist edge dips lower in relationship to the back waist edge. FIG. 1 illustrates the most preferred design for leg fit and buttocks coverage. The shape of the curve across the top of the leg may be considered. If the curve is too deep, the panty 12 will shift downward and backward resulting in a short front waist, increased back length and bagginess in the seat of the panty. This causes the panty 12 to appear tilted when worn as evidence by an unevenness around the waist of the wearer.
[0040] The leg openings 28 and 30 are important to the correct functioning of the panty 12 . With the panty 12 laid out flat as in FIG. 1, the majority of the back half of the leg opening preferably forms a straight line. More preferably the back edge of the leg opening is straight for a length, θ, of at least about 70% of the length of the entire back half. The straight section θ of the back half of the leg opening should form an acute angle with the longitudinal centerline, A-A, of the panty 12 . More preferably, the line, θ, forms an angle, α, with the centerline A-A of the panty 12 of between about 50° and 65° and most preferably about 60°. The majority of the edge of front half of the leg opening including lengths β and also preferably forms a straight line. More preferably, the lengths of edge β and of the leg opening is straight for at least about 70% of the length of the front half. The straight section β of the front half of the leg opening should form an angle with the centerline of the panty 12 of between about 75° and 110° and most preferably about 90°.
[0041] Likewise, the shape of the arc at the inner groin area is important. If the arc is too shallow, tightness may be experienced at the inner groin area. The preferred narrow crotch width reduces coverage of the buttocks. To compensate for such reduction, the back curve is preferably adjusted downward. The arc between the crotch edge of the leg opening and the back edge of the leg opening should start slightly in front of centerline B-B of the panty 12 , see FIG. 1. This allows the leg elastic to be positioned below the lower edge of the buttocks and helps prevent the panty 12 from riding up when walking. This means that the straight portion of the inner edge of the leg opening is entirely forward of the panty 12 centerline B-B.
[0042] The waist, leg and body elastics 22 , 32 , 34 and 44 , respectively, are attached to the panty 12 on the outer cover 13 in generally a stretched state by means known in the art, such as ultrasonic bonded, heat/pressure bonded or adhesively bonded. Materials suitable for elastics include a wide variety including but not limited to elastic strands, yarn rubber, flat rubber, elastic tape, film-type rubber, polyurethane and elastomeric, tape-like elastomeric or foam polyurethane or formed elastic scrim. Each elastic may be unitary, multipart or composite in construction.
[0043] The waist elastic 22 is about 0.5 inch (13 mm) wide. The elastic may comprise threads, ribbons, a film or composite. The threads or ribbons may be multiple and may be applied as a composite. Preferably, the waist elastic is threads, more preferably four threads are used as the elastic and the threads are spaced about 0.17 inch (4.3 mm) apart. The threads may be made of any suitable elastomeric material. One suitable material is spandex such as Lycra® threads available from Dupont located in Wilmington, Del. Suitable waist elastics include threads having a total decitex (g/10000 m) of about 3760 for 0.5 inch (13 mm) wide elastic. Adhesive 74 is used to bond the elastic to the outer cover 13 and the waist liner 26 . A suitable adhesive includes, for example, Findley H2096 hot melt adhesive which is available from Findley Adhesives located in Milwaukee, Wis.
[0044] The leg elastics 32 and 34 are about 0.5 inch (13 mm) wide. The elastic may comprise threads, ribbons, a film or composite. The threads or ribbons may be multiple and may be applied as a composite. The front and crotch leg elastics may be threads, preferably numbering three threads which are spaced about 0.17 inch (4.3 mm) apart. Back elastics numbering up to six threads should have a width of about 0.75 inch (19 mm) and a spacing of about 0.15 inch (3.8 mm) apart. The threads may be made of any suitable elastomeric material. One suitable material is spandex such as Lycra® threads available from Dupont located in Wilmington, Del. Suitable leg elastics include threads having a total decitex (g/10000 m) of about 3760 for a 0.5 inch (13 mm) wide elastic. Adhesive 74 is used to bond the elastic to the outer cover 13 and to the leg liner 38 .
[0045] To provide a snug leg fit and to draw up the sides of the crotch portion 18 to form the primary absorbent cradle, the leg elastics 32 and 34 are applied to the outer cover 13 under an elongation of about 250%. Preferably, during the application of the elastics, the elastics 32 and 34 are segmented into multiple segments, each segment being elongated to a different degree and applied to the outer cover 13 . In the case of two segments, the front segment is elongated less than the back segment. In the case of three segments, the front and crotch segments are elongated less than the back section. Preferably, the front and crotch segments are elongated to about 150% and the back segment is elongated to about 250%. The segmenting and differing tensions allow easier pad attachment, less tightness in the groin area, and less bunching of the crotch portion 18 caused by high leg elastic retraction. The back leg elastic is under higher elongation to help keep the seat of the panty from creeping up with movement during use.
[0046] The body elastics 44 circumferentially surrounding the body portions 14 and of the panty 12 act independently to conform to the contours of various body types and builds. This provides a smooth, snug, and comfortable fit within a given hip size range. Using higher elongation, closer spacing, and higher cross-sectional area in the waist elastic 22 than in the body elastics 44 , the panty 12 takes on a rounded shape and provides good waist fit across the waist to hip ratios encountered.
[0047] Preferably, in the front body portion the body elastics 44 adjoin both the waist elastic 22 and leg elastics 32 and 34 . In a panty 12 , the body elastics 44 are about 6.5 inches (166 mm) wide in the front and about 6.0 inches (153 mm) wide in the back. The body elastics 44 are preferably spaced about 0.25 inch (6 mm) apart.
[0048] The absorbent barrier composite 46 which extends up the front and/or back body portions toward the waist portion is conformed to the wearer's body by the body elastic 44 . The transition from the front and back lower portions to the front and back upper portions is thus smoothed.
[0049] The waist elastic 22 is desirably under a greater tension per unit width than the body elastics 44 in the upper body portion 40 to provide the snug waist fit over the range of waist to hip ratios of the various body shapes. In the preferred embodiment, the tension on the waist elastic 22 is coordinated with the tension of the body elastics 44 to form a snug fit about the waist opening while providing a smooth transition from the upper body portion 40 to the waist portion 16 .
[0050] In the front and back body portions 14 and 15 , the leg, waist and/or body liners may be expanded to cover the interior of the body portions 14 and 15 . The leg, waist and/or body liners may exclude the center crotch portion 18 which is covered by the application of the absorbent barrier composite 46 . In the body portions where the absorbent barrier composite 46 overlaps the liner, the composite is applied on top of any liner present so as to contact the wearer.
[0051] An acceptable range for the waist elastic tension is from about 380 grams to about 1000 grams. More preferably, the tension at the waist is from about 575 grams to about 750 grams. The preferred leg elastic tension is from about 375 grams to about 1000 grams. More preferably, the tension at the leg is from about 500 grams to about 700 grams. The preferred hip elastic tension is from about 500 grams to about 850 grams. More preferably, the tension at the hip is from about 650 grams to about 750 grams. The waist and leg tensions are determined as follows. The appropriate gauge rod distance is selected from Tables 1 and 2 for a given panty size and desired location measurement. This rod distance is the distance between the top of the upper peg and the bottom of the lower peg on the Chatillon DFG-2 Tensile Tester.
TABLE 1 Gauge Rod Distance Pant Size Waist Leg 5/6 354 mm 278 mm 7/8 392 mm 306 mm 9/10 468 mm 345 mm
[0052] [0052] TABLE 2 Gauge Rod Distance Pant Size Waist Leg 5/6/7 371 mm 288 mm 8/9/10 445 mm 328 mm
[0053] Measurements are recorded on the tester in kilograms, the HOLD/NORM switch is set at “NORM”, the T/C switch is set at “T” (tension). The samples are conditioned and the testing is conducted in a standard laboratory atmosphere of a temperature of 23±2° C. and a relative humidity of 50±5% RH.
[0054] For determination of the waist tension, the edge along the bonded seam of the panty 12 is placed over the upper peg of the tester. The panty 12 is allowed to hang freely from the upper peg and the weight of the specimen is tared out.
[0055] The lower block is lifted upwards and the opposing waist edge along the bonded seam is placed over the peg of the lower block. The block is lowered until the magnet of the tensile tester locks into place. The tester is activated and timed for two minutes. At two minutes, the tension displayed on the gauge is recorded. The tension in kilograms is converted to grams and the panty 12 is removed.
[0056] For determination of leg tension, the edge along the bonded seam near the crotch fold is placed over the upper peg. The panty 12 is allowed to hang freely from the upper peg and the weight of the specimen is tared out.
[0057] The lower block is lifted upwards and the bonded seam along the opposing leg opening edge is placed over the peg of the lower block.
[0058] The block is lowered until the magnet of the tensile tester locks into place. The tester is activated and timed for two minutes. At two minutes, the tension displayed on the gauge is recorded. The tension in kilograms is converted to grams and the panty 12 is removed. This measurement represents the right leg tension. The test is repeated for the left leg tension.
[0059] For determination of hip tension, the top and bottom side seams of the body portion of the panty 12 are placed in the upper and lower 8 inch wide jaws of an Instron Model 1122 equipped with a Sintech software system and the Interactive Materials Analysis Program (IMAP).
[0060] The tension program stretches the elastic body portion at a rate of 500 mm/minute until 1000 grams is reached. The crosshead then returns to the starting position and repeats a second cycle. The stress-strain graph can be plotted and tension data points printed at 50, 60, 70, 80, 90% of the full stretch (defined as length at 1000 grams) for first and second load and unload cycles. The tensions were taken from the second cycle unload values at about 85% of full stretch.
[0061] The side seams 64 and 70 may be made on the inside or outside of the panty 12 or formed flat against the panty 12 to give a more finished look to the panty 12 and to prevent the seams 64 and 70 from showing through clothing. Optionally, the lateral edges 60 , 62 , 66 and 68 of the front and back body portions are not overlapped but are formed flat and extend out laterally. The side seams 64 and 70 should be minimal in width while providing sufficient strength to be pulled up and down many times over a 24 hour wear period.
[0062] The side seams 64 and 70 , respectively, of the outer cover 13 are sealed by means known in the art, such as ultrasonic bonding, stitching, heat/pressure bonding or adhesive bonding. The maximum seam strength attainable is dependent upon materials used, bond pattern, pond width, and process settings of dwell time, power, and pressure. Suitable side seams typically utilize ultrasonic bonding to achieve a seam strength of at least 5 kg.
[0063] The seams 64 and 70 may have an unbonded portion outboard of the bonded area to provide for a soft edge to the seam. This unbonded portion can ranged from 2 to 3 mm in width. Alternatively, the entire seam width (bonded portion plus unbonded portion) may be less than about 0.25 inch (6 mm). If the seam is trimmed or cut close to the outer edge of the bond area, a sharp edge is produced along the seam edge which can catch on clothes or be irritating to the wearer's skin.
[0064] The panty 12 was compared to panties constructed of cotton and panties having a barrier but no secondary absorbent 50 . Seventeen women were retained for this comparison. Each woman wore a selected maxi pad with each panty type until the pad leaked onto that panty type. Loose-fitting cotton shorts were worn by each woman over the panty which could be worn under their normal loose-fitting clothing. At the end of each test, the pad, panty and cotton shorts were collected. The pad, panty and shorts were photographed. The results of the comparison found that cotton panties had leakage to outer garments in 35.3% of the women, panties with barriers but no secondary absorbent 50 had leakage in 41.2% of the women and the panty 12 of this invention had leakage in only 23.5% of the women.
[0065] Having thus described the invention in full detail, it will be readily apparent that various changes and modifications may be made without departing from the spirit of the invention. All such changes and modification are contemplated as being within the scope of the present invention, as defined by the following claims. | A three dimensional disposable panty for holding a sanitary pad. The panty may have elasticized leg and waist openings and be stretchable about the hip and stomach regions of a user. The panty provides backup leakage protection to the sanitary pad. The panty includes an absorbent barrier composite positioned in the crotch area and extending into the body of the disposable panty front and back and over the leg elastics to trap pad leakage inside the pant and prevent liquid strike through onto outer clothing and bed linen. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This U.S. non-provisional patent application claims the benefit of U.S. provisional patent application No. 61/942,787, filed on Feb. 21, 2014, the entire contents of which are incorporated by reference herein.
FIELD OF THE INVENTION
The present invention relates generally to the field of building supplies used in the construction of offices, homes, and other insulated structures. More particularly, the present invention is directed to an insulated drop panel that is selectively removable from a passageway to gain access to an attic.
BACKGROUND OF THE INVENTION
Modern structures today typically have several insulated spaces such as attics, crawl spaces and the like. Frequently, to gain access to these insulated spaces, a passageway or portal is provided through which an inner non-exposed region may be accessed. These passageways, or portals, are usually covered by an access panel that is movably coupled to a supporting peripheral frame of the passageway. However, there are scenarios where the access panel may become dislodged from the frame and thereby leave the passageway exposed. Some scenarios include: inadequate fitting between the access panel and the frame; improper installation; structural pressure differentials (i.e., air handlers, hurricane, tornado, thunderstorms, etc.); and combinations thereof. When the access panel becomes dislodged from the peripheral frame, undesired airflow within the structure will result and may adversely affect the thermal efficiency of the structure.
Additionally, even if the access panel does not become dislodged, the panel is frequently devoid of insulation material utilized in the surrounding space. The absence of insulation on the access panel provides an undesired thermal conduit through which a transfer of thermal energy occurs between the insulated space and the occupied portion of the structure. In an attempt to reduce this undesired thermal transfer, insulation may be applied to the access panel; however, previous methods of coupling the insulation to the access panel have proven problematic.
In one known solution, a piece of insulation is merely placed behind the access panel when reinstalling the panel. This known solution, while somewhat useful, has substantial drawbacks. As commonly experienced by homeowners, servicemen and construction workers, the handling of insulation material, especially fiberglass-based materials, causes uncomfortable itching and other undesired health effects such as the inhalation of dislodged glass fibers. This solution requires that the insulation material be handled each time the access panel is removed. Further, this solution does not secure the insulation material with respect to the panel which, in some instances, may allow the insulation material to fall into the insulated space.
Another known solution employs stapling/nailing the insulated material to the back face of the access panel. While this method affixes the insulation to the panel, it presents a substantial drawback. In order to staple/nail the insulated material to the panel, the insulation must be compressed to allow the staple/nail to penetrate the insulation backing and securely enter the panel surface. By compressing the insulation material the thermal efficiency (i.e., R-rating) of the material is adversely affected. Further, the more staples/nails that are used the larger the compressed surface area—resulting in an even greater loss of thermal efficiency.
Another frequently employed solution is to use an adhesive to bond the insulation to the access panel. This solution also has substantial drawbacks. Applying adhesive to the back face of the access panel is time consuming and, depending on the cure time of the adhesive, may delay installation of the panel. Additionally, the use of an adhesive limits coupling of an adjacent layer of insulation to the panel. Since the fibers of fiberglass insulation are readily separable from adjacent fibers, this frequently results in separation of the insulation material layers and, consequently, may reduce the thermal efficiency of the material.
Efforts to provide an insulated access panel that overcomes the drawbacks, disadvantages and limitations inherent in the prior art have not met with significant success to date. As a result, there is a need in the art for an insulation retainer capable of coupling a segment of insulation to an access panel that facilitates panel installation and removal without requiring a user to separately handle the insulation material, does not compress the insulation material, enhances retention of the access panel within the passageway and prevents layer separation of the insulation material.
SUMMARY OF THE INVENTION
The present disclosure is generally directed to an attic access drop panel for selectively closing a geometrically shaped attic passageway defined by structural elements of the attic. The attic access drop panel includes a planar rigid panel having an external periphery formed to fit within the structural elements defining the geometrically shaped attic passageway. An insulating member is on top of and supported by the planar rigid panel wherein the insulating member substantially conforms to the extra periphery of the planar rigid panel. A plurality of retainers are affixed about the periphery of the planar rigid panel wherein each retainer has a first leg affixed to the top of the planar rigid panel and a second leg extending upwardly from the top of the planar rigid panel. The second leg defines at least one protrusion retentively engaging the insulating member. The second leg also forms a bead at a top thereof for bearing against a structural element of the attic defining the attic passageway.
In another aspect, the bead extends outward beyond the external periphery of the rigid panel.
In still another aspect, the first leg and the second leg to form an obtuse angle therebetween.
In yet another aspect, the obtuse angle is approximately 102 degrees.
In a still further aspect, the second leg is approximately 4 inches in length between the first leg and the top of the second leg.
In yet another aspect, the second leg forms a second bead below the bead at the top of the second leg.
In another aspect, the second leg defines at least two protrusions for retentively engaging the insulating member, the two protrusions are positioned between the first leg and the second bead.
In another aspect, the second leg defines at least two protrusions for retentively engaging the insulating member; the two protrusions are positioned between the first leg and the bead at the top of the second leg.
In a still further aspect, the first leg defines a groove extending therealong and positioned approximately at a midpoint of the first leg.
In yet another aspect, a plurality of screws are utilized to affix the plurality of retainers to the planar rigid panel, each screw engages the first leg in the defined groove.
In another aspect, a retainer for fixing to a periphery of a planar rigid panel to form an attic access drop panel for retaining an insulating member thereon comprises a first leg for fixing to a top surface of the planar rigid panel and a second leg extending upwardly from the first leg. The second leg defines at least one protrusion extending inwardly in a direction of the first leg for engaging an insulating member and further forms a bead proximate to a top edge thereof.
In still another aspect, the first leg and the second leg intersect to form an apex therebetween and further wherein the bead extends outwardly from the second leg beyond the apex.
In yet another aspect, the first leg and the second leg form an obtuse angle at the apex.
In another aspect, the obtuse angle is approximately 102 degrees.
In still another aspect, the second leg is approximately 4 inches in length between the apex and the top of the second leg.
In a further aspect, the second leg forms a second bead below the bead at the top of the second leg.
In yet another aspect, the bead and the second bead combine to form an undulating wave.
In a still further aspect, the protrusion is wedge-shaped.
In another aspect, the second leg defines to wedge-shaped protrusions extending inwardly in a direction of the first leg, the two wedge-shape protrusions positioned between the apex and the bead.
In another aspect, the first leg defines a groove extending therealong and positioned approximately at a midpoint of the first leg.
These and other features, aspects, and advantages of the invention will be further understood and appreciated by those skilled in the art by reference to the following written specification, claims and appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described, by way of example, with reference to the accompanying drawings, where like numerals denote like elements and in which:
FIG. 1 presents an isometric view of an attic access drop panel embodying the present invention wherein an insulation layer is removed for clarity;
FIG. 2 presents an isometric view of a retainer of the attic access drop panel for retaining the insulation layer in the panel;
FIG. 3 presents a cross-sectional view of the retainer shown in FIG. 2 and taken along the line 3 - 3 , FIG. 2 ;
FIG. 4 presents an isometric view of an attic access drop panel seated in and closing an attic access passageway wherein the structure defining the attic access passageway is constructed of 2-inch×6-inch lumber;
FIG. 5 presents an isometric view of an attic access drop panel seated in and closing an attic access passageway wherein the structure defining the attic access passageway is constructed of 2-inch×4-inch lumber;
FIG. 6 presents a cross-sectional view of the attic access drop panel seated in and closing the attic access passageway of FIG. 4 and taken along section line 6 - 6 , FIG. 4 ;
FIG. 7 presents a cross-sectional view of the attic access drop panel seated in and closing the attic access passageway of FIG. 5 and taken along section line 7 - 7 , FIG. 5 ;
FIG. 8 presents an isometric view of a first retainer nested in a second retainer wherein the retainers are longitudinally translatable one with respect to the other;
FIG. 9 presents a cross-sectional view of the nested retainers shown in FIG. 8 and taken along section line 9 - 9 , FIG. 8 ; and
FIG. 10 presents an implementation of the invention with an exemplary alternate configuration of the trim component of an access passageway common in some homes.
Like reference numerals refer to like parts throughout the various views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
The following detailed description is merely exemplary in nature and is not intended to limit the described embodiments or the application and uses of the described embodiments. As used herein, the word “exemplary” or “illustrative” means “serving as an example, instance, or illustration.” Any implementation described herein as “exemplary” or “illustrative” is not necessarily to be construed as preferred or advantageous over other implementations. All of the implementations described below are exemplary implementations provided to enable persons skilled in the art to make or use the embodiments of the disclosure and are not intended to limit the scope of the disclosure, which is defined by the claims. For purposes of description herein, the terms “upper”, “lower”, “left”, “rear”, “right”, “front”, “vertical”, “horizontal”, and derivatives thereof shall relate to the invention as oriented in FIG. 1 . Furthermore, there is no intention to be bound by any expressed or implied theory presented in the preceding technical field, background, brief summary or the following detailed description. It is also to be understood that the specific devices and processes illustrated in the attached drawings, and described in the following specification, are simply exemplary embodiments of the inventive concepts defined in the appended claims. Hence, specific dimensions and other physical characteristics relating to the embodiments disclosed herein are not to be considered as limiting, unless the claims expressly state otherwise.
In one exemplary implementation of the invention, an attic access drop panel 100 is shown in FIG. 1 illustrating its various components wherein the attic access drop panel 100 is constructed of a planar rigid panel 110 having an upper surface 112 to which is fastened, utilizing a plurality of screws 106 , a plurality of retainers 120 about a periphery 114 of the planar rigid panel 110 . The planar rigid panel 110 is here shown having a rectangular plan form, however those practiced in the art will recognize that other geometric plan forms are contemplated herein. The retainers 120 , in combination with the upper surface 112 of the planar rigid panel 110 , define a cavity 102 in which an insulating member 118 ( FIGS. 6-7 ) having external dimensions approximating the external dimensions of the periphery 114 of planar rigid panel 110 is retained. The planar rigid panel 110 can be fabricated from known construction materials such as gypsum board, plywood, or the like. The insulating member 118 can be constructed of known insulating materials such as fiberglass batts, rigid foam, or the like.
As further illustrated in FIGS. 2-3 , and most clearly seen in cross-section in FIG. 3 , the retainer 120 has a first leg 122 for fastening to the top surface 112 of the rigid panel 110 . In a most preferred embodiment the first leg 122 has a width of approximately 1.0 inch, and can define on an upper surface 123 thereof, a groove 124 to facilitate the placement of screws 106 ( FIG. 1 ) for fastening the retainer 120 to the rigid panel 110 . The retainer 120 also has a second leg 132 extending upwardly from the first leg 122 such that the first leg 122 and the second leg 132 adjoin at an apex 126 defining an obtuse included angle of approximately 102°. In a most preferred embodiment the second leg 132 has a length of approximately 4.0 inches from apex 126 to a top edge 138 thereof. The second leg 132 has formed in a lower portion thereof at least one and most preferably two spaced apart, wedge-shaped protrusions 134 extending unidirectionally with the first leg 122 . Further, a top portion of the second leg 132 is formed as an undulating wave forming at least one and most preferably two spaced apart beads 136 extending away from the first leg 122 .
In use, and as illustrated in FIGS. 4-7 , an attic access drop panel 100 is shown engaged in and to close an attic passageway 200 . In FIGS. 4-5 , the insulating member 118 has been deleted for the sake of clarity. As shown in FIGS. 4 and 6 , the passageway 200 is defined by spaced apart 2-inch×6-inch lumber segments 202 , which could be lower members of a roof truss or other similar structural assembly. Interstitial 2-inch×6-inch lumber segments 204 extend between lumber segments 202 to fully define a rectilinear periphery of the attic passageway 200 . Panels 208 , such as gypsum panel, are typically affixed to the lumber segments 202 , 204 to form the ceiling of a room below the structure 202 , 204 defining the passageway 200 . Typically, the attic passageway 200 will be further defined by trim segments 210 affixed to the bottom surface of panels 208 and arranged in a manner such that an inner edge of the trim segments 210 extends into the attic passageway 200 forming a lip 212 .
The rigid panel 110 of the attic access drop panel 100 is formed to have an outer periphery smaller than the portion of the attic passageway 200 defined by the lumber segments 202 , 204 and larger than the inner periphery of the attic passageway 200 defined by the lip 212 . In this manner, the attic access drop panel 100 when placed in the attic passageway 200 will rest upon the lip 212 . Further, the retainers 120 , by reason of the obtuse included angle 128 , extend outwardly beyond the periphery of the rigid panel 110 in a manner such that the upper portion thereof contacts and bears upon the inner surface of structural segments 202 , 204 . In particular, since the structural segments 202 , 204 are 2-inch×6-inch lumber, an uppermost bead 136 of retainers 120 bear upon the structural segments 202 , 204 .
As illustrated in FIGS. 5 and 6 , the attic passageway 200 can alternatively be defined by structural segments 205 , 206 wherein the structural segments 205 , 206 are fabricated from 2-inch×4-inch lumber (Note: The remaining features and construction of the attic passageway 200 are identical as those described with respect to FIGS. 4 and 6 ). In this configuration, the uppermost of the beads 136 of retainers 120 extends above the structural elements 205 , 206 and thus a next lower bead 136 , in turn, bears against the inner surfaces of the structural elements 205 , 206 .
Therefore, regardless of the use of 2-inch×6-inch lumber or the use of 2-inch×4-inch lumber to construct the attic structure, a bead 136 of the retainers 120 will bear against the inner surface of the structure defining the attic passageway 200 , thereby providing an effective seal inhibiting airflow therethrough. Further, the installation of the attic access drop panel 100 within the attic passageway 200 as defined by the structural elements 202 , 204 or the structural elements 205 , 206 deforms the second leg 132 towards an interior of the attic passageway 200 . This deformation forces the wedge-shaped protrusions 134 against the edges of the insulating member 118 , thereby resulting in the positive retention of the insulating member 118 above the rigid panel 110 .
Referring now to FIGS. 8-9 , a first retainer 120 is illustrated in a nesting type relationship with an identical retainer 120 . The retainers 120 can be longitudinally translated one with respect to the other as illustrated by arrows A-A ( FIG. 8 ). In this manner, two retainers 120 can be utilized to conform to an edge dimension of the rigid panel 110 that is greater in length than a single retainer 120 .
Since many modifications, variations, and changes in detail can be made to the described preferred embodiments of the invention, it is intended that all matters in the foregoing description and shown in the accompanying drawings be interpreted as illustrative and not in a limiting sense. Thus, the scope of the invention should be determined by the appended claims and their legal equivalents. For example, referring now particularly to FIG. 10 , in an alternative implementation of the invention, and alternate configuration of the trim component of an access passageway is shown, which is common in some homes. Rather than a piece of molding Moll forming the lip onto which the panel rests, some builders will wrap the edge of the opening with gypsum board and utilize the edges of the gypsum board as a supporting lip for the scuttle hatch. | An attic access drop panel for selectively closing a geometrically shaped attic passageway includes a rigid panel having an external periphery formed to fit within the structural elements defining the attic passageway and an insulating member on top of the rigid panel conforming to the external periphery of the rigid panel. A plurality of angle brackets are affixed about the periphery of the rigid panel wherein each bracket has a first leg affixed to the top of the rigid panel and a second leg extends upwardly from the top of the rigid panel. The second leg defines at least one protrusion engaging the insulating member and forms a bead at a top of the second leg for bearing against a structural element of the attic defining the attic passageway. | 4 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a package for mounting a semiconductor device (chip) and a solder bump, and its manufacturing method.
[0003] 2. Description of the Related Art
[0004] Generally, when a semiconductor chip and solder bumps are mounted on terminals of a package by soldering or the like, it is impossible to mount the semiconductor chip and the solder bumps directly on the terminals, because the terminals are not made of rust proof material. Therefore, it is essential to electroplate Au or Ni/Au on the terminals before the semiconductor chip and the solder bumps are mounted.
[0005] In a prior art method for manufacturing a package for mounting a semiconductor device and a bump, an interposer substrate having a first surface for mounting the semiconductor device is prepared. Then, a conductive layer is formed on a second surface of the interposer substrate, and the conductive layer is patterned to form a wiring layer capable of being connected to the semiconductor device, a terminal connected to the wiring layer, and a plating layer connected to the terminal and terminated at an end of the package. Then, a mask layer having an opening exposing the terminal is coated, and the terminal is electroplated by supplying a current from the plating layer to the terminal (see: JP-A-5-95025 & JP-A-8-288422). This will be explained later in detail.
[0006] In the above-described prior art method, however, the plating layer is finally left. Therefore, when the operation frequency of this semiconductor chip is higher, the amount of signals reflected by the plating layer is increased. Also, the parasitic capacitance of the plating layer adversely affects signals from the semiconductor chip to the solder bump and vice versa.
SUMMARY OF THE INVENTION
[0007] It is an object of the present invention to provide a package and its manufacturing method capable of decreasing the amount of reflected signals and reducing the parasitic capacitance by plating layers.
[0008] According to the present invention, in a package for mounting a semiconductor device and a bump, an interposer substrate has a first surface for mounting the semiconductor device. A wiring layer capable of being connected to the semiconductor device, a terminal connected to the wiring layer for mounting the bump, and a plating layer are formed on a second surface of the interposer substrate. The plating layer is connected to one of the terminal and the wiring layer. The plating layer is terminated within the interposer substrate.
[0009] Also, in a method for manufacturing a package for mounting a semiconductor device and a bump, an interposer substrate having a first surface for mounting the semiconductor device is prepared. Then, a conductive layer is formed on a second surface of the interposer substrate, and the conductive layer is patterned to form a wiring layer capable of being connected to the semiconductor device, a terminal connected to the wiring layer, and a plating layer connected to the terminal or the wiring layer and terminated at an end of the package. Then, a mask layer having an opening exposing the terminal is coated, and the terminal is electroplated by supplying a current from the plating layer to the terminal. Finally, the plating layer is terminated within the package.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention will be more clearly understood from the description set forth below, as compared with the prior art, with reference to the accompanying drawings, wherein:
[0011] [0011]FIGS. 1A through 1I are cross-sectional views for explaining a prior art method for manufacturing a BGA type semiconductor device;
[0012] [0012]FIG. 2 is a plan view illustrating the interposer substrate of FIG. 1A;
[0013] [0013]FIG. 3 is a plan view illustrating the pattern layer of FIG. 1B;
[0014] [0014]FIG. 4 is a plan view illustrating the Au plating layers of FIG. 1H;
[0015] [0015]FIG. 5A is a plan view illustrating the BGA type semiconductor device obtained by the method as illustrated in FIGS. 1A through 1I;
[0016] [0016]FIGS. 5B and 5C are side views of the device of FIG. 5A;
[0017] [0017]FIGS. 6A through 6J are cross-sectional views for explaining a first embodiment of the method for manufacturing a BGA type semiconductor device according to the present invention;
[0018] [0018]FIG. 7 is a plan view illustrating the pattern layer of FIG. 6B;
[0019] [0019]FIG. 8 is a plan view illustrating the Au plating layers of FIG. 6H;
[0020] [0020]FIG. 9 is a plan view illustrating the Au plating layers of FIG. 6J;
[0021] [0021]FIG. 10A is a plan view illustrating the BGA type semiconductor device obtained by the method as illustrated in FIGS. 6A through 6J;
[0022] [0022]FIGS. 10B and 10C are side views of the device of FIG. 10A;
[0023] [0023]FIGS. 11, 12 and 13 are plan views illustrating modifications of FIGS. 7, 8 and 9 , respectively;
[0024] [0024]FIGS. 14, 15 and 16 are plan views illustrating other modifications of FIGS. 7, 8 and 9 , respectively;
[0025] [0025]FIGS. 17A through 17J are cross-sectional views for explaining a second embodiment of the method for manufacturing a BGA type semiconductor device according to the present invention;
[0026] [0026]FIG. 18 is a plan view illustrating the pattern layer of FIG. 17B;
[0027] [0027]FIG. 19 is a plan view illustrating the Au plating layers of FIG. 17H;
[0028] [0028]FIG. 20 is a plan view illustrating the Au plating layer of FIG. 17J;
[0029] [0029]FIGS. 21, 22 and 23 are plan views illustrating modifications of FIGS. 18, 19 and 20 , respectively; and
[0030] [0030]FIGS. 24, 25 and 26 are plan views illustrating other modifications of FIGS. 18, 19 and 20 , respectively.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] Before the description of the preferred embodiments, a prior art method for manufacturing a ball grid array (BGA) type semiconductor device will be explained with reference to FIGS. 1A through 1I.
[0032] Initially, an interposer substrate 101 made of polyamide as illustrated in FIG. 2 is prepared. Note that a dotted area PA designates a package area, and CA designates a current supply area.
[0033] Next, referring to FIG. 1A, an adhesive layer 102 is coated on a back surface of the interposer substrate 101 . Then, a copper foil layer 103 is formed on a front surface of the interposer substrate 101 .
[0034] Next, referring to FIG. 1B, the copper foil layer 103 is patterned by a photolithography and etching process to form a pattern layer as illustrated in FIG. 3. Each pattern of the pattern layer is constructed by wiring layers 103 a , terminals 103 b for mounting solder balls (outer bumps) and plating layers 103 c.
[0035] Next, referring to FIG. 1C, a solder resist layer 104 is coated on the entire front surface.
[0036] Next, referring to FIG. 1D, openings 104 a and 104 b are perforated in the solder resist layer 104 . The opening 104 a is used for forming an innerhole INH (see FIG. 1E), and the opening 104 b exposes the terminal 103 b.
[0037] Next, referring to FIG. 1E, an innerhole INH is perforated in the adhesive layer 102 and the interposer substrate 101 by a laser trimming process or the like. Note that the innerhole INH does not penetrate the wiring layer 103 a. Also, the innerhole INH corresponds to a terminal of a semiconductor chip which will be mounted on the back of the interposer substrate 101 .
[0038] Next, referring to FIG. 1F, a plating mask layer 105 made of insulating material is coated on the entire front surface. Then, an electroplating process is carried out by supplying a current to the pattern layer ( 103 a , 103 b , 103 c ) from the current supply area CA of FIG. 2 while the interposer substrate 101 is dipped into a plating solution. As a result, a bump (plug layer) 106 is buried in the innerhole INH.
[0039] Next, referring to FIG. 1G, the plating mask layer 105 is removed.
[0040] Next, referring to FIG. 1H, an Au electroplating process is carried out by supplying a current to the pattern layer ( 103 a , 103 b , 103 c ) from the current supply area CA of FIG. 2 while the interposer substrate 101 is dipped into an Au plating solution. As a result, as illustrated in FIG. 4, an Au plating layer 107 a is formed on the terminal 103 b on the front surface of the interposer substrate 101 , and an Au plating layer 107 b is formed on the plug layer 106 on the back surface of the interposer substrate 101 . Then, the current supply area CA of FIG. 2 is electrically separated from the package areas PA of FIG. 2.
[0041] Finally, referring to FIG. 1I, a terminal of a flip-chip type semiconductor chip 2 is mounted on the back surface of the interposer substrate 101 by using an ultrasonic pushing tool. Then, the semiconductor chip 2 is molded by resin. Also, a solder ball 3 is provided on the front surface of the interposer substrate 101 .
[0042] After that, a plurality of the package areas PA are separated by a cutting apparatus to obtain a plurality of BGA type semiconductor devices as illustrated in FIGS. 5A, 5B and 5 C, where FIGS. 5B and 5C are side views of FIG. 5A.
[0043] In the BGA type semiconductor device obtained by the method as illustrated in FIGS. 1A through 1I, however, the plating layer 103 c is left. Therefore, when the operation frequency of this BGA type semiconductor device is higher, the amount of signals reflected by the plating layer 103 c is increased. Also, the parasitic capacitance of the plating layer 103 c adversely affects signals from the semiconductor chip 2 to the solder bump 3 and vice versa.
[0044] A first embodiment of the method for manufacturing a BGA type semiconductor device will be explained next with reference to FIGS. 6A through 6J.
[0045] Initially, in the same way as in the prior art, an interposer substrate 11 made of polyimide as illustrated in FIG. 2 is prepared.
[0046] Next, referring to FIG. 6A, in the same way as in FIG. 1A, an adhesive layer 12 is coated on a back surface of the interposer substrate 11 . Then, a copper foil layer 13 is formed on a front surface of the interposer substrate 11 .
[0047] Next, referring to FIG. 6B, in a similar way to those of FIG. 1B, the copper foil layer 13 is patterned by a photolithography and etching process to form a pattern layer as illustrated in FIG. 7. Each pattern of the pattern layer is constructed by wiring layers 13 a , terminals 13 b for mounting solder balls (outer bumps), plating layers 13 c , and a ground plate 13 d . Note that the ground plate 13 d is connected to the plating layers 13 c . Also, the terminals 13 b marked by “G” are ground terminals, the terminals 13 b marked by “V cc ” are power supply terminals, and the terminals 13 b marked by “S” are signal input/output terminals.
[0048] Next, referring to FIG. 6C, in the same way as in FIG. 1C, a solder resist layer 14 is coated on the entire front surface.
[0049] Next, referring to FIG. 6D, in the same way as in FIG. 1D, openings 14 a and 14 b are perforated in the solder resist layer 14 . The opening 14 a is used for forming an innerhole INH (see FIG. 6E), and the opening 14 b exposes the terminal 13 b.
[0050] Next, referring to FIG. 6E, in the same way as in FIG. 1E, an innerhole INH is perforated in the adhesive layer 12 and the interposer substrate 11 by a laser trimming process or the like. Note that the innerhole INH does not penetrate the wiring layer 13 a . Also, the innerhole INH corresponds to a terminal of a semiconductor chip which will be mounted on the back of the interposer substrate 11 .
[0051] Next, referring to FIG. 6F, in the same way as in FIG. 1F, a plating mask layer 15 made of insulating material is coated on the entire front surface. Then, an electroplating process is carried out by supplying a current to the pattern layer ( 13 a , 13 b , 13 c , 13 d ) from the current supply area CA of FIG. 2 while the interposer substrate 11 is dipped into a plating solution. As a result, a bump 16 is buried in the innerhole INH.
[0052] Next, referring to FIG. 6G, in the same way as in FIG. 1G, the plating mask layer 15 is removed.
[0053] Next, referring to FIG. 6H, in the same way as in FIG. 1H, an Au electroplating process is carried out by supplying a current to the pattern layer ( 13 a , 13 b , 13 c , 13 d ) from the current supply area CA of FIG. 2 while the interposer substrate 11 is dipped into an Au plating solution. As a result, as illustrated in FIG. 8, an Au plating layer 17 a is formed on the terminal 13 b on the front surface of the interposer substrate 11 , and an Au plating layer 17 b is formed on the plug layer 16 on the back surface of the interposer substrate 11 . Then, the current supply area CA of FIG. 2 is electrically separated from the package areas PA of FIG. 2.
[0054] Next, referring to FIG. 9 as well as FIG. 6I, throughholes TH are perforated in the interposer substrate 11 , the adhesive layer 12 and the solder resist layer 14 by using metal molds. As a result, the plating layers 13 c connected to the power supply terminals V cc and the signal input/output terminals S are terminated at the throughholes TH. In this case, these plating layers 13 c serve as stubs. On the other hand, the plating layers 13 c connected to the ground terminals G remains and is still connected to the plate ground layer 13 d.
[0055] Finally, referring to FIG. 6J, in the same way as in FIG. 1I, a terminal of a flip-chip type semiconductor chip 2 is mounted on the back surface of the interposer substrate 11 by using an ultrasonic pushing tool. Then, the semiconductor chip 2 is molded by resin. Also, a solder ball 3 is provided on the front surface of the interposer substrate 11 .
[0056] After that, a plurality of the package areas PA are separated by a cutting apparatus to obtain a plurality of BGA type semiconductor devices as illustrated in FIGS. 10A, 10B and 10 C, where FIGS. 10B and 10C are side views of FIG. 10A.
[0057] In the BGA type semiconductor device obtained by the method as illustrated in FIGS. 6A through 6J, the plating layers 13 c connected to the power supply terminal V cc and the signal input/output terminals S are terminated at the throughholes TH. Therefore, even when the operation frequency of this BGA type semiconductor device is higher, the amount of signals reflected by the plating layers 13 c is decreased. Also, since the parasitic capacitance of the plating layers 13 c is decreased, signals from the semiconductor chip 2 to the solder bump 3 and vice versa are hardly affected thereby.
[0058] Also, in the first embodiment, since the ground plate 13 d covers a large area of the package, the noise at the signal input/output terminals S can be remarkably suppressed.
[0059] Further, in the first embodiment, if the terminals 13 b are signal input/output terminals S, a length L of each of the pattern layers 13 between the bump 16 and the throughhole TH should be as small as possible to decrease the capacitance, thus enabling a high speed operation. Also, a length L1 of each of the remaining plating layers 13 c connected to the signal input/output terminals S should be as small as possible to decrease the amount of reflected signals. Further, the length L of each of the pattern layers 13 connected to the signal input/output terminals S are equalized to homogenize the capacitance thereof, which is helpful in a high speed operation.
[0060] The first embodiment can be modified as illustrated in FIGS. 11, 12 and 13 , which correspond to FIGS. 7, 8 and 9 , respectively. That is, the ground plate 13 d of FIGS. 7, 8 and 9 is replaced by wiring layers 13 e . Even in this modification, the same effect except for the noise characteristics by the ground plate 13 d can be expected.
[0061] The first embodiment can be also modified as illustrated in FIGS. 14, 15 and 16 , which correspond to FIGS. 7, 8 and 9 , respectively. That is, the ground plate 13 d of FIGS. 7, 8 and 9 is replaced by plating layers 13 f . The plating layers 13 f are used in the Au electroplating process, and the plating layers 13 f as well as the plating layers 13 c are terminated by forming a throughhole TH. In FIGS. 14, 15 and 16 , note that each of the terminals 13 b provided in the periphery of the package PA can be any of a ground terminal G, a power supply terminal V cc and a signal input/output terminal S, while each of the terminals 13 b provided at the center of the package PA can be a signal input/output terminal S or a power supply terminal G. Even in this modification, the same effect except for the noise characteristics by the ground plate 13 d can be expected.
[0062] A second embodiment of the method for manufacturing a BGA type semiconductor device will be explained next with reference to FIGS. 17A through 17J.
[0063] Initially, in the same way as in the prior art, an interposer substrate 21 made of polyimide as illustrated in FIG. 2 is prepared.
[0064] Next, referring to FIG. 17A, in the same way as in FIG. 1A, an adhesive layer 22 is coated on a back surface of the interposer substrate 21 . Then, a copper foil layer 23 is formed on a front surface of the interposer substrate 21 .
[0065] Next, referring to FIG. 17B, in a similar way to those of FIG. 1B, the copper foil layer 23 is patterned by a photolithography and etching process to form a pattern layer as illustrated in FIG. 18. Each pattern of the pattern layer is constructed by wiring layers 23 a , terminals 23 b for mounting solder balls (outer bumps), plating layers 23 c , and a ground plate 23 d . Note that the ground plate 23 d is connected to the plating layers 23 c . Also, the terminals 23 b marked by “S” are signal input/output terminals. Further, since the ground plate 23 d surrounds the pattern layer ( 23 a , 23 b , 23 c ) so that the pattern layer is shielded by the ground plate 23 d , the inductance of the package can be decreased.
[0066] Next, referring to FIG. 17C, in the same way as in FIG. 1C, a solder resist layer 24 is coated on the entire front surface.
[0067] Next, referring to FIG. 17D, in the same way as in FIG. 1D, openings 24 a and 24 b are perforated in the solder resist layer 24 . The opening 24 a is used for forming an innerhole INH (see FIG. 17E), and the opening 24 b exposes the terminal 23 b.
[0068] Next, referring to FIG. 17E, in the same way as in FIG. 1E, an innerhole INH is perforated in the adhesive layer 22 and the interposer substrate 21 by a laser trimming process or the like. Note that the innerhole INH does not penetrate the wiring layer 23 a . Also, the innerhole INH corresponds to a terminal of a semiconductor chip which will be mounted on the back of the interposer substrate 21 .
[0069] Next, referring to FIG. 17F, in the same way as in FIG. 1F, a plating mask layer 25 made of insulating material is coated on the entire front surface. Then, an electroplating process is carried out by supplying a current to the pattern layer ( 23 a , 23 b , 23 c , 23 d ) from the current supply area CA of FIG. 2 while the interposer substrate 21 is dipped into a plating solution. As a result, a bump 26 is buried in the innerhole INH.
[0070] Next, referring to FIG. 17G, in the same way as in FIG. 1G, the plating mask layer 25 is removed.
[0071] Next, referring to FIG. 17H, in the same way as in FIG. 1H, an Au electroplating process is carried out by supplying a current to the pattern layer ( 23 a , 23 b , 23 c , 23 d ) from the current supply area CA of FIG. 2 while the interposer substrate 21 is dipped into an Au plating solution. As a result, as illustrated in FIG. 19, an Au plating layer 27 a is formed on the terminal 23 b on the front surface of the interposer substrate 21 , and an Au plating layer 27 b is formed on the plug layer 26 on the back surface of the interposer substrate 21 . Then, the current supply area CA of FIG. 2 is electrically separated from the package areas PA of FIG. 2.
[0072] Next, referring to FIG. 20 as well as FIG. 17I, a part of the plating layer 27 c on the side of the terminals S is removed by a laser trimming process or a photolithography and etching process. Note that a part of the solder resist layer 24 is also removed. As a result, the plating layer 23 c connected to the signal input/output terminal S is terminated at a location indicated by X. In this case, the plating layer 23 c serves as a stub.
[0073] Finally, referring to FIG. 17J, in the same way as in FIG. 1I, a terminal of a flip-chip type semiconductor chip 2 is mounted on the back surface of the interposer substrate 21 by using an ultrasonic pushing tool. Then, the semiconductor chip 2 is molded by resin. Also, a solder ball 3 is provided on the front surface of the interposer substrate 21 .
[0074] After that, a plurality of the package areas PA are separated by a cutting apparatus to obtain a plurality of BGA type semiconductor devices.
[0075] In the BGA type semiconductor device obtained by the method as illustrated in FIGS. 17A through 17J, the plating layers 23 c connected to the signal input/output terminal S is terminated at the location X. Therefore, even when the operation frequency of this BGA type semiconductor device is higher, the amount of signals reflected by the plating layers 23 c is decreased. Also, since the parasitic capacitance of the plating layers 23 c is decreased, signals from the semiconductor chip 2 to the solder bump 3 and vice versa are hardly affected thereby.
[0076] Also, in the second embodiment, since the ground plate 23 d covers a large area of the package, the noise at the signal input/output terminals S can be remarkably suppressed.
[0077] Further, in the second embodiment, a length L of the pattern layers 23 between the bump 26 and the location X should be as small as possible to decrease the capacitance, thus enabling a high speed operation. Also, a length L1 of each of the remaining plating layers 23 c should be as small as possible to decrease the amount of reflected signals.
[0078] The second embodiment can be modified as illustrated in FIGS. 21, 22 and 23 , which correspond to FIGS. 18, 19 and 20 , respectively. That is, the plating layer 23 c is connected between the ground plate 23 d and a portion of the wiring layer 23 a where the bump 26 will be provided.
[0079] The second embodiment can be also modified as illustrated in FIGS. 24, 25 and 26 , which correspond to FIGS. 18, 19 and 20 , respectively. That is, the plating layer 23 c is connected between the ground plate 23 d and a center portion of the wiring layer 23 a.
[0080] Even in the modifications, the same effect can be expected. In addition, the length L of the pattern layers 23 are equalized to homogenize the capacitance thereof, which is helpful in a high speed operation.
[0081] In the above-described embodiments, although the interposer substrate is made of single polyamide, the present invention can be applied to an interposer substrate made of other material or multi-structured materials. Additionally, the present invention can be applied to other packages than a BGA type package, such as a land grid array (LGA) type package.
[0082] As explained hereinabove, according to the present invention, since plating layers for supplying currents during an electroplating operation are finally terminated, even when the operation frequency of a semiconductor device is higher, the amount of signals reflected by the plating layers can be decreased. Also, since the parasitic capacitance of the plating layers is decreased, signals from the semiconductor device to its solder bumps and vice versa are hardly affected thereby. | In a package for mounting a semiconductor device and a bump, an interposer substrate has a first surface for mounting the semiconductor device. A wiring layer capable of being connected to the semiconductor device, a terminal connected to the wiring layer for mounting the bump, and a plating layer are formed on a second surface of the interposer substrate. The plating layer is connected to one of the terminal and the siring layer. The plating layer is terminated within the interposer substrate | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to the U.S. patent application titled “Distributed Detection with Diagnosis”, attorney docket number 317462.01/MSFT- 5744 ”, filed herewith. The contents of the application are hereby incorporated in its entirety.
BACKGROUND
[0002] Modern computers receive and transmit an increasingly large amount of packets. These packets represent communications with other computers, such as requests for services and data, for example. Because of the large volume of packets sent and received, it is difficult to determine problems and performance issues with the various services on the computer or that are available on the network.
[0003] Existing solutions to this problem generally rely on processing some type of alarm or error data to determine the cause of a particular problem. Other solutions repeatedly probe existing services to determine if they are available or working correctly. Processing alarm data fails to solve the problem because it may require a substantial infrastructure to be added to the system or network and may require dedicated hosts or applications to collect, aggregate and analyze the data. This alarm information is typically routed or collected at a central location, and may require data from various interdependent services. Often, the data is not particularly detailed, and it can be therefore difficult to determine what were the underlying causes of the alarms.
[0004] The repeated probing of services is also flawed in that there is a delay introduced before a problem can be detected. For example, if a system is set to probe each service every five minutes, then a problem may possibly go undetected for up to five minutes. Probing may also fail to detect intermittent errors, where a service is only working some of the time, but just happens to work when probed.
[0005] Furthermore, the perception of the behavior and performance of services may change depending on the viewpoint. For example, mailboxes may work for email users in Philadelphia, but may not work correctly for users in Europe. This problem may be a result of an error with the active directory service in Europe, and have nothing to do with the mailboxes themselves. However, conventional methods of error detection would initially attribute the error to the mail server and not the active directory service running in Europe. This added delay could result in increased expenses or losses, for example.
SUMMARY
[0006] An activity model is generated at a computer. The activity model may be generated by monitoring incoming and outgoing data in the computer. The collected data is analyzed to form a graph that describes and predicts what output is generated in response to received input and vice-versa. Later, a window of input and output data is collected from the computer. This collected window of data is used to query the activity model. The graph in the activity model is then used to give the probability that the collected window of data was consistent with the normal operation when the activity model was formed. A high probability indicates that the computer is performing normally, while a low probability indicates that the computer may be behaving erratically and there may be a problem with the computer.
[0007] Alternatively, a postulated window of input data may be considered by querying the activity model to provide the likely output from the computer were it to be presented with such input data.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is an illustration of a computer system including input and output channels;
[0009] FIG. 2 is an illustration of an exemplary method for creating an activity model;
[0010] FIG. 3 is an illustration of an exemplary activity model;
[0011] FIG. 4 is an illustration of an exemplary network of hosts including activity models;
[0012] FIG. 5 is an illustration of an exemplary screenshot of a connection view system;
[0013] FIGS. 6 and 7 illustrate applications of the activity model; and
[0014] FIG. 8 is a block diagram of an example computing environment in which example embodiments and aspects may be implemented.
DETAILED DESCRIPTION
[0015] FIG. 1 is an illustration of a computer system including input and output channels. As shown, the computer 110 includes a plurality of input and output channels. The input channels are labeled 121 - 126 , and the output channels are labeled 131 - 136 . Those skilled in the art will appreciate that the particular number of input and output channels shown is arbitrary, and for illustrative purposes only. There is no limit to the number of input and output channels that the system may support.
[0016] Input and output channels may represent connections to another computer on a network, or a connection to a particular service, for example. Services may include networked applications such as email, web, file browsing, and management applications, together with underlying protocols such as SMTP, RPC, HTTP, MSProxy, SMB, Netbios, Active Directory, DHCP, NTP, for example
[0017] Packets or messages are desirably received through input channels, and packets or messages are desirably sent through the output channels. These packets may contain information such as source or destination address, a name of a particular service associated with that packet, and the actual data payload containing information for the particular service to process or utilize.
[0018] An activity model may be generated for the computer 110 by keeping track of the packets that that are sent and received on the various input and output channels. This activity model may then be used as a reference to describe the normal behavior of the host computer 110 . For example, after some period of observation, it may be known that typically, when a packet is received at input channel 121 , two packets are sent from output channel 134 . Later, this information can be used to identify a possible problem in computer 110 . For example, if a packet received on input channel 121 does not result in two packets on output channel 134 as expected there might be a problem in the system. The activity model, and its construction, is described further with respect to FIGS. 2 and 3 .
[0019] FIG. 2 is an illustration of an exemplary method for creating an activity model. At 205 , a window is desirably chosen. The window is the length of time that packets will be collected or observed on the various input and output channels into the computer. The window may also be defined in terms of the number of packets collected or observed. The information collected during this window will be used to construct the activity model. The length of time, or amount of packets, selected for the window is a trade off between the accuracy of the model and the resources needed to create the model. A larger window will yield a more accurate model, but at the expense of the increased processing time and other resources required to manage the larger amount of data. Any method known in the art for determining an optimal window size may be used.
[0020] At 210 , the system may begin to collect packets according to the specified window size. In one embodiment, only the origin and destination address (i.e, the input and output channels) of the particular packet is recorded. However, additional data regarding the packet may also be collected such as the payload data and any associated application or service. This additional data can be used to create a more detailed activity model that can predict system behavior using the associated payload data as well as the packet origin and destination information. However, the greater the amount of information collected, the greater the system resources needed and more complicated the resulting activity model will become.
[0021] At 220 , the system may begin to construct, or modify, the activity model. The activity model may be constructed using a variety of statistical methods and machine learning techniques. These methods are described in more detail with respect to FIG. 3 , for example. However, those skilled in the art will appreciate that a wide variety of techniques may be used.
[0022] Because the activity model is dynamic, and may change over time, the model is desirably continuously updated. The activity model is desirably updated automatically, in a way that is transparent to a user of the particular host computer. The activity model may be updated at the end of every window of data collection, or at whatever frequency a user of administrator may desire.
[0023] FIG. 3 is an illustration of an exemplary activity model. As shown, the activity model may be represented by a graph where nodes represent the input and output channels. In the current embodiment, each node represents one channel, i.e., an IP address of a packet. However, in other embodiments the nodes could further represent other aspects of a packet such as the service associated with the packet, or the particular data fields or payload comprising the packet, for example.
[0024] In the example graph, and edge between any two nodes represents an observed probabilistic relationship between the nodes. For example, the line between node 121 and 131 represents a high probability that a packet received on channel 121 will result in a packet output on channel 131 . Similarly, the line from 124 to 132 and 134, represents a high probability that a packet received on channel 124 will result in a packet output on channels 132 and 134 .
[0025] In one embodiment, the probabilistic graph of the activity model is generated using the noisy-or method. In this method the graph of the activity model may comprise a bipartite graph with a set of nodes Q representing the incoming packets or channels, and a set of nodes P representing the output packets or channels. The model assumes that the graph only comprises edges from nodes in Q to nodes in P. Further, the model also assumes that the relationship between a node in P and its parents in Q is logical-or with noise. To achieve this, a statistical parameter Z is associated with each edge, and the probability of a particular output packet from a particular node is modeled as a logical function depending on the particular Z values associated with the edges into that node.
[0026] In another embodiment, the probabilistic graph of the activity model is implemented as a bipartite Bayesian network with arbitrary parameterization. In contrast with the previous embodiment, this model removes the noisy-or structural assumption, to allow for more complex probabilistic relationships between the input and output nodes.
[0027] In another embodiment, the probabilistic graph is implemented using a Bayesian classifier model. The graph is modeled with classification problems, using one for each output in the host system. The host inputs are the classification features and the “class” comprises the host output activity. Different Bayesian classifiers may be used including Naïve and TAN, for example.
[0028] In yet another embodiment, the activity model is implemented using arbitrary graph structures. As illustrated in FIG. 3 and described in the two models above, the graph only comprises edges from input to output nodes. However, a more complete activity model may also consider probabilistic relationships between multiple input, or multiple output nodes. For example, when an input is received on channel 121 , there may be a high probability that an input is also received on channels 122 and 124 . However, if there is no associated output packet that is sent with a high probability, the above two models would be unable to express the probabilistic relationship between the inputs because the models do not allow edges between input nodes. Removing the restriction on the graph structure will increase the predictability of the activity model, but requires a greater investment to create and maintain the resulting activity model.
[0029] As illustrated in FIG. 3 , the activity model can be used to determine the probability of a particular observed set of input and output packets. The system desirably accepts a query 306 , such as an observed set of inputs and an observed set of outputs, for example. The system may then use the generated activity model to determine the probability that the observed inputs and outputs are consistent with the activity model. For example, the system might use the activity model to generate a Z value for that set of input. The Z value may then be referenced against a Gaussian distribution to determine how unusual the particular observed sets of inputs and outputs are. This probability may comprise the Result 308 . Those skilled in the art will recognize that the particular methods for determining the probability of a given set of inputs and outputs depend on the statistical methods used to generate the underlying activity model. Similarly, those skilled in the art will also recognize that a wider variety of statistical methods may be used.
[0030] FIG. 4 is an illustration of an exemplary network of hosts including activity models. As illustrated, there are several host computers shown. These include hosts 410 , 420 , 430 , 440 , and 450 . Each of these hosts may be connected to one another through a variety of channels, illustrated by the arrows connecting the hosts. Further, each of these hosts may have an activity model along with some type of activity model client that maintains the activity model, as well as responds to queries made to the activity model. Note that while the illustrated network comprises only five hosts, it is for illustrative purposes only, and not meant to limit the invention to networks of five hosts. There is no limit to the number of hosts that may be supported.
[0031] The system illustrated in FIG. 4 desirably allows hosts to not only query their own activity models, but also the activity models of the other hosts on the network. For example, a user at host 430 may learn that a some users are having difficulties with their email. Accordingly, the user may query the activity model of the host 430 using an API such as one discussed above. However, rather than simply taking a window of packets and comparing them against the activity model to determine if there is a statistically significant change in the behavior of the system that may indicate a problem, the revised API may take the further step of recursively querying the activity models of the hosts on the network that the host 430 receives packets from, or has channels with. These hosts may then recursively query the activity models of the hosts that they receive packets from, and so forth.
[0032] The results from each of the various hosts are then returned to the host 430 who is then able to see which, if any, of the various hosts on the network may be the cause of the email difficulty. Once the host 430 determines which host is not behaving correctly according to its activity model, the host 430 may use its own activity model to isolate the various channels and packets that connect it to that particular hosts and further query its activity model using a window comprising those packets to further determine the service or cause of the failure.
[0033] In another embodiment, when the host 430 queries its activity model, the activity model may only recursively query the activity models of hosts who have a high connectivity to other hosts on the network. The, the activity model can be used to determine, given a particular input, which computers is the host computer likely to send output packets to. In a similar way, it may be determined which hosts the particular host 430 is most connected to or most dependent on. Therefore, when determining the source of an error by recursively querying active directories, the host 430 may conserve resources by first only querying hosts who it is highly connected to, and that are therefore the most likely candidates for the source of the error.
[0034] FIG. 5 is an illustration of an exemplary screenshot of a connection view system. The connection view system desirably provides a user or administrator of a host computer with a graphical view of the computers, and or service, that the particular host computer may depend on. As shown, the host computer 515 depends, or receives packets from computers 525 , 545 , 535 , and 555 . In addition, the host computer 515 indirectly depends on computer 565 through its dependency on computer 555 .
[0035] As described above, the particular computers shown in the dependency graph are desirably determined using the activity model associated with host computer 515 . The activity model of the host computer 515 can determine which computers send packets to the host computer, and which computers receive packets from the host computer. Accordingly, these computers may be shown in the connection view. In one embodiment, all computers that are connected to the host computer 515 are shown. In another embodiment, only computers that meet some connectivity threshold are illustrated. This threshold may be determined by a user or administrator, for example. Any system, method, or technique known in the art may be used.
[0036] As shown in FIG. 5 , the relative importance or strength of the connection between the computers and the host computer 515 is illustrated by the thickness of the line connecting the computers. For example, the thick line between computer 525 and host computer 515 denotes a strong or high dependency. Similarly, the hashed line between computer 545 and host computer 515 denotes a weaker or low dependency. In addition, colors may be used to illustrate the dependency. Those skilled in the art will recognize that the relative dependency of the computers may be illustrated by a variety of well known methods. Any technique known in the art may be used.
[0037] The connection view system may be further used to illustrate to a user the health of the host computer and the health of those computers connected to it. For example, the activity model of the host computer may be queried, along with the activity models of the various computers connected to the host computer. If the activity models report that their respective systems are behaving normally, then the corresponding icons for those systems may be displayed normally, or with a shade of green to indicate everything is working correctly. Similarly, if an activity model shows that a particular system is behaving strangely, then the system may display the icon associated with that computer in some way to illustrate the problem, such as a shade of red, for example.
[0038] Another aspect of the connection view system may be to display to the user which services or resources are associated with the computers displayed in the connection view. As described above, the activity model may be allowed to inspect the received and sent packets to determine which service or services they may be associated with. Also, separate service specific activity models may be kept to help determine if the particular service is behaving correctly. Using these features, the activity model may be referenced to determine which services are provided from, or associated with, each displayed host. The service or services may be displayed next to the associated computer. In addition, the activity models of the associated computers may be additionally queried to determine if these services appear to be working correctly. These services may they be displayed in such a way as to indicate their health, e.g., red or green.
[0039] As described above, the connection view may initially only show the computers that have connections to, or send packets to, the host computer 515 . However, an alternative embodiment may include the feature of allowing a user to select and expand a particular host computer to view the computers connected to the selected host. For example, as illustrated in FIG. 5 , computer 565 is connected to computer 555 , which is connected to the host computer 515 . Initially computer 565 may not be displayed to a user of the host computer 515 because it is not directly connected to it. However, the user may be able to expand the view by clicking, or otherwise selecting computer 555 . After expanding the view the user may be presented with one or more additional computers connected to computer 555 , for example. The computers that connect to computer 555 may be determined by querying the activity model of computer 555 .
[0040] As will be apparent to those skilled in the art, the activity model, particularly the activity model capable of querying other activity models in a networked environment, may be useful for a variety of specialized applications. For example, one such application may be anomaly detection. A particular system may continuously query its own activity model in order to detect anomalies. If the detected behavior is not predicted by the activity model, or differs from the activity model in a statistically significant way, then it may be useful to alert a user that an anomaly has been detected.
[0041] Similarly, in a networked environment, systems on the network that detect anomalies may alert other systems on the network to query their activity models to see if they detect a similar anomaly, or to warn them of possible anomalies. This may be particularly useful for the detection of flash crowds, or a denial of service attack for example.
[0042] The activity model may be particularly useful for the differentiation between flash crowds and denial-of-service attacks. A flash crowd is when an unusually large number of users attempt to view a particular web site at the same time. This is usually the result of the posting of an article referencing the web site on a popular internet site that serves to direct a large number of users to the particular web site. In contrast, a denial-of-service attack is a concentrated malicious attack that attempts to crash, or otherwise render inoperable, a web server by repeatedly resending requests to it.
[0043] Often web pages are served not by a single web server, but by several web severs, each with a separate IP address. When a typical user makes a request for a web page, the actual server that serves the request is not known to the user, but may be selected according to some load balancing algorithm, for example. In contrast, when a malicious web user or users attempt a denial of service attack, they generally specify the IP address of the server they are attacking. This observation can be used by the activity models to differentiate between the two types of attacks. Thus, when a server under heavy load queries its activity model, and determines that the amount of traffic it is receiving is unusually high it desirably first recursively queries the activity models of the other servers connected to it. If the activity models of the other servers generally show that they are also experiencing unusually high traffic, then it may be assumed that a flash crowd is taking place. However, if few servers are also experiencing the high traffic, then it may be assumed that a denial-of-service is taking place and appropriate action may be initiated.
[0044] FIG. 6 illustrates yet another application of the activity model. In this example, the activity model may be used to perform a service dependency performance analysis. At 605 , a user or administrator may desire to make a particular change to a service, for example. However, rather than actually make the change and observe the effects, the user may wish to use the activity models to generally predict the impact of the service change to the overall system or network.
[0045] At 615 , the particular host or host(s) where the initial service change has been determined to take place, may have their activity models examined or queried to determine which systems on the network will be affected by the change in the service. This may be determined by using the activity model to identify which systems receive output packets from the particular host or host(s) that are deemed to be part of the changed service, for example.
[0046] At 625 , the set of computers on the network that depend or will be most affected by the change in the service have their activity models queried to determine which services or resources on those computers will be affected by the change in the service. This may be accomplished by using the incoming packets that were found to be associated with the changed service to determine the outgoing packets that are statistically associated with the incoming packets according to the activity model. These services may be presented to the user in a report at 630 , or if desired, the computers associated with the outgoing packets may in turn have there activity models queried and so forth. In this way the number of computers potentially affected by the change in service can be determined to whatever degree the user may desire.
[0047] At 630 , the user may be presented with a report indicating the effect of the proposed service change to the system. This report may be similar to that illustrated and described with respect to FIG. 5 , for example, and show the computers most effected by the proposed change in service. In addition, the services that may be affected as determined by the activity models may also be displayed along with an indicator of the probability that they will be affected, for example. However, those skilled in the art will appreciate that the report data may be displayed to the user using a variety of techniques known in the art for the presentation of data.
[0048] FIG. 7 illustrates yet another application of the activity model. Here, the network of activity models is used to determine the cause of a detected network outage or failure. At 710 , the computers comprising the computer network may begin maintaining a buffer of the last N packets sent to, or received from, other computers on the network. These packets may then be used later to reconstruct the network activity prior to a detected failure. The actual number of packets chosen to buffer is a tradeoff between the memory required to store the packets, and the desire to have as much information available to reconstruct the network activity prior to the failure.
[0049] At 720 , a network failure or outage may be detected. This failure may be a service failure, or the failure of one or more of the computers on the network. The failure may be detected by a user or administrator, one or more of the activity models available on the network, or by the computers themselves.
[0050] At 730 , after detecting the network failure, one or more of the computers on the network may use the buffered packets to query their activity model to determine the source of the failure. The buffered packets desirably serve as a snapshot of the network activity just prior to the detected failure. Accordingly, the computer where the failure was detected may query its activity model with the recorded packet activity. In addition, the other computers on the network may similarly query their activity models using their collected packets. Depending on the results of the queries, service specific activity models may also be queried in order to further determine the source of the failure.
[0051] At 740 , the user may be presented with a report indicating the possible sources of the network failure as detected by the activity models. This report may be similar to that illustrated and described with respect to FIG. 5 , for example. However, those skilled in the art will appreciate that the report data may be displayed to the user using a variety of techniques known in the art for the presentation of data.
Exemplary Computing Arrangement
[0052] FIG. 8 shows an exemplary computing environment in which example embodiments and aspects may be implemented. The computing system environment 800 is only one example of a suitable computing environment and is not intended to suggest any limitation as to the scope of use or functionality. Neither should the computing environment 800 be interpreted as having any dependency or requirement relating to any one or combination of components illustrated in the exemplary operating environment 800 .
[0053] Numerous other general purpose or special purpose computing system environments or configurations may be used. Examples of well known computing systems, environments, and/or configurations that may be suitable for use include, but are not limited to, personal computers, server computers, hand-held or laptop devices, multiprocessor systems, microprocessor-based systems, set top boxes, programmable consumer electronics, network PCs, minicomputers, mainframe computers, embedded systems, distributed computing environments that include any of the above systems or devices, and the like.
[0054] Computer-executable instructions, such as program modules, being executed by a computer may be used. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. Distributed computing environments may be used where tasks are performed by remote processing devices that are linked through a communications network or other data transmission medium. In a distributed computing environment, program modules and other data may be located in both local and remote computer storage media including memory storage devices.
[0055] With reference to FIG. 8 , an exemplary system includes a general purpose computing device in the form of a computer 810 . Components of computer 810 may include, but are not limited to, a processing unit 820 , a system memory 830 , and a system bus 821 that couples various system components including the system memory to the processing unit 820 . The processing unit 820 may represent multiple logical processing units such as those supported on a multi-threaded processor. The system bus 821 may be any of several types of bus structures including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. By way of example, and not limitation, such architectures include Industry Standard Architecture (ISA) bus, Micro Channel Architecture (MCA) bus, Enhanced ISA (EISA) bus, Video Electronics Standards Association (VESA) local bus, and Peripheral Component Interconnect (PCI) bus (also known as Mezzanine bus). The system bus 821 may also be implemented as a point-to-point connection, switching fabric, or the like, among the communicating devices.
[0056] Computer 810 typically includes a variety of computer readable media. Computer readable media can be any available media that can be accessed by computer 810 and includes both volatile and nonvolatile media, removable and non-removable media. By way of example, and not limitation, computer readable media may comprise computer storage media and communication media. Computer storage media includes both volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer readable instructions, data structures, program modules or other data. Computer storage media includes, but is not limited to, RAM, ROM, EEPROM, flash memory or other memory technology, CDROM, digital versatile disks (DVD) or other optical disk storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to store the desired information and which can accessed by computer 810 . Communication media typically embodies computer readable instructions, data structures, program modules or other data in a modulated data signal such as a carrier wave or other transport mechanism and includes any information delivery media. The term “modulated data signal” means a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal. By way of example, and not limitation, communication media includes wired media such as a wired network or direct-wired connection, and wireless media such as acoustic, RF, infrared and other wireless media. Combinations of any of the above should also be included within the scope of computer readable media.
[0057] The system memory 830 includes computer storage media in the form of volatile and/or nonvolatile memory such as read only memory (ROM) 831 and random access memory (RAM) 832 . A basic input/output system 833 (BIOS), containing the basic routines that help to transfer information between elements within computer 810 , such as during start-up, is typically stored in ROM 831 . RAM 832 typically contains data and/or program modules that are immediately accessible to and/or presently being operated on by processing unit 820 . By way of example, and not limitation, FIG. 8 illustrates operating system 834 , application programs 835 , other program modules 836 , and program data 837 .
[0058] The computer 810 may also include other removable/non-removable, volatile/nonvolatile computer storage media. By way of example only, FIG. 8 illustrates a hard disk drive 840 that reads from or writes to non-removable, nonvolatile magnetic media, a magnetic disk drive 851 that reads from or writes to a removable, nonvolatile magnetic disk 852 , and an optical disk drive 855 that reads from or writes to a removable, nonvolatile optical disk 856 , such as a CD ROM or other optical media. Other removable/non-removable, volatile/nonvolatile computer storage media that can be used in the exemplary operating environment include, but are not limited to, magnetic tape cassettes, flash memory cards, digital versatile disks, digital video tape, solid state RAM, solid state ROM, and the like. The hard disk drive 841 is typically connected to the system bus 821 through a non-removable memory interface such as interface 840 , and magnetic disk drive 851 and optical disk drive 855 are typically connected to the system bus 821 by a removable memory interface, such as interface 850 .
[0059] The drives and their associated computer storage media discussed above and illustrated in FIG. 8 , provide storage of computer readable instructions, data structures, program modules and other data for the computer 810 . In FIG. 8 , for example, hard disk drive 841 is illustrated as storing operating system 844 , application programs 845 , other program modules 846 , and program data 847 . Note that these components can either be the same as or different from operating system 834 , application programs 835 , other program modules 836 , and program data 837 . Operating system 844 , application programs 845 , other program modules 846 , and program data 847 are given different numbers here to illustrate that, at a minimum, they are different copies. A user may enter commands and information into the computer 20 through input devices such as a keyboard 862 and pointing device 861 , commonly referred to as a mouse, trackball or touch pad. Other input devices (not shown) may include a microphone, joystick, game pad, satellite dish, scanner, or the like. These and other input devices are often connected to the processing unit 820 through a user input interface 860 that is coupled to the system bus, but may be connected by other interface and bus structures, such as a parallel port, game port or a universal serial bus (USB). A monitor 891 or other type of display device is also connected to the system bus 821 via an interface, such as a video interface 890 . In addition to the monitor, computers may also include other peripheral output devices such as speakers 897 and printer 896 , which may be connected through an output peripheral interface 895 .
[0060] The computer 810 may operate in a networked environment using logical connections to one or more remote computers, such as a remote computer 880 . The remote computer 880 may be a personal computer, a server, a router, a network PC, a peer device or other common network node, and typically includes many or all of the elements described above relative to the computer 810 , although only a memory storage device 881 has been illustrated in FIG. 6 . The logical connections depicted in FIG. 6 include a local area network (LAN) 871 and a wide area network (WAN) 873 , but may also include other networks. Such networking environments are commonplace in offices, enterprise-wide computer networks, intranets and the Internet.
[0061] When used in a LAN networking environment, the computer 810 is connected to the LAN 871 through a network interface or adapter 870 . When used in a WAN networking environment, the computer 810 typically includes a modem 872 or other means for establishing communications over the WAN 873 , such as the Internet. The modem 872 , which may be internal or external, may be connected to the system bus 821 via the user input interface 860 , or other appropriate mechanism. In a networked environment, program modules depicted relative to the computer 810 , or portions thereof, may be stored in the remote memory storage device. By way of example, and not limitation, FIG. 6 illustrates remote application programs 885 as residing on memory device 881 . It will be appreciated that the network connections shown are exemplary and other means of establishing a communications link between the computers may be used.
[0062] Although the subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims. | An activity model is generated at a computer. The activity model may be generated by monitoring incoming and outgoing data in the computer. The collected data is analyzed to form a graph that describes and predicts what output is generated in response to received input. Later, a window of input and output data is collected from the computer. This collected window of data is used to query the activity model. The graph in the activity model is then used to give the probability that the collected window of data was collected from the computer used to generate the activity model. A high probability indicates that the computer is performing normally, while a low probability indicates that the computer may behaving erratically and there may be a problem with the computer. | 7 |
BACKGROUND OF THE INVENTION
1. Nature of The Invention
This invention is concerned with reducing the wax content of distillate hydrocarbon fractions by conversion of straight or slightly branched paraffin hydrocarbons contained therein.
2. Prior Art
Distillates obtained from crude oil, such as gas oils have been processed heretofor to produce fuel oil products, including home heating oil, diesel fuel, furnace oil and the like. Specifications for these products normally include a requirement that the pour point may not exceed a certain maximum value. In some instances it is necessary to subject these distillate fuels to additional processing whose principle purpose is to reduce the pour point of the feed stream.
One such process is catalytic hydrodewaxing in which gas oil is contacted with hydrogen and a shape selective catalyst adapted to selectively crack or hydrocrack the paraffinic molecules in the gas oil. Initially the catalysts used were those zeolite cracking catalysts which had pore openings sized so that they would admit and crack only normal paraffins and exclude all the other gas oil components. An example is an erionite-type zeolite. More recently U.S. Pat. No. RE 28,398 has disclosed an improvement in this process where ZSM-5 type zeolites are used in place of the previously used erionite-type cracking catalyst. U.S. Pat. No. RE 28,398 is incorporated herein by reference. This process permits lowering of the gas oil pour point in a very efficient manner. The product of this hydrodewaxing process may be suitably fractionated to produce high yields of dewaxed gas oil boiling in the same range as the feed.
In a hydrodewaxing operation as presently practiced, the vaporized distillate is introduced into a bed of ZSM-5 type crystalline zeolite catalyst at a temperature maintained within the range of 650° F. to 1000° F., a pressure of 100 to 3000 psig and a liquid hourly space velocity of 0.1 to 10 and a hydrogen/hydrocarbon mole ratio between 1 and 20. The hydrodewaxing reaction within the catalytic bed is an endothermic reaction. It is thus necessary ordinarily to superheat the change before admitting it to the catalyst bed. The amount of heat available is controlled by the heat capacity of the super heated reactants and/or inerts used. In an adiabatic commercial unit the temperature drop throughout the reaction bed may be as high as 20° to 50° F. As feeds of an increasing wax content are hydrodewaxed in this process, endotherms or temperature drops as high as 130° F. may be anticipated. As the temperature declines in the reaction bed, the rate of reaction and consequently the rate of dewaxing of the oil diminishes
One object of this invention is to provide an improved catalytic dewaxing process wherein the temperature decline in the catalyst bed is minimized. Still another object of this invention is to provide an improved catalytic hydrodewaxing process.
SUMMARY OF THE INVENTION
Briefly stated this invention comprises a process for the catalytic hydrodewaxing of distillates wherein the distillate is fed to a catalyst bed and there is cofed with the distillate a reactant which reacts exothermally, but independently of the distillate, in the presence of the catalyst to provide the heat necessary to maintain the hydrodewaxing reaction within the bed. Preferably the reactant added is a carbon oxygenate such as methanol, ethanol, their respective ethers or mixtures thereof.
DESCRIPTION OF THE INVENTION
The novel process of this invention is concerned with dewaxing of hydrocarbon feedstocks. The term "dewaxing" is used in a specification and claims in its broadest sense and and is intended to mean the removal of those hydrocarbons which will readily solidify (waves) from petroleum stocks. Feedstocks which can be treated include lubricating oil stocks as well as those which have a freeze point or pour point problem, that is, petroleum stocks boiling above about 350° F. The dewaxing can be carried out at either cracking or hydrocracking conditions.
Typical cracking conditions include a liquid hourly space velocity between about 0.5 and about 200, a temperature between about 550° F. and about 1100° F. and a pressure between about subatmospheric and several hundred atmospheres.
When hydrocracking operations are carried out, operating conditions include temperatures between 650° F. and 1000° F., a pressure between 100 and 3000 psig, but preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0.1 and 10, preferably between 0.5 and 4 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 20 preferably between 4 and 12.
As indicated above, a reactant such as methanol, which will react independently in the presence of the catalyst used in the hydrodewaxing operation is mixed with the incoming feedstock. The catalyst which is used in the catalyst bed, preferably is one from the ZSM-5 zeolite family. The family of ZSM-5 composition has the characteristic X-ray diffraction pattern set forth in U.S. Pat. RE 28,948 and 3,702,886. ZSM-5 compositions can also be identified in terms of mole ratios of oxides, as follows:
0.9±0.2 M.sub.2/n O:W.sub.2 O.sub.3 :5-100 YO.sub.2 :zH.sub.2 O
wherein M is a cation, n is the valence of said cation, W is selected from the group consisting of aluminum and gallium, Y is selected from the group consisting of silicon and germanium, and z is from 0 to 40. In a preferred synthesized form, the zeolite has a formula, in terms of mole ratios of oxides, as follows
0.9±0.2 M.sub.2/n O:Al.sub.2 O.sub.3 :≧5 SiO.sub.2 :zH.sub.2 O
and M is selected from the group consisting of a mixture of alkali metal cations, especially sodium, and tetraalkylammonium cations, the alkyl groups of which preferably contains 2-5 carbon atoms.
In a preferred embodiment of ZSM-5, W is aluminum, Y is silicon and the silica/alumina mole ratio is at least 10 and ranges up to about 1000.
Representative of the ZSM-5 type zeolites are ZSM-5, ZSM-11, ZSM-23, ZSM-35 and ZSM-38. ZSM-5 is disclosed and claimed in U.S. Pat. No. 3,702,886 and U.S. Pat. No. RE 29,948; ZSM-11 is disclosed and claimed in U.S. Pat. No. 3,709,979. Also, see U.S. Pat. No. 3,832,449 for ZSM-12; U.S. Pat. No. 4,076,842 for ZSM-23; U.S. Pat. No. 4,016,245 for ZSM-35 and U.S. Pat. No. 4,406,839 for ZSM-38. The disclosures of these patents are incorporated herein by reference. Of these zeolites ZSM-5 is most preferred. Ordinarily the zeolites will be present as a composite with an inactive porous support material.
As the mixture of feedstock and other reactant passes through the catalyst bed, the independent reactant in this instance methanol, is dehydrated into oxygenated products and water. The dehydration reaction results in the evolution of heat which maintains the temperature at a higher level necessary to effect dewaxing in the reaction bed. We have discovered that in some cases it may be desirable to make the addition of methanol to the oil in an intermittent or pulsing fashion rather than on a continual basis. We have discovered that the presence of methanol in the hydrocarbon stream flowing through the catalyst bed, necessitates a slight increase in temperature to maintain the hydrodewaxing process in the catalyst bed. The presence of the methanol, however, apparently serves to increase the activity of the catalyst. When injection of methanol is suspended, the catalyst is sufficiently active to maintain hydrodewaxing at a stabilized rate as the temperature declines in the reactor bed.
Activity does eventually decline to a point where the injection of methanol must be resumed to introduce more heat into the catalyst bed. The ratio of independent reactant (such as methanol) to the feedstock flowing through the catalyst bed preferably is between about 0.1 and about 10.0 parts by weight of feedstock to one part of oxygenate. The rate of injection of methanol on a pulsed basis can be readily determined by simple experimentation.
EXAMPLE 1
A Nigerian gas oil having an initial pour point of 85° F. was flowed through a fixed catalyst bed of a steamed nickel impregnated acid form of ZSM-5 zeolite in a procedure approximating that described in U.S. Pat. No. RE 28,398. The reaction conditions were 400 psig, 1.0 LHSV and a flow rate of 2500 standard cubic feet of hydrogen per barrel. During this time no additional methanol was added to the stream being processed. Flow was continued over a period of 15 days during which time as the activity of the catalyst declined the reaction temperature was periodically increased to product a gas oil product having a pour point of 0° F. At the end of this 15 day period 5% by volume of methanol was cofed with the gas oil into the reactor bed for a total of 5 days. During this period all of the methanol was converted to hydrocarbons and water. The temperature required to maintain dewaxing activity in the catalyst bed increased significantly while cofeeding the methanol. The reaction temperature necessary to obtain 0° F. pour point gas oil product increased to nearly 790° F. in contrast to the original starting temperature of about 770° F. After the flow of methanol into the reactor bed was discontinued an improvement in catalyst dewaxing activity occurred. The reaction temperature required to obtain the 0° pour point decreased by nearly 50° F. to about 750° F. These results indicate that cofeeding of methanol or other oxygenates can result in an improved dewaxing operation by balancing the heat loss due to the dewaxing reaction. The benefits of pulsed cofeeding of methanol is supported by the data above showing the decline in the temperature necessary to effect dewaxing after the injection of methanol. It should be noted that the increased temperature required to maintain the dewaxing reaction when methanol is cofed is still considerably less than the temperature which would ultimately be required if methanol were not a part of the feed to the catalyst bed.
EXAMPLE 2
A distillate fuel oil having the properties shown in Table 1 was dewaxed using a conventional ZSM-5 zeolite catalyst under reaction conditions of 700° F., 400 psig, 1.0 LHSV and a hydrogen to oil ratio of 2500 standard cubic feet of hydrogen per barrel of oil. Hydrodewaxing was carried out with and without the co-injection of 5% by volume of methanol into the reaction system. The distillate fuel oil products from both reactions were analyzed and their properties are shown in Table 2. A 55% yield of 330° F.+ distillate was obtained when methanol was added to the dewaxing system. In the absence of any added methanol a yield of distillate of only 50% resulted and the pour point was must higher(+45°F.). A completely unexpected beneficial result is illustrated in this example. Note that the volume of distillate recovered is 57 percent of the original charge utilizing the process of our invention (column B) as compared with only 50 percent recovered in the more conventional dewaxing process (column A). This represents a 15 percent increase in recovery.
TABLE 1______________________________________°D API Gravity 35.2ANALYSISHydrogen, % wt. 13.71Sulfur, % wt. 0.082Nitrogen ppm 89basic ppm 25CCR, % wt. 0.07Paraffins, % wt. 71.4Napthenes, % wt. 4.8Aromatics, % wt. 23.9Pour Point, °F. 110KV CS @ 100° C. 2.48Distillation (D-1160)IBP % vol 491° F. 5 61210 64250 71290 74995 755______________________________________
TABLE 2______________________________________Process Charge A B______________________________________Reactor ConditionsVol. % of cofeed -- -- 5% CH.sub.3 OHTemperature, °F. -- 670 700Pressure psig -- 400 400LHSV -- 1.0 1.0H.sub.2 at In1et SCF/BBL -- 2500 2500Product Distribution, % wt.:C1-C3 -- 3.8 6.3C4's -- 8.7 11.4C5 - 330° F. naphtha -- 38.8 27.2330° F. + Distillate 100.0 50.0 57.2Pour Point, °F. 110 45 -40______________________________________ | The hydrodewaxing of distillate is enhanced by mixing therewith a product which will react exothermally in supplying heat necessary for the dewaxing operation. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates, in general, to aircraft flight instrumentation and, more particularly, to an artificial horizon raster generator in which a two color display is specified entirely by the horizon line or transition line parameters. More specifically, the invention relates to a dedicated artificial horizon raster generator which requires no memory and removes the horizon line computation burden from the on board host processor.
2. Description of the Prior Art
Two basic methods have been used by prior art artificial horizon raster systems. The most basic method is to represent every screen pixel with a memory element. While this bit per pixel method is very flexible, the large amount of memory required is costly and requires extensive host processor computations. A typical two color display consisting of 256 lines with 256 pixels per line requires 65,536 memory elements.
By making use of the artificial horizon display's simplicity, a second prior art method uses character blocking to reduce memory requirements. The two color display is divided into many blocks, each consisting of many screen pixels. Each block is then assigned a character to define the colors of the individual pixels. Typically, 90% of the display can be produced using only two characters, one character representing sky shading and the other character representing ground shading. The remaining 10% of the display, which comprises the transition region or horizon boundary line between sky shading and ground shading, may be defined using a few more characters. A typical two color horizon display consisting of 256 lines with 256 pixels per line, divided into four by four pixel blocks, can be defined with 128 different characters assigned to the 4,096 blocks. Such an implementation requires 30,720 memory elements. While this character blocking method reduces the amount of memory required, the host processor's computation burden is still extensive and the amount of memory used remains considerable.
A technique for further reducing the host processor's computation burden is discussed in U.S. Pat. No. 4,149,148 entitled "Aircraft Flight Instrument Display System", invented by Miller et al. and assigned to the assignee of the present invention. As taught by Miller, the horizon display may be reduced to a straight line which separates the two color areas. The entire display may then be specified simply by specifying the transition line parameters, that is, the slope of the horizon line, the starting color, and the horizontal and vertical coordinates of the point at which the raster scan will first encounter or intersect the horizon boundary line. The entire display is then generated by computing each transition point intersected by each raster scan line and storing these points in memory. Also stored in memory is the video shading information representative of the appropriate sky or ground shading corresponding to each raster line. Thus the sky-ground shading is provided by addressing memory in synchronism with the raster scan, and changing the shading from sky to ground or vice versa in accordance with the information stored in the memory. It is noted that this method requires the host processor to compute each transition point intersected by the raster scan line, thus placing a burden on the host processor. Second, the transition points so computed must be stored in memory for later use. These two requirements are considered undesirable since the host processor is usually responsible for controlling a plurality of flight instruments. Assigning the processor the additional task of controlling the artificial horizon raster generator necessarily results in speed retarding interrupts and an increased memory budget. These disadvantages become even greater when one considers the impact of increasing the display resolution. For example, a change from a display of 256 lines containing 256 pixels per line to a display of 512 lines containing 512 pixels per line would double the number of host processor computations and double the amount of memory needed to store the transition points.
SUMMARY OF THE INVENTION
The present invention alleviates the above mentioned problems by removing the computation burden from the host processor and by eliminating the need for memory in connection with generating the artificial horizon.
The invention is intended to operate in conjunction with a conventional display apparatus having a display face for displaying sky-ground shading thereon, including means for generating a raster in the usual fashion. The horizon boundary line between sky and ground shadings is parametrically represented by a crossover word representing the point at which the raster line first crosses the horizon boundary, and by a slope signal representing the slope of the horizon boundary line, and further by a shading signal representing the starting shading. These parameters may be provided by the host processor in a conventional fashion.
The invention comprises a first digital timing circuit for providing a signal synchronous with the raster lines and a second digital timing circuit for providing a second digital signal synchronous with the pixels of each raster line. A transition point computing circuit provides in response to the slope signal parameter, a current or present transition point signal representing the intersection of the horizon boundary line with the raster line currently being generated and an overflow status signal. Thus, the current transition point signal is provided in real time, that is, immediately before its associated raster scan line is drawn.
The invention further comprises a first comparator responsive to the current transition point signal and to the second digital timing signal for providing a left-right signal indicating whether the pixel currently being generated is to the left or to the right of the horizon boundary line. A second comparator, responsive to the first digital timing signal and to the initial crossover word, provides an above-below signal indicating whether the raster line currently being generated is above or below the horizon boundary line.
A logic circuit responsive to the left-right signal, to the above-below signal, to the overflow status signal, to the slope signal, and to the initial shading signal determines whether the currently generated pixel is of a sky or ground shading. Depending upon the initial shading signal, the raster scan line represents one of either sky or ground shadings when the raster scan line, prior to the current transition point, is being generated and the other of said shadings when the raster scan line, subsequent to the current transition point, is being generated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic block diagram of the invention.
FIG. 2 is a diagram illustrating geometrical parameters utilized in generating the horizon shading.
FIG. 3 is a second diagram illustrating the horizon shading.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 2, a pictorial representation of a typical horizon shading is illustrated. A display apparatus denoted generally by reference numeral 10 comprises a display face 12 for displaying thereon a sky-ground representation. The display face may be, for example, the face of a conventional CRT display, or comparable liquid crystal display, as well as other electrically actuated displays.
A conventional raster generator 14 provides, in the conventional fashion, a raster on the display face comprising raster lines 16 made up of individual pixels 18. It will be understood that these raster lines may be generated sequentially, each raster line containing a number of sequentially generated pixels. The typical display might consist of 256 raster lines, each containing 256 pixels. Greater resolution may be had by increasing the number of lines or the number of pixels per line in a given display face area.
An artificial horizon line is represented on the display face by utilizing two colors or shadings, a ground shading and a sky shading. In the presently preferred embodiment the horizon boundary line is defined as the transition line between the ground shading and the sky shading. In FIG. 2 the horizon boundary line is denoted by reference numeral 20, and is exemplary of a horizon line having a negative slope. As used herein, slope will denote the ratio of rise to run, that is, ΔY/ΔX, in an X-Y cartesian coordinate system. FIG. 3 illustrates an exemplary horizon boundary line having a positive slope.
For purposes of describing the invention, it will be assumed that raster generator 14 generates a raster beginning at the origin O in the upper left hand corner of display face 12 and then draws a raster line horizontally by holding the Y deflection constant while ramping the X deflection signal through these successive pixels of the first line. At the end of the first line the Y deflection is incremented to the second line and the X deflection is initialized. A second raster line is then drawn horizontally by holding the Y deflection constant while ramping the X deflection signal. In this fashion, the entire raster pattern is generated. Alternatively, the raster may be generated in both directions on alternate lines. The present invention is applicable, as will be understood, regardless of the particular sequence chosen to implement the raster. Furthermore, the starting point or origin O in the upper left-hand corner is chosen for convenience, and is not to be construed as a limitation of the invention.
With continued reference to FIGS. 2 and 3, the horizon boundary line 20 has an initial crossover point 22, defined as the point at which the horizon boundary line first coincides with or intersects the raster line currently being generated. It will be seen that raster lines occurring above this initial crossover point, that is occurring earlier in time, do not intersect the horizon boundary line. Raster lines in this non-intersecting region are located in FIGS. 2 and 3 in the area denoted by the reference numeral 24. The initial crossover point 22 may be characterized in terms of a numerical word, hereinafter referred to as the initial crossover word, representing the Y axis position or coordinate (line number) and X axis position or coordinate (pixel number) of the initial crossover point. In FIG. 2, for example, the initial crossover point occurs at approximately the 51st line down from the origin and at the 0th pixel position to the right of the origin. Thus the initial crossover word would comprise an X axis coordinate of 0 and a Y axis coordinate of 51. In FIG. 3, in contrast, the initial crossover point 22 occurs approximately 51 lines down from the origin at the 255th pixel position, that is with an X axis coordinate of 255 and a Y axis coordinate of 51.
Referring now to FIG. 1, the presently preferred embodiment is illustrated in conjunction with a conventional host processor 30 and raster generator 14. The host processor generates in the conventional fashion those parameters necessary to define the horizon boundary line as taught in U.S. Pat. No. 4,149,148, the disclosure of which is incorporated herein by reference. Briefly, the host processor 30 provides the initial crossover word comprising the X and Y coordinates of the initial crossover point. The host processor also provides a slope signal determined by the magnitude and sign of the slope of the horizon boundary line. The host processor also provides an initial shading signal representing one of the sky or ground shadings. As used herein, the initial shading is used synonymously with the term start color and is taken to mean the first color or beginning color of any raster line which passes through the horizon boundary line. The terminology "hot" start color denoted as start color represents the second shading or color of any line after it has passed through the horizon boundary line. In FIG. 2, line 60 has a start color corresponding to a ground shading, whereas in FIG. 3 line 60 has a start color corresponding to a sky shading. It is noted that line 5, for example in both FIGS. 2 and 3, does not intersect with the horizon boundary line. Thus, the concept of start color is not applicable to line 5.
The invention comprises four latches 32, 34, 36, and 38 receptive of the horizon boundary line parameters and the initial shading information from host processor 30. Latch 32 receives the start color or initial shading characteristic of the first raster line to cross the horizon boundary line. For example, if the horizon boundary line is exemplified by FIG. 2, the initial shading or start color is the ground shading. If the horizon boundary line is exemplified by FIG. 3, the start color is the sky shading. Latches 34 and 36 receive the horizon boundary line slope inforamtion from host processor 30. Latch 34 receives the initial crossover word representing the X axis coordinate where the raster line first crosses the horizon boundary line. For a horizon boundary line exemplified by FIG. 2, this X axis initial crossover coordinate is seen to be zero, whereas for the horizon boundary line of FIG. 3 the X axis initial crossover coordinate is 255. Note that an X axis initial crossover coordinate of zero corresponds to a negative slope, whereas an X axis coordinate of 255 cooresponds to a positive slope. Thus, the X axis coordinate of the initial crossover point, for the conditions shown in FIGS. 2 and 3, can be used to indicate the sign of the slope.
Latch 36 receives a numerical value or delta transition factor based on the slope of the horizon boundary line as computed by the host processor, the numerical value being calculated according to the formula (ΔX/ΔY). The sign of this computed value may be used to unambiguously determine the sign of the slope.
Latch 38 receives the Y axis coordinate of the initial crossover point. In FIGS. 2 and 3, this Y axis initial crossover coordinate is approximately 51, meaning that the first 50 lines are generated in one color without making a single transition.
The presently preferred embodiment further comprises a bit counter or pixel counter 40, initialized by raster generator 14 via lead 42 at the beginning of each raster scan, that counts in synchronism with the pixels being generated to provide the second digital timing signal. A line counter 44, initialized by the vertical sync coupled from raster generator 14 via lead 46, counts in synchronism with the raster lines being generated to provide the first digital timing signal. Thus taking the bit counter 40 and line counter 44 together, the invention generates a pixel number and line number corresponding to the pixel address currently being generated by the conventional raster generator. In terms of the XY cartesian plane, bit counter 40 generates the X position and line counter 44 the Y position.
The invention further comprises a transition point adder and accumulator 48. The adder and accumulator 48 receives the initial X axis crossover coordinate on lead 50 as well as the delta transition factor signal on lead 52. The adder and accumulator 48, initialized by the vertical sync coupled from raster generator 14 via lead 49, causes the initial X axis crossover coordinate to be stored in the accumulator. The adder accumulator 48 updates the transition point value after each raster scan and provides the current transition point value on output lead 54. An enable signal, yet to be explained, is coupled to the adder accumulator 48 from lead 56 to indicate when the current raster line is no longer in the non-intersecting region denoted by reference numeral 24 in FIGS. 2 and 3. When enabled, the adder/accumulator 48 updates the transition point for the next succeeding raster line by adding to the current transition point value stored in the accumulator the delta transition factor in latch 36. It will be seen that this factor to be added is equal to the negative reciprocal of the slope. After being computed the new transition point is stored in the accumulator and may be accessed on lead 54.
The invention employs two comparators, the first comparator 62 for testing whether the pixel currently being generated is to the right or to the left of the horizon boundary line. The second comparator 64 determines whether the current raster line being generated is above or below the initial crossover point 22. In other words, comparator 64 tests whether the current raster line is within or not within the area 24 of FIGS. 2 and 3.
More particularly, comparator 62 receives a signal indicative of the current pixel via output lead 63 from bit counter 40. Comparator 62 compares this value with the current transition point stored in adder/accumulator 48 via lead 54. If the numerical output of bit counter 40 is greater than or equal to the numerical output of adder accumulator 48, comparator 62 outputs a logical high signal on lead 66. Otherwise the output signal on lead 66 is low.
Comparator 64 receives a signal indicative of the current raster line being generated from the line counter via lead 65 and compares the numerical value of this signal with the initial Y axis crossover word stored in latch 38. If the output of line counter 44 is greater than or equal to the initial crossover word stored in latch 58, comparator 64 outputs a logical high signal on lead 68. Otherwise the signal on lead 68 is low. The signal on lead 68 is coupled to lead 56 and is utilized as the enable signal for the adder/accumulator 48.
The invention further comprises a color logic circuit 70. Color logic circuit 70 receives the start color signal stored in latch 32 via lead 71. The color logic circuit 70 also receives the output of comparators 62 and 64 via leads 66 and 68 respectively. In the presently preferred embodiment the color logic circuit provides an enable signal on lead 56, as previously discussed, for signifying when the line count stored in line counter 44 is greater than or equal to the initial Y axis crossover coordinate stored in line delay latch 58. It will be seen that this enable signal may be supplied by other means, as well. For example, the enable signal may be derived from the output of comparator 64. The color logic circuit further provides an output lead 72 on which a logical signal signifying either a sky shading or a ground shading is provided. It will be understood that this color or shading signal may be connected (not shown) to the display apparatus in order to control the shading or color of each pixel as it is generated.
The color logic circuit 70 also receives a signal, via lead 74, indicating whether the current transition point is on or off the display screen. With reference to FIG. 2, it will be seen that the transition points corresponding to raster lines in the region denoted by reference numeral 25 are off the display screen. In contrast, referring to FIG. 3, it will be seen that the transition point is always on the screen. The signal indicating whether the current transition is on or off the screen may be derived from the overflow bit within the adder/accumulator 48. In the usual fashion, this overflow bit would contain a zero unless a borrow or carry is performed by the adder. Such a borrow or carry would normally occur when the number to be stored in the accumulator is negative or exceeds the number of pixels per line, typically 256.
Color logic circuit 70 also receives a signal, via lead 76, indicating whether the slope of the horizon boundary line is positive or negative. In the preferred embodiment, this signal is indicated by the sign bit of the delta transition factor utilized by the adder/accumulator to update the current transition point value.
The operation of the color logic circuit 70 may be further understood with reference to the following table.
TABLE 1______________________________________Color LogicLead 74 Lead 68 Lead 76 Lead 66 Lead 72Transition Line> = Sign of Bit> = Coloroff Screen? Delay Delta Transition Output______________________________________a No No Positive Don't care Not Startb No Yes Positive No Startc No Yes Positive Yes Not Startd Yes Don't care Positive Don't care Starte No No Negative Don't care Startf No Yes Negative No Startg No Yes Negative Yes Not Starth Yes Don't care Negative Don't care Not Start______________________________________
In Table 1, the first four columns denote the possible states on color logic circuit input leads 74, 68, 76 and 66. The fifth column gives the color output corresponding to the particular input states given. It will be recalled that the start color stored in latch 32 and supplied to the color logic circuit via lead 71 may be either the sky shading or the ground shading as determined by the host processor 30. The color output signal on lead 72 thus indicates whether the pixel currently being generated should take on the start color or the not start color.
For illustration of the operation consider the horizon display of FIG. 2, and assume that the display consists of 256 horizontal scan lines, each consisting of 256 pixels per line starting in the upper left corner. The host processor 30 might compute the initial crossover X-coordinate to be zero and the initial crossover Y-coordinate to be 51, for example. Likewise, the host processor would compute the slope of the horizon boundary line and provide its negative inverse, the delta transition factor, to latch 36. In this example, the delta transition factor might equal 1.4655. The host processor also supplies the start color, in this case, the ground shading.
After the host processor puts the above computed data into the associated latches 32, 34, 36, and 38, the horizon raster generator 14 is started. The raster generator initalizes the hardware for a new display by setting the transition point adder/accumulator 48 to the initial transition point and by initializing the line counter 44 to 1. A raster line is then drawn horizontally by holding the Y deflection constant while ramping the X deflection signal. During this time the bit counter 40 is counting, each count corresponding to a display pixel, and the color logic circuit 70 is monitoring the status of the other hardware. The entire first raster line is drawn with the color equal to not start color (sky shading), since the line count of line counter 44 is not yet greater than or equal to the initial crossover Y-coordinate stored in line delay latch 58, see Table 1, line a. At the end of the raster line, the line counter 44 is incremented to 2, the Y deflection signal is moved down one line width and the X deflection signal is initialized once again. The next fifty lines are drawn similarly, all sky shading.
When the line counter 44 is incremented to 51, the color logic circuit 70 detects that the line count is now greater than or equal to the line delay. At the beginning of the line, the count in bit counter 40 is equal to 1 and the color logic circuit determines the color to be not start color (sky shading), since the bit count is greater than or equal to the transition point, namely zero, see Table 1, line c. The same is true for the remainder of the line. At the end of the line, the line counter 44 is incremented to 52, the Y deflection signal is moved down one line width and the X deflection signal is initialized. Now that the line count of line counter 44 is greater than or equal to the line delay value in latch 58, the adder/accumulator 48 is enabled by a signal on lead 56. This causes the adder/accumulator 48 to add the delta transition factor to the X-coordinate of the initial crossover point stored in latch 34 to thereby compute the new transition point for the next line.
At the beginning of line 52, the bit counter 40 is reset to one and the new transition point in adder/accumulator 48 is 1.53846. The color logic circuit 70 sets the color to the start color since the count in bit counter 40 is not greater than or equal to the transition point. See Table 1, line b. As the bit counter increments as the line is drawn, the color logic circuit 70 detects when the count in bit counter 40 is greater than or equal to the transition point in adder/accumulator 48. When this occurs, the color logic circuit 70 selects the not start color (sky shading). See Table 1, line c. The resulting line 52 will thus contain one ground shaded pixel followed by 255 sky shaded pixels. The next 164 lines are drawn similarly. For example, line 135 is drawn with 128 ground shaded pixels followed by 128 sky shaded pixels.
When the transition point is updated at line 217 to a value greater than 256, the overflow bit on lead 74 changes from 0 to 1 and the color logic circuit 70 detects that the transition point is now off the screen. The remaining 38 lines will thus all be drawn with the color equal to the start color(ground shading). See Table 1, line d.
While the invention has been described in its preferred embodiments, it is to be understood that the words which have been used are words of description rather than limitation and that changes may be made within the purview of the appended claims without departing from the true scope and spirit of the invention in its broader aspects. | An artificial horizon display generator determines either sky shading or ground shading in real time as each pixel of a raster display is generated. Transition line parameters are specified by host processor, whereupon the display generator computes whether the raster line currently being generated will intersect the horizon boundary line, and if so, at what X-Y transition point. Pixels generated prior to the transition point are of the initial shading; pixels generated subsequent to the transition point are of the opposite shading. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to sewing machines and, more particularly, to an arrangement for informing the sewing machine operator as to the amount of thread remaining on the bobbin of the sewing machine.
There are a number of known arrangements in the prior art for signalling a sewing machine operator as to the impending depletion of bobbin thread. Such an arrangement is desirable in order to warn an operator of impending bobbin exhaustion which might interfere with the appearance of a long seam. A number of these arrangements utilize a light source and a light detector arranged so that when there is thread on the bobbin the optical path from the light source to the light detector is blocked, this path being opened when the amount of thread remaining on the bobbin is depleted below some threshold value. Upon the occurrence of this latter condition, appropriate circuitry activates an alarm, or indicator, that warns the operator amount of thread remaining on the bobbin is below the predetermined threshold. Such an arrangement is disclosed, for example, in U.S. Pat. No. 4,188,901. Another arrangement of this general type is disclosed in U.S. Pat. No. 4,212,257 wherein an operator is advised both of impending depletion of the bobbin and also when the bobbin is full, the latter being for the purpose of preventing overwinding of the bobbin.
The prior low bobbin thread detection systems sense when the threaded bobbin diameter is below some threshold level. However, the bobbin thread is typically depleted from the bobbin in a non-uniform and unpredictable manner so that the threaded diameter of the bobbin is not uniform along the bobbin axis. Thus, there will be occassions wherein the optical path between the light source and the light detector is blocked by thread along one portion of the bobbin hub whereas another portion of the bobbin hub may have the thread completely depleted therefrom. Accordingly, the above-mentioned arrangements may not provide an entirely accurate indication of the amount of thread remaining on the bobbin. It is therefore an object of the present invention to provide a bobbin thread level detection and display system which is insensitive to variations in the threaded bobbin diameter along the axis of the bobbin.
The aforedescribed arrangements inform an operator when the amount of thread on the bobbin is above or below some critical value but do not provide any other information to the operator. It would be desirable to be able to inform the operator as to the level of thread on the bobbin even before the operator is advised as to the impending depletion of the thread. It is therefore another object of the this invention to provide an arrangement whereby the operator is continuously informed of the thread carrying condition of the bobbin over a range of such conditions.
SUMMARY OF THE INVENTION
The foregoing and additional objects are attained in accordance with the principles of this invention by providing a bobbin thread level detection and display system in a sewing machine which includes means for sensing the thread carrying condition of the bobbin, the sensing means including a light source and a light detector. The inventive arrangement comprises a display device including a plurality of light emitting elements positioned in a regular array and energizing means responsive to the amount of light impinging on the light detector for controlling the energization of the plurality of light emitting elements to produce a visible light pattern in the display device that is related to the thread carrying condition of the bobbin.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing will be more readily apparent upon reading the following description in conjunction with the drawings in which like reference characters in different figures thereof denote like elements and wherein:
FIG. 1 is an enlarged view of a portion of the head end and loop taker of a sewing machine shown partially in section in order to show more detail thereof and in which this invention may be incorporated;
FIG. 2 is a plan view of the loop taker and bobbin area of the sewing machine indicating the placement of a light detector and box therefor and a light source; and
FIG. 3 is a schematic diagram of circuitry constructed in accordance with the principles of this invention for detecting and displaying the thread carrying condition of the bobbin of the sewing machine shown in FIGS. 1 and 2.
DETAILED DESCRIPTION
Referring now to the drawings, FIG. 1 shows a portion of a sewing machine having a bed 12 and a sewing head 18 overhanging the bed 12. The bed 12 is formed with a cavity 13 in which a loop taker 14 is rotatably carried on one extremity of a shaft 15 oriented so as to have a vertical axis. The shaft 15 is driven by bevel gears 20 which are driven in the usual manner by the main sewing machine drive motor (not shown). The loop taker 14 rotates in timed synchronization to the reciprocation of the needle bar 16, the needle 17 carried by the needle bar 16 being driven in endwise reciprocation through a work material supported on the bed 12 for cooperation with the loop taker 14 carried therein in the formation of stitches. A feed dog 19 is visible which is a portion of a feeding system (not shown) for feeding work material under the sewing needle 17 in order to generate a pattern of stitches. The work material is pressed against the feed dog 19 by a presser foot 22 supported on the end of a presser bar 23 which is urged downwardly in a manner well known in the sewing machine art. A throat plate 24 supports the work material and is fashioned with an orifice (not shown) through which the sewing needle 17 may project. The throat plate 24 is further formed with slots 25 through which the feed dog 19 may extend.
The loop taker 14 supports on a race 27 thereof a bobbin case 28. The bobbin case 28 is restrained from rotary motion with the loop taker 14 by a position plate 52 (FIG. 2). The bobbin case 28 is fashioned with a cavity 29 within which is supported a bobbin 30 for the carrying of lower thread for a lockstitch. A further explanation of the loop taker 14, the bobbin case 28 and bobbin 30 arrangement and how thread may be wound thereupon may be had by reference to U.S. Pat. No. 3,693,566. The teachings of this patent have been modified somewhat by extending the bobbin case 28 above the level of the loop taker 14 in order that bores 32, 33 might extend therethrough roughly tangent the hub 31 of the bobbin 30 (FIG. 2). The purpose of the bores 32, 33 is to allow the passage of light from a light source 35 as focused by a lens 36. The light rays extending from the bore 33 pass through orifices 38 in a mask box 40, which box 40 supports a light detector 42 on an inner wall thereof aligned with the orifices 38 and the bores 32, 33. A printed circuit board 44 is affixed to the bed 12 by means of a screw 45 and the mask box 40 is supported on the printed circuit board 44 with the light detector 42 having electrical connections thereto.
Referring now to FIG. 2, there is shown a plan view of the left side of the bed 12 showing the cavity 13 therein with the throat plate 24 removed and with a bed slide 50 thereof slid back to expose the loop taker 14, the bobbin case 28 and the bobbin 30. There is also visible a portion of the position plate 52 and a position finger 54 which serve to retain the bobbin case 28 in a stationary position against rotation with the loop taker 14 while permitting thread to be cast thereabout.
In accordance with the principles of this invention, a display device is provided, illustratively on the head 18, for displaying the thread carrying condition of the bobbin 30. This display device illustratively includes three light emitting elements 61, 62 and 63. As will be described in full detail hereinafter, this display functions as a bar graph display and is of an analog nature to inform continuously the sewing machine operator as to how much thread remains on the bobbin 30. Illustratively, when the bobbin is full, all of the light emitting elements 61, 62 and 63 will be off. Then, as the bobbin 30 begins to be depleted, the light emitting element 61 will first turn on, then the light emitting element 62 will turn on while the light emitting element 61 remains on, and finally when the bobbin 30 is nearly empty, all three light emitting elements 61, 62 and 63 will be turned on. A feature of the present invention, as will be described hereinafter, is that the light emitting elements 61, 62 and 63 will gradually brighten, rather than abruptly turn on, with decreasing bobbin thread levels.
FIG. 3 shown an illustrative circuit constructed in accordance with the principles of this invention for controlling the aforedescribed display device. Illustratively, each of the light emitting elements 61, 62 and 63 is a light emitting diode (LED). As shown in FIG. 3, the photodetector 42 is illustratively a phototransistor having its collector connected to a source 64 of positive DC voltage, illustratively 15 volts, through a resistor 65. The emitter of the phototransistor 42 is coupled to the base of a transistor 66 whose emitter is connected to ground. Thus, the transistors 42 and 66 are connected in the well known Darlington configuration to provide for increased current gain. The resistor 65 is relatively large, illustratively 120 kilohms, to eliminate dark current effects of the phototransistor 42. As thread is depleted from the bobbin 30, more and more light passes from the source 32 and through the lens 36 and the bores 32 and 33 to impinge upon the base of the phototransistor 42. As the amount of light impinging on the base of the phototransistor 42 increases, increasingly more current flows from the collector to the emitter of the transistor 42. This increasing current to the base of the transistor 66 increases the conductivity of the transistor 66, allowing more current to flow from the collector to the emitter of the transistor 66.
The LED's 61, 62 and 63 are connected in series between the collector of the transistor 66 and the voltage source 64. Additionally, the anodes of each of the LED's 61, 62 and 63 is connected to the voltage source 64 through a respective resistor 71, 72, and 73. Illustratively, each of the resistors 71, 72 and 73 has a resistance value of 560 ohms. Accordingly, as the transistor 66 becomes increasingly more conductive, current will start to flow from the voltage source 64 through the resistor 71, through the LED 61, and through the collector to emitter path of the transistor 66 to ground. This causes the LED 61 to emit increasingly more light. During this time, current is also flowing through the resistor 72 and the LED 62, and also through the resistor 73 and the LED 63, which currents add to the current flowing through the LED 61 from the resistor 71. However, the current levels through the LED's 62 and 63 are insufficient to cause the LED's 62 and 63 to emit visible light until some threshold current level through the LED's is attained. As the bobbin thread becomes more depleted, more light impinges on the base of the phototransistor 42, causing it to become more conductive, which in turn causes the transistor 66 to become more conductive. More current then flows through the LED 61, and the LED 61 becomes increasingly brighter. As the current through the transistor 66 increases, current flow through the resistor 72 and then through the LED 62 will increase, thereby gradually turning on the LED 62. It will be noted that any current flowing through the LED 62 will also flow through the LED 61, so that the LED 62 can never be brighter than the LED 61. As the current through the transistor 66 rises still further, current flow through the resistor 73 and through the LED 63 will increase. This current will also flow through the LED 62 and the LED 61. Thus, as the bobbin thread is depleted, first the LED 61 will turn on, then become increasingly brighter, then the LED 62 will turn on, and become increasingly brighter, and finally the LED 63 will turn on, and become increasingly brighter. Accordingly, the number of LED's that are on, and their relative brightnesses, function as a bar graph display to continuously provide the sewing machine operator with an indication of the amount of thread remaining on the bobbin 30. The aforedescribed arrangement is insensitive to the manner in which the thread is taken off the bobbin 30, and only responds to the overall amount of thread remaining on the bobbin 30.
Accordingly, there has been disclosed an improved bobbin thread level detection and display arrangement for a sewing machine. It is understood that the above-described embodiment is merely illustrative of the application of the principles of this invention. Numerous other embodiments may be devised by those skilled in the art without departing from the spirit and scope of this invention, as defined by the appended claims. For example, although three light emitting devices have been disclosed, this number can be either increased or decreased, depending upon the desired resolution of the arrangement. Further, although a phototransistor and light emitting diodes have been disclosed, other suitable elements may be substituted therefor. | A bobbin thread level detection and display arrangement for a sewing machine includes an array of light emitting diodes which are activated to convey to the sewing machine operator an indication of the quantity of thread left of the bobbin. To control the light emitting diodes, an arrangement utilizing a light source and a phototransistor is arranged proximate the bobbin. The circuitry for controlling the activation of the light emitting diodes also provides for a "fading in" of the individual light emitting diodes to provide a display in the nature of a bar graph. | 3 |
This is a continuation of application Ser. No. 07/894,769, filed on Jun. 10, 1992, which was abandoned upon the filing hereof.
The present invention relates to a stabilized arginase batch, a method for the enzymatic conversion of arginine to ornithine in aqueous solution and an arginase kit useful for this purpose.
BACKGROUND OF THE INVENTION
Arginase (L-arginase, L-arginine amidino hydrolase: E. C. 3.5.3.1) is an enzyme which has been known for more than 50 years and which catalyzes the enzymatic production of L-ornithine from L-arginine. This catalysis takes place in vivo in the liver of mammals in the last stage of the urea cycle, during which urea and L-ornithine (2,5-diaminopentanoic acid) are formed by hydrolysis from (L-arginine 2-amino-5-guanidino pentanoic acid). The enzyme can correspondingly be obtained from mammal liver, e.g. calf's liver; however, it also occurs in the flora kingdom as well as in several microorganisms.
Arginase has a molecular weight of approximately 138,000 and consists of 4 identical subunits. Mn 2+ as well as Co 2+ and Ni 2+ can be added as typical activator.
L-ornithine is an amino acid which occurs in the body of mammals but is not produced during anabolism and is therefore not incorporated in proteins, that is, a natural but non-proteinogenic amino acid.
L-ornithine can replace L-arginine, an amino acid essential in infants and children, in all functions. Since the salts of L-ornithine entail a lesser stressing with urea of the organism and exhibit in part a better solubility behavior than L-arginine, L-ornithine has considerable commercial potential. A deficiency of arginine or ornithine can result in injury, in some cases in death, e.g. by means of an elevated ammonia level on account of high amino acid adsorption after a period of fasting or malnutrition.
Arginase has long been used as a diagnostic enzyme. However, this enzyme could not be used hitherto for the production of L-ornithine from L-arginine on an industrial scale since it exhibits only a very slight stability under reaction conditions and correspondingly can not be recovered or can be recovered only to a slight extent from an enzyme batch. Therefore, because of the high enzyme expense, the enzymatic production of L-ornithine from L-arginine is not cost effective on an industrial scale.
Therefore, the only potential candidates for industrial production of L-ornithine and its salts have included only fermentation from glucose with strains of Brevibacterium, Corynebacterium and Arthobacter, and the chemical hydrolysis of L-arginine in addition to the enzymatic method. However, the chemical hydrolysis results in many byproducts, e.g. in the partial hydrolysis to L-citrulline (2-amino-5-ureido pentanoic acid) or in the racemization of L-arginine or L-ornithine. Fermentation to L-ornithine is economical only in high tonnages.
Although arginase exhibits a satisfactory activity and selectivity for the hydrolysis of L-arginine to L-ornithine, the stability of the enzyme for industrial use is insufficient. In order to obtain good activity, the addition of bivalent manganese ions in addition to the enzyme to the reaction solution is necessary. However, when the reaction is carried out at the generally adjusted pH of the reaction of 9.5, which corresponds to the activity optimum of arginase published in the literature, the oxidation of bivalent manganese to tetravalent manganese frequently causes precipitatation of manganese dioxide after a brief time. A deactivation of the arginase also occurs (M. Munakata et al., Bioinorganic Chemistry 1976, 6, pp. 133-42; V. Rossi et al., Int. J. Peptide Protein Res. 1983, 22, pp. 239-50).
SUMMARY OF THE INVENTION
The object of the present invention is to provide a stabilized form of an arginase batch which can be used in a rather broad pH range without becoming excessively deactivated. A further object of the invention is to provide arginase in a form which can be separated after the reaction for reuse. A still further object of the invention is to provide a corresponding arginase kit and a method for the enzymatic conversion of L-arginine to L-ornithine in solution in which method the arginase can be reused.
These and other objects are provided by a stabilized arginase batch which contains a reducing agent dissolved in the water in a molar concentration which is at least 10-fold relative to the arginase.
As used herein, the term "arginase batch" refers to a composition which contains, dissolved in water, the enzyme arginase, a substrate which is to be converted by the enzyme and, if necessary, Mn 2+ . In accordance with the present invention, the arginase batch also contains a reducing agent in a molar concentration at least tenfold times the concentration of the arginase.
For reasons of concentration and expense, a molar amount of the reducing agent 10 6 times greater than the enzyme is set as upper limit of the excess. Additions of the reducing agent in 10 2 to 10 4 -fold excess relative to the arginase are advantageous; the reducing agent is advantageously present in a concentration of 10 -7 -10 -1 moles/liter, preferably 10 -5 -10 -3 . Mercaptoethanol, dithiothreitol and, especially advantageously, ascorbic acid (L-ascorbic acid, vitamin C) have proven to be effective reducing agents.
The arginase reaction takes place preferably at a 10 -8 to 10 -5 molar concentration (moles/liter) of arginase. It is advantageous for good arginase activity if Mn 2+ ions are present in a 10 to 10 6 -fold excess relative to the arginase. The solvent is preferably purely aqueous. The enzyme, e.g. arginase from calf's liver, is advantageously used between 1000 and 10,000 U/l; Mn 2+ is added preferably between 10 -4 and 10 -2 moles/liter, preferably as manganese sulfate. It has been determined, in this connection, that an especially good stability of the arginase is achieved at a stoichiometric deficiency of the reducing agent relative to the Mn 2+ ions, especially at a molar ratio between reducing agent to Mn 2+ ions of 0.01-0.9. The stability is greatest if the molar ratio of reducing agent to Mn 2+ ions is between 0.1 and 0.5. These ratios are especially preferred if the arginase reaction is started at a pH of 8.5-10.5. The pH can be adjusted to 8.5-10.5 by the addition of acids (e.g. H 2 SO 4 or HCl) to the arginine solution; acid, arginine and/or ornithine form a buffer system.
It is advantageous to add 0.1 to 2.0 moles/l arginine to the arginase batch as substrate, in which instance a saturated solution containing undissolved arginine can be present. In the case of buffer-free batches, the ornithine formed can also precipitate. In particular, arginine concentrations between 0.5 to 1.5 moles/l, optimally up to 1.0 mole/l, have have been established as providing good arginase activity and high recovery rates of arginase. The arginine solution does not have to be buffered, that is, the initial pH of the solution may be approximately above 10.5 up to 11.5, preferably 11 to 11.5. This value is determined primarily by the intrinsic pH of the arginine. This pH then drops in the course of the reaction to approximately 9.5, conditioned by the conversion of arginine to ornithine. Especially at this initial pH, the concentration of the reducing agent should be at least 10 -5 moles/l.
It was found in this connection that, contrary to the pH optimum of 9.5 described in the literature, the enzyme is active for at least two days and even displays its greatest activity at pH's up 11.5.
The method of the invention for the enzymatic conversion of arginine to ornithine is therefore carried out by reacting arginine (optionally only partially dissolved) in aqueous solution with an arginase and optionally in the presence of Mn 2+ and optionally in the presence of a buffer system and that a reducing agent is present in the solution in at least a 10-fold molar amount relative to the arginase. In principle, the special requirements of the above-described arginase batch apply in a corresponding manner to the preferred measures of the method of the invention.
The reaction should take place in a quiescent solution, i.e., not agitated or shaken, since the shear forces which occur in a moving solution can deactivate the enzyme. The reaction time is customarily 24-72 hours, which provides total conversion of the L-arginine. The progress of the reaction can be followed, in particular in the case of non-buffered batches, using the decrease of the pH--the pH drops toward the end of the reaction to approximately 9.5, the intrinsic pH of the L-ornithine which is being produced.
The addition of the reducing agent in accordance with the invention, therefore, permits using arginase batches having a considerably broader pH range than is the case with arginase batches without reducing agent, in which the pH should be close to 9.5. This has the advantage that one can work with higher initial arginine concentrations and without an additional buffer system and nevertheless high recovery rates of arginine permit converting several batches with a single quantity of enzyme. Working in buffer-free or buffer-poor systems has the advantage of decreasing the salt concentration in the process. In contrast to the previous arginase batches, the addition of the reducing agent lowers the deactivation of arginase to less than one tenth of the values observed without addition of reducing agent, that is, the arginase is stabilized by at least a factor of 10 by the addition of reducing agent in accordance with the invention.
The stabilization can be expressed as enzyme consumption number, that is, as consumption of units of arginase per kg of ornithine produced during the recycling of the enzyme from each batch. This consumption number is, for an arginase batch using conditions as in Example 1.
5890 with pump motion without reducing agent,
5000 without pump motion without reducing agent and
270 without pump motion with reducing agent.
This stabilization renders possible an economic recovery of arginase after the reaction, which can proceed practically completely. Although according to the literature L-ornithine inhibits arginase, the influence is not controlling in the reaction of the invention. For recovery, the enzyme from the arginase batch is separated from the lower-molecular components at least to a large extent by means of ultrafiltration, preferably with a capillary ultrafiltration flowthrough cartridge (e.g. Romicon, separation limit 10,000 daltons). The batch flows in the cartridge with precipitated manganese dioxide through the capillaries, at which time the greatest part of the solution with the lower-molecular, dissolved components penetrates the pores of the capillaries and the enzyme together with the precipitated manganese dioxide in a small part of the batch (of the solution) leaves the capillaries at the discharge end in concentrated form. The manganese dioxide can be subsequently separated from the enzyme, preferably by filtration. The separated enzyme can be immediately reacted again with L-arginine in the same manner or stored for later use.
It is possible that this unusually high stabilization arises, among other things, because of the fact that the reducing agent partially prevents the oxidation of the Mn 2+ to Mn 4+ , yet the oxidation must not be totally prevented since small amounts of Mn 4+ are probably favorable for the activity of the enzyme. That is to say, given a relatively low pH, that is, between 8.5 and 10.5, the reducing agent should be present in a deficiency relative to the Mn 2+/4+ system in order that the oxidation of the Mn 2+ is not totally prevented. On the other hand, in the case of a higher pH, in the present instance up to approximately 11.5, the reducing agents which can be customarily used in enzyme reactions are not sufficiently strong to totally prevent the oxidation of the Mn 2+ ; correspondingly, even an excess of reducing agent relative to the Mn 2+ can be used in that case. The pH and the reducing agent should therefore be coordinated in such a manner with one another that a slow precipitation of manganese dioxide is assured, since this probably results in a buildup of a protective layer on the ultrafiltration membrane via which the enzyme can be separated again from the educts and products. The ultrafiltration membrane can be arranged and operated in an enzyme membrane reactor or also as separate unit. The reduction is therefore carried out with advantage in the presence of MnO 2 , which can also be formed during the reaction.
The components necessary or advantageous for the arginase batch are so stable individually and in mixture or in partial mixture that they can be advantageously offered and stored as a kit. That is, a kit contains amounts of arginase and reducing agent which are coordinated with one another. It is advantageous if the kit also contains Mn 2+ as e.g. manganese sulfate or manganese chloride and/or optionally also a substrate such as arginine as well as optionally also L-ornithine. L-ornithine is a competitive inhibitor of the enzyme but functions as a stabilizer during the storage of arginase (in solution and in lyophilized form). Then, in order to prepare the batch, the kit needs only to be dissolved in the appropriate amount of preferably sterilized water. The kit can also comprise a part of the required devices such as e.g. capillary ultrafiltration cartridges, especially if disposable products are desired.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The invention is described further below in examples and drawings, in which:
FIG. 1 shows an apparatus for an arginase batch; and
FIG. 2 shows a method for the enzymatic production of ornithine from arginine.
The batch ultrafiltration reactor 1 in FIG. 1 comprises reaction vessel 2 and ultrafiltration cartridge 3, which are connected to each other via valve 4. Reaction vessel 2 which contains reaction batch 14, can be sealed and is connected to pressure line 5. After the reaction is over, reaction batch 14 can be forced, without great turbulance, by nitrogen supplied via pressure line 5 and with open valve 4, through cartridge 3. Cartridge 3 comprises a plurality of porous capillaries 6 whose one end 7 is connected via valve 4 to reaction vessel 2 and whose other end 8 is connected to return line 9, via which the enzyme which passed the capillaries can be returned into reaction vessel 2. Filter 10 is located in return line 9 for separating the manganese dioxide which passed cartridge 3. The capillary exterior is connected via discharge 11 to product storage tank 12, in which the lower-molecular components of reaction batch 14 (ornithine, optionally non-converted arginine, buffer salts, reduction agent residues and Mn 2+ ) are collected.
An arginase batch can be charged with the returned enzyme.
The method illustrated in FIG. 2 comprises batch ultrafiltration reactor 1, which is similar to the reactor shown in FIG. 1. However, discharge 11 of cartridge 3 is connected to cation exchange column 15, on which the ornithine of the filtrate on cartridge 3 is retained whereas urea and anions pass the column. Column 15 charged with ornithine is washed and eluted with ammonia solution. The eluted ornithine is concentrated until saturation of the solution in container 16, neutralized with acid (e.g. HCl, H 2 SO 4 , L-aspartate, α-ketoglutaric acid, acetic acid) until adjusted to be weakly acidic and is combined in precipitation container 21 with approximately threefold the amount of ethanol. The corresponding ornithine salt precipitates thereby, with agitation by stirrer 17, is separated via filter 18 and brought in drier 19 to the desired degree of dryness. Each new batch is supplemented via closable opening 20 in reaction vessel 2 with the appropriate components (consumed enzyme, H 2 O, reducing agent, etc).
EXAMPLE 1
2.5×10 -4 moles manganese sulfate×H 2 O, one half of an equivalent, that is, 1.25×10 -4 moles ascorbic acid, as well as 10,000 units calf's liver arginase (Boehringer Mannheim, Germany) are added to 1 liter of a 0.75 molar solution of L-arginine which had been adjusted with sulfuric acid to pH 9.5. After 24 hours, the conversion of L-arginine was 98% and after a further 24 hours 100%.
After ultrafiltration via a hollow fiber module (Amicon, MWCO 10,000, 0.03 m 2 ), the filtrate was placed over an acidic ion exchanger, eluted with approximately 1 liter 5% ammonia, concentrated by evaporation to 500 ml, adjusted with approximately 26-28 ml concentrated sulfuric acid to a pH of 6.9 and the ornithine sulfate precipitated with 1.5 liter ethanol. 114.3 g pure ornithine sulfate were obtained (84.6% of theory).
EXAMPLE 2
A procedure analogous to that of Example 1 was used, but a concentration of L-arginine of 0.5 mole/l and 6600 units of the enzyme were used. 82.2 g L-ornithine sulfate (91.3% of theory) were obtained.
EXAMPLE 3
A procedure analogous to that of Example 1 was used, but a concentration of L-arginine of 1 mole/l and 9400 units of calf's liver arginase were used. The yield of L-ornithine sulfate was 141.4 g (78.5% of theory).
EXAMPLE 4
30 ml of a 0.75 molar L-arginine solution were combined with 2.5×10 -4 moles manganese sulfate×H 2 O with various amounts of ascorbic acid and mixed with 370 units calf's liver arginase once at the intrinsic pH of arginine (approximately pH 11.5) and once stabilized with hydrochloric acid at an initial pH of 9.5. After 23 hours at room temperature, the conversions of arginine were determined. The enzyme was then separated via an ultrafilter and reused in the next batch.
______________________________________Initial pH 9.5 Clean MembraneClean Membrane Loss of Con- Asorbic Conver- Ascorbic Man-Batch version Acid sion Acid ganeseNo. (%) (mol./l) (%) (mol/l) Dioxide______________________________________1 52 2.5 × 10.sup.-4 67 1.25 × 10.sup.-42 37 56 1.25 × 10.sup.-43 13 41 1.25 × 10.sup.-44 7 37 1.25 × 10.sup.-45 4 30 0 *6 0 29 0 *7 -- 29 0 *8 -- 28 0 *______________________________________Initial pH 9.5 Membrane Coated With Manganese Dioxide Conversion Ascorbic AcidBatch No. (%) (mole/l)______________________________________1 59 2.5 × 10.sup.-42 313 194 165 126 107 88 7______________________________________Initial pH 11.5 Membrane Coated With Manganese Dioxide Clean Membrane Acorbic Ascorbic Conversion Acid Conversion AcidBatch No. 4 (%) (mol/l) (%) (mol/l)______________________________________1 79 2.5 × 10.sup.-4 79 2.5 × 10.sup.-42 73 733 69 724 70 655 67 616 66 617 66 628 66 61______________________________________
At an initial pH of 9.5, the enzyme is deactivated both in the case of a membrane initially coated with manganese dioxide and in the case of a clean membrane because, at this pH and with sufficient ascorbic acid, the membrane cannot hold a manganese dioxide coating. However, if ascorbic acid is not added, or if insufficient ascorbic acid is added, a layer of manganese dioxide forms and the enzyme is no longer strongly deactivated. At pH 11.5, however, a layer of manganese dioxide rapidly forms on a clean membrane and the enzyme deactivates only a little in each instance.
EXAMPLE 5
A 0.75 molar L-arginine solution is placed in an enzyme-membrane recycling reactor which has a a volume of 12 liters and 0.51 g manganese sulfate×H 2 O (2.5×10 -4 molar), 0.53 g and 0.265 g ascorbic acid (2.5 and 1.25×10 -4 molar) as well as 60,000 units (5,000 units/l) calf's liver arginase are added and the pH is adjusted with sulfuric acid to 9.5. After 23 hours reaction time in the stationary recycle medium, the conversion was determined, the enzyme was separated with nitrogen pressure delivery via a 2.4 m 2 ultrafiltration hollow fiber module from the Romicon company and returned to the reaction in the next batch.
______________________________________Initial pH 9.5Clean Membrane Clean Membrane Ascorbic AscorbicBatch Conversion Acid Conversion AcidNo. (%) (mol/l) (%) (mol/l)______________________________________1 70 2.5 × 10.sup.-4 88 1.25 × 10.sup.-42 50 2.5 × 10.sup.-4 86 1.25 × 10.sup.-43 35 2.5 × 10.sup.-4 90 1.25 × 10.sup.-44 20 2.5 × 10.sup.-4 84 1.25 × 10.sup.-45 4 2.5 × 10.sup.-4 84 1.25 × 10.sup.-46 1.5 2.5 × 10.sup.-4 84 1.25 × 10.sup.-47 0 2.5 × 10.sup.-4 83 1.25 × 10.sup.-48 -- 84 1.25 × 10.sup.-4______________________________________
Given an equimolar addition of manganese sulfate, the enzyme deactivates rapidly whereas in the case of a semi-equivalent addition a slight loss of manganese dioxide was apparent after 23 hours and the arginase deactivated only slightly.
EXAMPLE 6
Production of L-ornithine acetate
42.3 mg manganese sulfate hydrate (2.5×10 -4 molar), 21.8 mg ascorbic acid (1.25×10 -4 molar) and 15000 units calf's liver arginase of the Boehringer Mannheim company were added to 1 liter of a 0.75 molar L-arginine solution. After 48 hours the conversion was 100% according to HPLC. The mixture was adjusted with acetic acid to pH 6.8, three quarters of the water drawn off and the ornithine acetate precipitated with one liter ethanol at room temperature. After 15 min. of postagitation the precipitate was filtered off, postwashed with ethanol and dried in a vacuum (40 mbars). The yield of pure ornithine acetate was 137.0 g, 95% of theory). Amount of rotation (c=5 in water)+10.0° (theoretical: +9.0 to +11.0).
EXAMPLE 7
______________________________________Arginase kit for 1 liter batch10,000 units arginase170 mg (1 mmole) L-ornithine × HCl42.3 mg (0.25 mmole) manganese sulfate × H.sub.2 O43.7 mg (0.125 mmole) L-ascorbic acid174.2 g (1 mole) L-arginine.______________________________________
The enzyme (in lyophilized form) and the L-ornithine are supplied in mixture in a vessel (ampoule) in which, in particular, the manganese sulfate and the ascorbic acid can also be mixed in. The arginine is normally put in separately but can also be present mixed in with the other components.
For the batch, everything is added to one liter of water and allowed to stand approximately 2 days. | An arginase batch capable of producing ornithine with reduced consumption of enzyme. The arginase batch is stabilized by the addition of a reducing agent in at least a 10-fold molar amount relative to the arginase. | 2 |
BACKGROUND OF THE INVENTION
(d,l)2-Mercaptomethyl-5-guanidinopentanoic acid is reported as a potent inhibitor of carboxypeptidase B [Ondetti, M. A., Condon, M. E., Reid, J., Sabo, E. F., Cheung, H. S., and Cushman, D. W., Biochemistry 18, 1427-1430 (1979)]. More recently, this compound has been shown to have excellent activity in inhibiting serum carboxypeptidase N (SCPN) [Hugli, T. E., Gerard, C., Kawahara, M., Scheetz, M. E., Barton, R., Briggs, S., Koppel, G., and Russell, S., Molecular and Cellular Biochemistry 41, 59-66 (1981)].
Ondetti et al, supra, details a multi-step sequence for the preparation of (d,l)2-mercaptomethyl-5-guanidinopentanoic acid. It is to a modification of the described method of preparation that this invention is directed. In the sequence described by Ondetti et al., supra, an intermediate, 2-acetylthiomethyl-5-aminopentanoic acid, is prepared. The trifluoroacetate salt of this material, as described in the Ondetti et al. reference, obtained as a pale yellow impure oil, is converted to the above intermediate by a cumbersome chromatographic procedure employing AG50WX2, a cation exchange resin. It has been discovered that this conversion and product recovery can be accomplished by a simple and rapid method using a base and a polar solvent.
SUMMARY OF THE INVENTION
Therefore, this invention is directed to a process for recovering 2-acetylthiomethyl-5-aminopentanoic acid of increased purity from an impure acid addition salt thereof, which comprises treating the impure acid addition salt in a polar organic solvent with a base.
DETAILED DESCRIPTION OF THE INVENTION
A schematic representation of the preparation of (d,l)2-mercaptomethyl-5-guanidinopentanoic acid from readily available starting materials is as follows: ##STR1##
The abbreviations used herein have the following meanings:
DCHA--Dicyclohexylamine
DMF--N,N-Dimethylformamide
Et--Ethyl
TFA--Trifluoroacetic acid
The portion of the foregoing sequence that illustrates the process of this invention involves the conversion of the trifluoroacetate salt of 2-acetylthiomethyl-5-aminopentanoic acid (X) to 2-acetylthiomethyl-5-aminopentanoic acid (XI) [Step 8, part 3]. In the Ondetti et al., supra, reference, this conversion and product recovery is carried out using a cumbersome chromatographic procedure. By the process of this invention, the product rapidly forms and, under the defined conditions, precipitates from the reaction mixture.
In treating the trifluoroacetate salt of 2-acetylthiomethyl-5-aminopentanoic acid in accordance with the process of this invention, two conditions must be met. First, a reagent must be employed that will generate the free amino acid product. This reagent, a base, will be used in an amount representing at least an equivalent of the amino acid salt starting material. Typical such reagents are alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, and the like; amines, such as diethylamine, triethylamine, diisopropylamine, tri-n-propylamine, benzylamine, and the like. A preferred base is an amine, and, in particular, triethylamine.
Secondly, generation of the free amino acid must be carried out in a medium which affords solubility for the amino acid salt starting material with accompanying precipitation of the free amino acid product. Polar solvents are suitable for this purpose. Examples are nitriles, such as acetonitrile, and the like; alcohols and glycols, such as methanol, ethanol, ethylene glycol, and the like; nitromethane; nitrobenzene; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, and the like; and other typical polar solvents. Amides are preferred for use, and, in particular, N,N-dimethylformamide.
Typically, the process of this invention is carried out by dissolving the acid addition salt of 2-acetylthiomethyl-5-aminopentanoic acid, generally as the relatively impure trifluoroacetate oil, in the selected polar solvent, usually DMF. To this solution then is added the selected base, typically triethylamine. The base effects production of the free amino acid which, under the process of this invention, precipitates from the mixture and is readily recovered therefrom in pure form.
The following represents a detailed example of the preparation of (d,l)2-mercaptomethyl-5-quanidinopentanoic acid, including that portion of the overall preparation which illustrates the process of this invention.
EXAMPLE
A. Ethyl N-(p-methoxybenzyl)nipecotate hydrochloride (III)
To 7 liters of toluene were added 695 grams (4.4M) of ethyl nipecotate, 1304 grams (4.8M) of p-methoxybenzyl trichloroacetate, and 660 grams (4.8M) of potassium carbonate. The mixture was refluxed for 72 hours under a nitrogen atmosphere after which it was cooled, and the solvent was removed in vacuo. The resulting oil was dissolved in chloroform, and the solution was washed with 10% aqueous potassium carbonate followed by 10% aqueous hydrochloric acid. The solution then was dried over sodium sulfate and concentrated in vacuo. The resulting oil was triturated with ethyl ether, yielding 783 grams of the title compound as a solid.
B. N-(p-Methoxybenzyl)nipecotic acid (IV)
To a mixture of 1 liter of water and 5 liters of methanol were added 783 grams (2.5M) of the product from part A and 211 grams (5.3M) of sodium hydroxide. The mixture was stirred at room temperature for 17 hours after which the solvents were removed in vacuo. Toluene was added to the residue and removed in vacuo to obtain 1055 grams of crude title compound.
C. 1-(p-Methoxybenzyl)-3-methylene-2-piperidone (V)
A mixture of 800 grams (crude) of the product from part B, 6 liters of acetic anhydride, and 1 liter of triethylamine was refluxed for 4 hours. The solvents then were removed in vacuo. The resulting residue was dissolved in chloroform, and the chloroform solution was washed with water, dried over sodium sulfate, and concentrated. The resulting oil was chromatographed over silica gel using a 1:1 mixture of hexane and ethyl acetate as eluant to obtain 219 grams of the title compound.
D. 3-Methylene-2-piperidone (VI)
A mixture of 219 grams (0.99M) of the product from part C, 276 grams (2.6M) of anisole and 3 liters of trifluoroacetic acid was refluxed for 48 hours under a nitrogen atmosphere. The solvents then were removed in vacuo, and the residue was chromatographed over silica gel using ethyl acetate as eluant to afford 115 grams of the title compound.
E. 2-Methylene-5-aminopentanoic acid, hydrochloride salt (VII)
To 8 liters of 6N hydrochloric acid were added 177 grams (1.59M) of the product as prepared in part E. The resulting mixture was refluxed for 40 hours after which it was cooled and extracted with methylene chloride. The aqueous layer then was concentrated in vacuo, toluene was added, and the solvents were again removed in vacuo. The resulting residue was recrystallized from isopropyl alcohol to obtain 44.6 grams of the title compound as a solid. A second crop yielded 26.9 grams of product as an oil.
F. 2-Methylene-5-(p-methoxybenzyloxycarbonyl)aminopentanoic acid (VIII)
To a solution of 3.8 grams (53 mmol) of the product from part E in 100 ml. of water were added 6.4 grams (159 mmol) of magnesium oxide with stirring followed by a solution of 12.2 grams (59 mmol) of p-methoxybenzyloxycarbonyl azide in 100 ml. of p-dioxane. The resulting slurry was stirred at room temperature for two days. The mixture then was filtered through Hyflo and diluted with 200 ml. of ethyl acetate. AG50W-X2 Dowex 50 ion-exchange resin (200 ml. wet volume) was added, and the mixture was stirred at room temperature for 2 hours. The resin then was removed by filtration and washed with water. The filtrate layers were separated, and the aqueous layer was extracted twice with 200 ml. of ethyl acetate. The combined ethyl acetate solution was dried over magnesium sulfate and concentrated in vacuo to give 15.5 grams of the title compound as an oil.
G. 2-Acetylthiomethyl-5-(p-methoxybenzyloxycarbonyl)aminopentanoic acid, dicyclohexylamine salt (IX)
To 15.5 grams of the oil containing the product from part F were added 50 ml. of thioacetic acid. The solution was allowed to stand at room temperature for 48 hours. The thioacetic acid then was removed in vacuo without addition of heat, and three portions of benzene were added and removed in vacuo to remove excess thioacetic acid. The resulting viscous oil was dissolved in ethyl ether, and the cloudy solution was treated with a slight excess (10%) of dicyclohexylamine. The mixture was cooled to less than 0° C., and crystals formed. The crystals were harvested to give 18.2 grams of the title compound.
H. 2-Acetylthiomethyl-5-aminopentanoic acid (XI)
The product from part G (12.5 grams; 22.7 mmol) was dissolved in 200 ml. of chloroform. The resulting solution was washed with two 200 ml. portions of 10% potassium bisulfate solution. The chloroform solution then was dried over magnesium sulfate and concentrated in vacuo.
The residue was dissolved in 18 ml. of anisole, and the mixture was cooled to 0°-5° C. Trifluoroacetic acid (115 ml.) was added dropwise over a 15 minute period, and the resulting solution was stirred at 0°-5° C. for 1 hour. The excess trifluoroacetic acid then was removed in vacuo. The residue was dissolved in water, and the aqueous solution was extracted with ethyl ether. The aqueous layer then was lyophilized to a pale yellow oil (X).
The yellow oil was dissolved in 65 ml. of dry N,N-dimethylformamide, and 8.6 ml. of triethylamine were added with stirring. A precipitate formed immediately. The resulting mixture was filtered, and the solid was washed with dry N,N-dimethylformamide. The residue then was dried in vacuo overnight. The resulting dried clumps were dissolved in water and lyophilized to give 3.9 grams (19.0 mmol; 84% yield) of the title compound as a floculant off-white solid.
n.m.r.: (D 2 O) 1.66 (m, 4, β and γ methylenes), 2.49 (m, 1, >CH--CO 2 H), 2.99 (m, 4, --CH 2 NH 2 and --CH 2 SCOCH 3 ).
Analysis, Calculated for C 8 H 15 NO 3 S (205): C, 46.81; H, 7.37; N, 6.82; S, 15.62. Found: C, 46.59; H, 7.07; N, 6.80; S, 15.77.
I. (dl)2-Mercaptomethyl-guanidinopentanoic acid (XIII)
To 100 ml. of 1.0N sodium hydroxide were added 4.9 g. (24.4 mmol.) of 1-guanyl-3,5-dimethylpyrazole nitrate. The resulting free base was extracted three times with 100 ml. of ethyl acetate. The ethyl acetate solutions were combined, dried over sodium sulfate, and concentrated in vacuo. The resulting residue was dissolved in 15 ml. of water, and 1.00 g. (4.9 mmol.) of the product from part H was added. The solution was degassed by evacuation, and argon atmosphere was introduced, and 1.4 ml. (9.8 mmol.) of triethylamine were added. The reaction apparatus was closed, and the solution was stirred at 40° C. for 3 hours. The aqueous solution was then washed four times with two-fold volumes of ethyl acetate. The aqueous solution was frozen and lyophilized to give 1.3 g. of a slightly impure, white solid, (mass spec shows on M-1, 246 ion; NMR good for desired product.)
The white solid (1.0 g.; 4.0 mmol.) was dissolved in 15 ml. of water, and the solution was degassed by evacuation. An argon atmosphere then was introduced. Concentrated NH 4 OH (15.0 ml.) was added dropwise over a 5 minute period, and the solution was stirred at room temperature for 1 hour after completion of the addition. The reaction mixture then was degassed in vacuo for two hours, frozen, and lyophilized to a colorless syrup. The resulting syrup was dissolved in a minimum volume of 0.05M ammonium acetate beffer, pH 4.15, and the solution was applied to a Bio-Rex 70 cation exchange column (3.5 cm.×38 cm.) equilibrated with the same buffer. Elution with the buffer was continued, and 20 ml. fractions were collected. All Sakaguchi positive fractions were pooled and lyophilized to give 0.310 g. of the title compound as a white solid, representing a total yield of 40% based upon the product from part H.
n.m.r.: (D 2 O) 1.60 (m, 4, β and γ methylenes), 2.42 (m, 1, >CHCO 2 H), 2.63 (m, 2, --CH 2 SH), 3.22 (m, 2, --NH--CH 2 --).
Mass Spectroscopy: 206 (M + +1), 205 (M + ), 174. | A process is described for recovering 2-acetylthiomethyl-5-aminopentanoic acid from an impure acid addition salt thereof by treating the latter in a polar organic solvent with a base. | 2 |
BACKGROUND OF THE INVENTION
[0001] This invention relates to an power generating apparatus and more particularly to an improved generator that produces a large power output at a lower driven speed, one that can be easily mounted in its operating location and as a unit, one which may be driven by a pair of internal combustion engines each of which has its own starting mechanism, one in which a wide variety of power outputs can be achieved with minimum power input, one in which the powering units and the output element are well cooled and also an arrangement where the driving members and the driven generating apparatus can be easily and compactly coupled together.
[0002] The use of electrical generators powered by a prime mover such as an internal combustion engine are well known. Although various constructions have been proposed, the generator normally is comprised of an armature having a number of ferromagnetic pole teeth around which electrical coils are wound. These coils or more particularly the pole teeth face a plurality of circumferentially spaced permanent magnets and one of the elements, generally the one carrying the magnets is rotated so as to induce a current flow through the coils.
[0003] Such an internal combustion engine driven generator is shown in Japanese Published Application JP Hei 8-80095. As is well known the amount of electrical power generated by such a generator is generally proportional to the speed at which it is driven. Therefore when large electrical power outputs are required, the speed of the driving engine is increased.
[0004] However when the engine speed is increased, the engine noise may become objectionable. This can be avoided if a step up transmission of some type is interposed between the engine and the generator to increase the rotational speed in relation to the engine speed, but the inertial force of the generator is proportional to the square of the speed at which it is driven, putting increased loading on the bearings and causing vibrations both of which will adversely affect the unit life and increase the need for servicing.
[0005] Therefore it is a principal object of the invention to provide a driven generator that can produce greater electrical power without requiring high rotational speeds achieved by either higher engine driving speeds or the use of step up transmissions.
[0006] In the co-pending application Ser. No. 10/904,882 of which I am a co-inventor with other and which is assigned to the assignee hereof there is disclosed an electrical generator having two relatively rotatable elements each of which is driven in its respective direction by a prime mover arrangement so as to increase the power output without increasing the driving speed. However all of the embodiments disclosed therein require separate mounting bases for several of the components that makes the mounting of the assembly complicated and may also suffer detrimental effects if alignment is not maintained.
[0007] Therefore it is a first principal object of this to provide a power generating apparatus that can produce high power outputs and which is formed as a unitary assembly to facilitate mounting and insure the desired alignment of the various components.
[0008] Here it should be noted that although the aforenoted co-pending application produces electrical power output, the same arrangement may be employed for producing power outputted in another form such as fluid power with certain types of pumps.
[0009] By driving the generator elements in opposite directions the power can be increased relative to the driving speed avoiding the problems of vibration and noise. In addition it has been discovered that the driving speeds of the prime movers, if two are employed, can be varied independently thus providing a greater range of outputted power. It is therefore a further object of this invention to provide a power generator having a greater range of power outputs at reduced overall driving speed.
[0010] If the power generator is an electrical power generator. brushes may be required to output the electrical power. If the component with which the brushes contact is continuously rotated then there might be high wear. Therefore it is a further object of the invention to provide an electrical generator that produces high electrical power when required but which also may be operated in a mode where brush wear is reduced to minimize servicing requirements.
[0011] With any power generator, heat dissipation is a problem. Where higher power outputs are obtained by the type of generator shown in the co-pending application, the amount of heat generated can become substantial. It is therefore another principal object of the invention to provide a power generator that has a very effective and compact cooling arrangement.
[0012] Where the generator is driven by one or more internal combustion engines. It is also desirable that the engine or engines are also well cooled. In accordance with another feature of the invention to provide cooling for the power generator that also is effective to cool the powering prime mover arrangement.
[0013] If the power generator is driven by one or more internal combustion engines, it is desirable that the powering engine or engines have self starters. When this is done, however, it is desirable that the starter or starters do not place a load on the system once the apparatus has started. It is therefore a further principal object of the invention to provide an improved engine driven power generator that embodies at least one electric starter motor that is disengaged when the apparatus has started.
SUMMARY OF THE INVENTION
[0014] A first feature of the invention is adapted to be embodied in a power generating apparatus comprised of a pair of prime movers. There is also a power generating device comprised of a pair of relatively moveable elements adapted to generate a source of power upon movement of one of said elements relative to the other. Each of the prime movers is adapted to move the elements in opposite directions. In accordance with the invention, a housing arrangement encloses the prime movers and the power generating device for mounting as a single unit.
[0015] In accordance with another feature of the invention as set forth in the preceding paragraph, the power generating device comprised an electrical generator.
[0016] Another feature of the invention also is adapted to be embodied in a power generating apparatus comprised of a pair of prime movers in the form of internal combustion engines. There is also a power generating device comprised of a pair of relatively moveable elements each driven by one of the engines and together adapted to generate a source of power upon movement of one of said elements relative to the other. Each of the engines is provided with a respective starting system.
[0017] Another feature of the invention is embodied in a power generating apparatus as set forth in the preceding paragraph and the respective starting systems comprise electric motors that drive the engines through one way clutches.
[0018] In accordance with yet another feature as set forth in the immediately preceding paragraph the one way clutches also act as one way brakes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a side elevational view of a first embodiment of the invention, with portions broken away and shown in section.
[0020] FIG. 2 is an enlarged cross sectional view of the left hand area of the embodiment shown in FIG. 1 .
[0021] FIG. 3 is an enlarged cross sectional view of the right hand area of the embodiment shown in FIG. 1 .
[0022] FIG. 4 is a cross sectional view taken along the line 4 - 4 in FIG. 2 .
[0023] FIG. 5 is a cross sectional view taken along the line 5 - 5 in FIG. 3 .
DETAILED DESCRIPTION
[0024] Referring now in detail to the drawings and initially primarily to FIG. 1 , the reference numeral 11 indicates generally a power generating unit and specifically in this embodiment an electricity generating unit. The power generating apparatus 11 is made up of a prime mover arrangement, indicated generally by the reference numeral 12 , that is in the illustrated embodiment comprised of spaced left 13 and right 14 four-stroke cycle internal combustion engines.
[0025] Disposed between the engines 13 and 14 is a power generator 15 , specifically in this embodiment an electric generator that is driven by the prime mover arrangement 12 in a manner to be described. This assembly is mounted on a fixed member 16 in the form of a pedestal, for directly supporting the prime mover arrangement 12 . The power generator 15 is supported through the prime mover arrangement 12 on the fixed member 16 .
[0026] The power generator 15 includes a first, generally cup shaped element 17 journalled for rotation about a horizontal axis 18 and supporting a plurality of circumferentially spaced permanent magnets 19 . Cooperating with these magnets 19 is a second element 21 also rotatable about the axis 18 and supporting a plural number of generator coils 22 wound around circumferentially spaced pole teeth 23 . The magnets 19 and the coils 22 closely face each other about the axis 18 . The first rotated element 17 and the second rotated element 21 are supported on the side of the fixed member 16 for rotation about the axis 18 .
[0027] The first rotated generator element 17 includes a hub part 24 detachably taper-fit to and supported with the free end of a crankshaft portion 25 of the left engine 13 along with the magnets 19 held to the inside round surface of the yoke 16 , removably attached to the first rotational crankshaft 25 by a fastener 26 provided at the free end of the first crankshaft 25 .
[0028] The second rotated generator element 21 includes a second rotational crankshaft 27 of the right engine 14 also rotatable about the axis 18 . Fixed to the end of the crankshaft 27 is the core 28 of second generator element which is made of laminated magnetic steel plates around which the coils 22 are wound. As best seen in FIG. 3 these laminations of the core 28 are detachably taper-fit to the free end of the second rotational crankshaft 27 by a threaded fastener 29 .
[0029] The first and second rotated elements 17 and 21 are placed so that both free ends of the first crankshaft 25 and the second crankshaft 27 closely face each other in the direction of the axis 18 . The prime mover arrangement 12 includes the left engine 13 for rotary-driving the first rotated element 17 in one direction A about the axis 18 and the right engine 14 drives the second rotated element 21 in the opposite direction B about the axis 18 . The fixed member 16 has spaced lugs for supporting the left engine 13 and the right engine 14 separately from each other.
[0030] The end of the first element 21 carrying the magnets 19 and driven by the left engine 13 extends in the direction of the axis 18 , further than the free end of the first crankshaft 25 toward the second crankshaft 27 . In a like manner an end of the core 28 and the coils 22 on the second crankshaft 27 of the right engine 14 projects more than the free end of the second crankshaft to provide a more compact arrangement. In addition the second crankshaft 27 extends a greater distance from its cylinder bore than that of the first crankshaft 25 from its cylinder bore for a reason that will become apparent as this description proceeds.
[0031] The power generating apparatus 11 includes a first starting device, indicated generally at 31 , for starting the left engine 13 by rotating it in the direction A about the axis 18 . There also is a second starting device 32 for starting the right engine 14 by rotating it in the opposite direction B.
[0032] The starting arrangement for the prime mover arrangement 12 also includes a first one-way brake 31 interposed between the left engine 13 and the first starting device 31 to permit the rotation of the first rotated element 17 only in the one direction A through the left engine 13 . In a like manner, a second one-way brake 32 is interposed between the right engine 14 and the second starting device 32 to permit the rotation of the second rotated element 21 only in the opposite direction B through the right engine 14 . Alternatively, only one of the first and second one-way brakes 31 and 32 may be provided.
[0033] Each of the engines 13 and 14 includes a crankcase 35 made by aluminum alloy casting and supported a respective lug of the fixed member 16 . In addition each engine 13 and 14 has its crankshaft 25 and 27 supported with a plural number (a pair) of bearings 36 , 37 in the respective crankcase 35 for respective rotation about the axis 18 .
[0034] Each engine 13 and 14 has a cylinder block 38 formed by aluminum alloy casting and projecting vertically upward from the crankcase 35 and which forms a respective cylinder bore in which a piston 39 reciprocates. As is common in the engine art, a connecting rod 41 connects the pistons 39 to their respective crankshaft 38 for its rotation.
[0035] The piston 39 and cylinder block 38 of each engine form a respective combustion chamber 42 . As is well known in the art intake and exhaust passages serve the combustion chambers 42 to admit a combustible charge (formed in any desired manner) to them and to discharge the burnt charge to the atmosphere through a suitable exhaust system. One such flow passage is shown at 43 along with a respective flow controlling valve 44 that is operated in any desired manner.
[0036] The charge in the combustion chambers 42 of the left and right engines 13 and 14 is ignited, for example, by a spark plug 45 that is fired by a respective ignition system 46 (only one of which is shown in conjunction with the left engine 13 . These ignition systems 46 are operated in any desired manner and may receive inputs from one or more sensors, indicated schematically at 47 . Again it is to be understood that the engines 13 and 14 may have any desired configuration and/or type except as will be hereinafter described.
[0037] The speed of each engine 13 and 14 may also be controlled in any desired manner, such as by well known throttle valves in their induction systems, and independently of each other, as will be described later in more detail.
[0038] As previously mentioned, the construction of the left and right engines 13 and 14 and their operation and speed control may be of any type and although spark ignited engines have been shown either or both may be Diesel or rotary type if desired. However, in accordance with the invention, the crankcase 35 and the cylinder block 38 of each engine 13 and 14 constitute a portion of an outer shell assembly, indicated generally at 48 . The cylinder block 38 and one part, indicated at 49 , of the crankcase 35 of the left engine 13 are respectively of the same size and shape as the cylinder block 38 and the one part 49 of the crankcase 35 of the right engine 14 .
[0039] Each of the crankcase portions 49 of the left and right engines is completed to form the respective crankcase 35 by a second crankcase member, each indicated by the reference number 51 . These portions of each crankcase assembly 35 are generally the same but that of the right engine 14 is slightly different because of the greater length of the crankshaft 27 than that of the crankshaft 25 of the left engine 13 .
[0040] The second crankcase parts 51 are each fixed to respective cylinder blocks 38 along oppositely inclined faces 52 thereof that mate with like inclined faces of the cylinder blocks 38 by respective threaded fasteners 53 that are received in tapped holes in the cylinder blocks 38 .
[0041] Facing outer ends 54 of the second crankcase parts 51 are enlarged and cylindrical in shape. Because of the longer length of the crankshaft 27 from that of the crankshaft 25 the second crankcase part 51 of the right engine 14 is longer than the corresponding part 51 of the left engine 13 . Nevertheless the facing ends 54 are still spaced from each other in the direction of the axis 18 .
[0042] To fill this gap and to provide additional rotational support for the longer crankshaft 27 a cylindrical bridging member 55 is interfitted between the crankcase portions 51 . The bridging member 55 has a wall 56 that supports another bearing 57 is provided so that the crankcase 35 provides further support for the crankshaft 27 .
[0043] The opposing portions 54 of the outer shell members 48 of the first and second engines 13 , 14 are removably secured to each other with the bridging member 55 sandwiched between them using a plural number of (four) fasteners 58 . These fasteners 58 pass through bosses 59 formed in one of the portions (that of the left engine 13 as shown) and received in tapped bosses 62 in the other portion.
[0044] Both the opposing portions 54 and the bridging member 55 are made in a cylindrical shape to face each other on the axis 18 . The projecting ends of the opposing portions 54 are made in complementarily stepped shapes to detachably fit to the bridging member 55 and to control the spacing between the ends of the crankshafts 25 and 27 .
[0045] The entire power generator 15 is housed in the internal space of the opposing portions 54 and the bridging member 55 . The first and second engines 13 and 14 , and the first and second rotated elements 17 and 21 may be separated from each other in the direction of the axis 18 as the fastening pieces 58 are unfastened. As they are separated, the first and second rotated elements 17 and 21 are exposed respectively out of the power generator 15 . On the other hand, as the second rotated element 21 is attracted toward the magnets 19 with the magnetism of the magnets 19 of the power generator 15 , the mutual fitting of the opposing portions 54 up to the desired dimension is assisted.
[0046] One part 51 of the crankcase 35 is coupled to the cylinder block 38 of each of the engines 13 and 14 to form a single body that supports the respective crankshaft 25 and 27 between the bearings 36 and 37 . The cylinder block 38 crankcase part 49 of each of the engines 13 and 14 carries the bearing 36 . The crankcase part 51 of the crankcase 35 of each engine 13 and 14 carries the bearing 37 .
[0047] As has also been noted, the mating surface 52 of the respective parts 49 and 51 of each of the crankcases 35 slants downwardly in a straight line so as to be more distant from the facing outer end 54 in the direction of the axis 18 . Also as has been noted, the one parts 49 and 51 of the crankcase 35 are removably secured to each other using a plural number of threaded fasteners 53 with their axes extending perpendicular to the mating surfaces including the surface 52 .
[0048] Referring now primarily to FIG. 3 , the power generator 15 includes a plurality of slip rings 62 (three in the illustrated embodiment), located on the axis 18 , supported with and rotating together with the second crankshaft 27 . These slip rings 62 thus also rotate in unison with the core 28 of the generator 15 and are electrically connected to respective ends of the windings of the coils 22 , as is well known in the art.
[0049] Cooperating with the slip rings 62 are a plurality of brushes 63 , supported by the other part 51 of the crankcase 35 and specifically from a wall 64 thereof that carries the bearing 37 . As is also well known in the art, the slip rings 62 transmit the electrical power from the coils 22 to the brushes 63 .As shown schematically in FIG. 1 , an electrical wire 65 for conducts the power from the brushes 63 to an electricity receiving device 66 such as an external battery.
[0050] From the foregoing description it should be readily apparent that the construction is very robust and the axial alignment of the various components is maintained with high rigidity. This facilitates the mounting of the complete power generating unit as a unit. However this also results in some problems in connection with the cooling of the engines 13 and 14 and the power generator 15 , each of which generates heat in its operation.
[0051] Therefore, the power generating unit 11 is provided with an air type cooling device, indicated generally by the reference numeral 67 , which is comprised of a plurality of fans. The cooling device 67 includes: a first cooling fan 68 supported with and rotating together with the first generator element 17 and specifically formed integrally with its hub portion 24 and a second cooling fan 69 supported with and rotating together with the second generator element 21 and specifically integrally with the portion connecting it to the crankshaft 27 .
[0052] These fans 68 and 69 cool the electrical generator 15 . The fan 68 operates by drawing atmospheric air through a first air intake opening 71 formed in the lower part of the opposing portion 54 of the crankcase 35 of the left engine 13 . This air passes across the elements of the electrical power generator 15 and the heated air is discharged through a first air discharge opening 72 formed radially outside the first cooling fan 68 in the upper part of the opposing portion 54 of the crankcase 35 of the left engine 13 . This air flow is represented by the arrows C in the drawings.
[0053] In addition, a second air intake opening 73 is formed in the lower part of the facing outer end 54 of the crankcase 35 of the right engine 14 . This permits atmospheric air drawn by the action of the fan 69 to enter and pass through a communication passage 74 formed in the partition wall 56 . The air then passes through the interior of the bridging member 55 to cool the electrical generator and pass out of a second air discharge opening 75 formed radially outside the second cooling fan 69 in the upper part of the bridging member 55 as shown by the arrows D.
[0054] In addition to the aforedescribed cooling system 67 for the electrical generator 15 , it also includes an engine cooling fan 76 secured to the other end of the crankshafts 25 and 27 of the left and right engines 13 and 14 , respectively. A respective cowling 77 is secured to each of the crankcases 35 of the left and right engines 13 and 14 to partially cover each engine cooling fan 76 . An air intake opening 78 is formed in the outer face and lower portion of the cowling 77 . In addition, an air discharge opening 79 is formed in the upper part of the cowling 77 in facing relation to the respective cylinder block 38 to permit cooling air flow in the direction of the arrows E.
[0055] In the illustrated embodiment, the first and second starting devices 31 , 32 comprise recoil starters each including a respective housing 81 secured to the crankcase 35 of the respective engine 13 and 14 through its cowling 77 by means of threaded fasteners 82 . The starters 31 and 32 each include a respective recoil rope 83 contained in the housing 81 with one end comprising a grip portion (not shown) exposed outside the housing 81 . A respective starter clutch 85 contained in the housing 81 permits the transmission of pulling action of the recoil rope 83 to the crankshaft 38 only when a pulling force is applied.
[0056] The housing 81 is placed to cover the air intake opening 78 of the cowling 77 , and is provided with another air intake opening 85 for air to enter the air cooling system of each of the engines 13 and 14 .
[0057] The one-way brakes 33 and 34 are each interposed between the outer end of each crankshaft 25 and 27 and a stopper plate 87 secured to the cowling 77 using the threaded fasteners 82 and other fastening pieces. If the first element 17 tends to rotate together with the crankshaft 25 in a direction opposite the one direction A, or if the second element 21 tends to rotate together with the crankshaft 27 in a direction opposite the direction B, the first and second one-way brakes 33 , 34 engage with the crankcase 35 through the stopper plate 87 and the cowling 77 , to act as a one way brake so that the elements are prevented from rotating in the respectively reverse directions.
[0058] On the other hand, when the first and second engines 13 , 14 operate and both the crankshafts 25 and 27 rotate by themselves in their respective normal directions A and B, the first and second one-way brakes 33 , 34 and both the starter brakes 84 are released and the crankshafts 25 and 27 can turn freely.
[0059] Because of this arrangement each of the engines 13 or 14 may be started independently of the other without causing the other engine to be driven in a reverse direction from its normal rotation. In a like manner if both engines 13 and 14 are being operated either one may be stopped without causing the other to be driven in a reverse direction.
[0060] When both of the engines 13 and 14 are operated, the left engine 13 rotary-drives the first rotated element 17 in one direction A while the right engine 14 rotary-drives the second rotated element 21 in the opposite direction B from the one direction A. As a result, the magnets 19 and the coils 22 rotate in opposite directions to magnify the electrical power relative to machines where only one of the elements is rotated and the other is fixed. Thus electric current is generated in the coils 22 and outputted as a three-phase alternate current through the slip rings 62 , the brushes 63 , and the electrical wire 65 to the electricity receiving device 66 .
[0061] In the above case, it is made possible to regulate the rotary speeds (R 1 and R 2 ) of the first and second engines 13 and 14 respectively by the operation of by way of example the firing of the spark plugs 45 or throttle valves of the first and second engines 13 and 14 by the operation of the controller 46 , at the respective absolute rotary speeds R 1 and R 2 .
[0062] To put it more specifically, the rotary speeds of the first and second engines 13 , 14 may be optionally and individually chosen to be at any of low speed (3000 rpm in the eco-mode), high speed (5000 rpm), and normal speed (4000 rpm). This choice makes it possible for example to operate the power generating apparatus 11 in a state in which the absolute rotary speed R 2 of the second rotated element 21 is higher than the absolute rotary speed R 1 of the first rotated element 17 . It is also possible to operate only one of the first and second engines 13 and 14 .
[0063] As has been noted, the rotary motion of the crankshaft 25 of the left engine 13 is transmitted to the first cooling fan 68 which causes air present below the power generator 15 of the power generating apparatus 11 to be drawn through the first air intake opening 71 to the interior of the opposing portion 54 of the crankcase 35 of the left engine 13 to air-cool the first rotated element 17 and the magnets 19 , then is discharged to the atmosphere through the first air discharge opening 72 in upper part of the power generator 15 as shown by the arrows C in FIGS. 2 and 4 . Thus if only the engine 13 is operated there will be enough air flow to cool the electrical generator, considering it will not produce maximum power and accordingly maximum heat.
[0064] In a similar manner,. the rotary motion of the crankshaft 27 of the right engine 14 drives the second cooling fan 69 which causes air present below the power generator 15 of the power generating apparatus 11 to be drawn through the second air intake opening 73 to the interior of the crankcase portion 54 to air-cool the slip rings 62 and the brushes 63 . After that, the air is drawn through the communication passage 74 to the interior of the projecting end 59 of the bridging portion to cool the second rotated element 21 and the coils 22 , then through the second air discharge opening 75 to the atmosphere as shown by the arrows D in FIGS. 3 and 5 . Thus if only the engine 14 is operated there will be enough air flow to cool the electrical generator, considering it will not produce maximum power and accordingly maximum heat.
[0065] When both engines 13 and 14 are operated the greater heat generated by the generator 15 will be dissipated adequately by the operation of both cooling air flows. In this regard it should be noted that when only the engine 13 is operated the slip rings 62 will not be rotated so there will be no significant heating in this area to require cooling.
[0066] In a similar manner, the cooling systems 67 for the engines 13 and 14 comprised of the fans 76 only operate when necessary, that is when the respective engine 13 and/or 14 is started and running. Along with the rotary motions of either or both of the crankshafts 25 and 27 the respective engine cooling fans 76 will rotate. This causes external air to be drawn through the other air intake openings 85 to the interior of respective housings 81 of the first and second starting devices 31 and 32 to air-cool the starter clutches 84 . After that, the air is drawn through the air intake openings 78 to the interior of the cowlings 77 to air-cool the first and second one-way brakes 33 , 34 , then discharged through the air intake openings 78 of the cowlings 77 toward the cylinders 38 to air-cool the cylinder block 38 as shown by the arrows E in FIGS. 2 and 3 . Incidentally, because the first and second one-way brakes 33 and 34 normally do not contact the crankshafts 25 and 27 , the air-cooling described above is not always necessary.
[0067] As has been noted, it is possible to individually change the absolute rotary speeds R 1 , R 2 of the first and second rotated elements 17 and 21 by respectively changing the rotary speeds of the first and second engines 13 and 14 or even stop one of them while the other continues to operate to set the power generating apparatus 11 to an intended state of operation. Because the first and second elements 17 and 21 are rotated in opposite directions from each other, the relative speed between the both elements 17 and 21 can be increased, even with the respective rotation speed of the elements 17 and 21 is small. Therefore, the generation output can be drastically increased to be doubled, for example, compared to the prior art where only one of the elements is rotated at the same rotation speed as above. Such an increase in the generation output derives not simply from a high rotation speed of the rotors, but from the first and second rotors 17 and 21 being rotated in opposite directions. In other words, since the generation output can be increased even when the engines 13 and 14 for driving the first and second elements 17 and 21 is driven at a lower speed, which can be achieved while suppressing noise from the engines 13 and 14 .
[0068] In addition since an increase in the generation output does not rely solely on an increase in the rotation speed of the elements 17 and 21 as described above, the rotation speed of the elements 17 and 21 can be kept low so as not to cause large vibrations in the elements 17 and 21 , thereby preventing problems with the service life of the generating apparatus 11 while achieving an increase in the generation output.
[0069] Since the brushes 63 and slip rings 62 are associated with the element 21 driven by the engine 14 it would be preferable either not operate the engine 14 or to run it at a lower speed than the engine 13 to reduce wear on these components.
[0070] In the case single-phase alternating current is to be outputted with the power generating apparatus 11 , the number of the slip rings 22 may be two. To output in two kinds, three-phase alternating and single-phase alternating, five slip rings 22 in all suffice.
[0071] The opposing portions 54 , of the outer shell assemblies 48 of the first and second engines 13 and 14 opposing each other on the axis 18 are secured to each other. As a result, the first and second engines 13 and 14 are joined together more directly, so that a common framework for supporting the first and second engines 13 , 14 may be dispensed with, and bringing the power generating apparatus 11 to an intended state of operation may be accomplished with a simple construction and the rigidity of the power generating apparatus 11 as a whole may be achieved without an increase in the weight of the power generating apparatus 11 . Also because the opposing portions 54 and bridging member 55 are made in a cylindrical shape the rigidity of the power generating apparatus 11 as a whole may be accomplished without employing a separate reinforcing member. This also facilitates assembly and disassembly and the interposition of the electrical generator 15 adds to its protection and the overall strength and compactness.
[0072] It should be noted that the aforedescribed structure well meets the objects of the invention. However those skilled in the art will readily understand that various modifications may be made without departing from the scope of the invention, as set out in the appended claims. For example only, the power generator 15 may be directly supported with the fixed member 16 and /or, the power generator 15 may be a liquid pump where the first rotated element 17 comprises a pump housing, and the second rotated element 21 is an impeller. Furthermore, the engines 13 and 14 and the power generator 15 need not be placed on the same axis 18 . Also, the fixed member 16 may or may not be a common framework for the first and second engines 13 and 14 . Furthermore, the power generator 15 may be connected to interlock with the first and second engines 13 and 14 through an interlocking means such as a V-belt girdling mechanism. The magnets 19 may be constituted with coils energized through slip rings from outside. The axis 18 may be vertical or tilted.
[0073] As other possible modifications within the general concept of the invention, either or both the first and second engines 31 and 33 may be of the two-cycle type and their specifications may be freely selected in terms of number of cylinders, total displacement, and engine layout such as in-line type, V-type, and the like. The specifications of the engines may be different from each other. Also, the first and second starting devices 31 and 32 may use an electric motor as a drive source. As noted above, those skilled in the art will readily understand that various other modifications than those specifically mentioned may be made without departing from the scope of the invention, as set out in the appended claims. | An improved power generator having a pair of relatively rotatable elements each of which may be selectively driven in an opposite direction and at a desired speed by one of a pair of oppositely rotating prime movers to vary the power output and achieve a greater maxim power at a lower speed than conventional devices to reduce vibration and provide a longer life. The unit is comprised of a number of interconnected housing elements so that it can be compact, easily assembled and mounted. A clutch and brake arrange is incorporated to facilitate starting of the prime movers and to insure that one does not drive the other particularly in the wrong direction. In addition a cooling arrangement is provided that accomplishes the necessary cooling with respect to the amount op power generated. | 5 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from provisional application Ser. No. 61/272,490, filed Sep. 29, 2009.
FIELD OF THE INVENTION
[0002] The present invention relates to a novel, low density, high porosity chemical mixture of, primarily, basic lead sulfate salts which is useful as a carrier to convey other materials into a chemical process, to processes for its use, and to products made thereby. For example, the material of the invention can be used as a carrier for other materials which act to inhibit excessive crystal growth in lead-acid battery paste, which yields improved battery performance.
BACKGROUND OF THE INVENTION
[0003] Significant background material on the manufacture of lead-acid batteries can be found in the inventor's prior U.S. patent application Ser. No. 11/234,077 and corresponding PCT application PCT/US2005/034214, published as WO 2006/034466 and incorporated herein by this reference. Some of this material is reproduced below.
[0004] An important and time-consuming aspect of manufacture of lead-acid batteries is the curing of wet active paste material precursor into a dry porous mass. The paste precursor typically is in the form of flakes of “leady oxide”, i.e. flakes of solidified lead particles which have a PbO coating. The leady oxide is made into a wet, pliable dough (“paste”) by mixing it with water and then with sulfuric acid. The dough then is extruded onto mechanically rigid, electrically conductive grids in a process called “pasting”. The resulting pasted grids are cured at elevated temperature and humidity to react PbO with sulphuric acid, to form lead sulfate salts, and to oxidize the lead core of the leady oxide to PbO to form additional lead sulfate salts.
[0005] Lead sulfate salts which provide mechanical strength and porosity to the leady oxide paste, and ultimately become part of the active material, include tribasic lead sulfate 3PbO·PbSO 4 ·H 2 O (“3BS”) and tetrabasic lead sulfate 4PbO·PbSO 4 (“4BS”).
[0006] The 3BS typically forms at low temperature and low humidity, whereas 4BS typically forms at higher temperatures (>70° C.) and higher humidity. The 3BS typically forms as small needle-like crystals which measure about 3 microns long and less than about 1 micron in each of width and thickness. The 4BS crystals are larger, and grow in length from several microns to several hundred microns. The longer 4BS crystals have width and thickness in proportion to length. For example, a 300 micron long 4BS crystal might have a width of 60 microns and a thickness of 50 microns. A 4BS crystal that measures 300 microns long by 60 microns wide and 50 microns thick has a surface area of 72000 square microns, and a volume of 900,000 cubic microns. This volume, if tightly packed with the smaller 3BS crystals, would hold about 10 7 3BS crystals which have a total surface area of about 7.2×10 6 square microns, i.e. 1000 times greater surface area. The size and shape of the crystals in the cured paste can be measured by scanning electron microscopy (SEM). The amounts of the 3BS and 4BS crystals may be determined by x-ray diffraction (XRD).
[0007] In general, the useful capacity of a battery, particularly its ability to deliver high current for short periods of time, as required for example in the starting of internal combustion engines, is improved by increase in the surface area of the lead compounds in the cured paste. Accordingly, large crystals of 4BS are less desirable than smaller crystals, although the presence of 4BS is itself desirable.
[0008] The production of 4BS generally requires very careful control of temperature and humidity during cure of the pasted plates. Premature dryout and/or cooling of the plates during the curing process inhibit the formation of 4BS. Some battery manufacturers specify control and uniformity to ±2° C. and ±1% relative humidity (RH) compared to setpoints during cure. It has generally been observed that addition of red lead (Pb 3 O 4 ) allows adequate processing flexibility to allow production of 4BS over a larger range of temperature and relative humidity relative to setpoints; however, in controlled experiments, the red lead addition appears to interfere with free Pb oxidation.
[0009] Production of 4BS entails nucleation of crystals and their subsequent growth. Nucleation is effected by exposing the pasted plates to temperatures of about 70° C. or higher at high humidity at the beginning of cure. Nucleation and crystal growth during cure can require an induction period of about 10 hours since 4BS forms as molecules, which slowly coalesce by diffusion into seeds. These seeds can react with additional nearby material to grow into crystals. The growth rate of the 4BS crystals depends on various factors such as the composition of the lead oxide used, the oxide to sulphuric acid ratio in the paste mixture, the mixer type, mixing time, mixing temperature, temperatures between process steps, flash drying conditions, as well as the temperature and humidity inside the curing chamber, as mentioned above.
[0010] The growth of 4BS can proceed by two mechanisms. Large isotropic and “regular”, i.e. uniaxial, crystals, can be prepared by preferential deposition of a material onto one face of a seed crystal by a screw-dislocation or a slip-plane mechanism. Since only one face of each crystal grows, the process is slow. Crystals grown by this mechanism have smooth crystal faces and sharp angles between adjacent faces. Alternatively, crystals that grow anisotropically may be produced faster by fractal growth. Fractal growth entails growing the crystals at many locations and in many different directions simultaneously, i.e. multiaxially. The resulting fractal crystals are irregular and smaller in size. Fractal crystal growth may be confirmed by plotting “quantity produced” vs. time. Regular growth provides a straight-line linear plot. Fractal growth provides a straight-line log-log plot. Fractal crystal growth may produce greater mechanical strength in a paste pellet because the multiaxial crystals interlock better than the uniaxial crystals do. Fractal growth also may produce better electrical conductivity when it occurs in the paste.
[0011] Some battery manufacturers prefer 3BS rather than 4BS for engine cranking (also known as SLI, for “starting, lighting, and ignition”) batteries, which may be flooded, gelled, or absorptive glass mat (AGM) in design. To some degree this is because traditional curing processes tend to create highly variable yields of 4BS which have a large crystal size and a small amount of very large pores, and hence low surface area per unit weight. This variability in yield and the undesired crystallinity and porosity tends to cause variable (and generally poor) battery cranking performance in SLI batteries. Accordingly, many manufacturers prefer to avoid formation of 4BS insofar as possible.
[0012] When curing conditions are adjusted to preclude nucleation and growth of 4BS, a predominance of 3BS is produced. The 3BS has uniform crystal shape and size (3 microns X approximately 0.5 microns X approximately 0.5 microns). When a plate is pasted with 3BS the plate has uniform porosity and high cranking performance.
[0013] Historically, free Pb was a desired component of battery paste. The free Pb was thought to generate heat during cure of the pasted battery plates to enhance production of 3BS, 4BS and porosity. This heating, however, was uncontrolled and erratic, and the resultant plates did not always have the composition and/or porosity desired. Free Pb is now considered undesirable. A high amount (more than about 2 wt. %) of free Pb at the end of curing can lead to shedding and spalling failure of the positive plates and/or high self-discharge of “formed” PbO 2 plates.
[0014] The amount of free Pb in leady oxides typically is about 25 wt. %, but can form in amounts of 20 to 40 wt. % free Pb depending on the apparatus and the process settings. It is difficult and costly to produce a leady oxide with about 15 wt. % or less free Pb, and even more costly to produce a nonleady oxide. This latter usually requires a subsequent thermal processing, in small batches. Discharge capacity of a battery depends on the porosity and surface area of the porous battery electrode. Both the positive electrode, which for a lead-acid battery is the lead dioxide electrode, and the negative electrode, which for the lead-acid battery is the sponge Pb electrode, need porosity. The porosity of negative plates, during battery use, is improved by the well-known use of “expander” additives, which are comprised of barium sulfate, carbon black and lignosulfonic acid salts. All lead-acid electrodes which have a larger surface area have a higher discharge capacity, and higher utilization of the active material at any rate of discharge. In high discharge rate batteries such as SLI batteries, 3BS has been the preferred active material precursor, but if the undesirable growth of large crystals of 4BS can be inhibited, as provided by the invention, 4BS would also be desired in SLI applications. 4BS is the preferred material precursor for deep cycle and long-life stationary batteries. 4BS is also now the preferred precursor for use in modern nonantimonial grid batteries, the so-called “maintenance-free” batteries for SLI, float or cycling application, because the 4BS helps prevent PCL (premature capacity loss), i.e. short battery life. According to the present invention, the best features of 3BS and 4BS can be obtained simultaneously, without any apparent shortcomings, as described below.
[0015] Curing promotes adhesion of battery paste to the grids. The battery paste, which has an alkaline pH, reacts with (corrodes) lead alloy in the grid to partially convert the lead alloy to Pb compounds and ultimately to 3BS and 4BS. Generally, the higher the temperature employed during cure, the better the adhesive bond produced.
[0016] As mentioned above, production of 4BS depends on nucleation and growth of 4BS crystals. One way to get 4BS nuclei immediately into a battery paste is to use 4BS seed crystals, such as those prepared by grinding large crystals of pure 4BS. Large 4BS crystals can be made by any of several well-known aqueous slurry processes. These processes, however, are slow, and yield only a small amount of 4BS in copious amounts of liquid. Accordingly, this is very costly. Another way to produce 4BS is to use an Eirich mixer wherein 4BS is made into a more concentrated slurry, and then removing excess water by vacuum and heat. A pyrometallurgical reactor (Barton pot) also may be used to make 4BS. A slurry reactor and reactive grinding may be also be used to make 4BS. These methods, however, do not produce multiaxial crystals of 4BS, or seed crystals which can grow multiaxial crystals in battery plate pastes.
[0017] Ser. No. 11/234,077 discloses a paste curing additive (“PCA”) for battery paste for use in, for example, lead acid battery positive plates, and its methods of manufacture and use. The PCA limits production of larger 4BS crystals by nucleating growth of numerous 4BS crystals, so that more and therefore smaller 4BS crystals are present in the final product, as well as to grow the 4BS in multiaxial crystal groupings. PCA, which itself contains little 4BS, can be used to make more 4BS, and may be used to reduce the cure time of active material paste, as well as to reduce the amount of energy required during curing.
[0018] PCA also may be used to enhance production of 3BS during mixing and cure of battery paste. The PCA may be used to enhance curing of pasted battery plates, especially pasted battery plates intended for SLI lead-acid batteries.
[0019] PCA also may be used to achieve greater porosity in the form of higher numbers of pores as well as larger sizes of pores in the cured plate. PCA also may be used to speed oxidation of free lead residue in pasted plates during cure. PCA also may be used to enhance adhesion of the cured paste to the grid. These may provide greater utilization of the active material and easier conversion from the non-active “paste” state to the “active material” state.
[0020] PCA in amounts of about 1 wt. % to about 12 wt. % based on the weight of leady oxide may be used to speed the cure of battery plates at temperatures of about 56° C. to about 100° C. at RH of about 10% to about 100%.
[0021] Lead acid battery plates which include PCA may also cure faster and may show improved performance. In side-by-side tests for lead-acid traction battery positive plates, PCA outperformed a commercial ground 4BS crystal seed material: <2% free Pb was achieved in <20 hr with PCA, in 24 hr with the competitor material and in >40 hr with no additive (control). When these cured plates were tested in a cycling (charge/discharge) regime, controls operated <1000 cycles, the competitor material operated approximately 1500 cycles and PCA operated to >2500 cycles to end of life. The PCA cells were removed from test to allow testing of other cells; from the data trend it appears that PCA should have operated to >3000 cycles, which is twice the industry standard requirement of 1500 cycles.
[0022] The use of PCA may improve development of crystals of lead sulfate such as 3BS and 4BS, and may enhance more rapid development of porosity and the oxidation of free lead.
[0023] In one exemplary process, PCA is produced as the reaction product formed by heating a battery paste to a temperature of about 80° C. to about 90° C. for about 5 min. to about 10 min., wherein the battery paste includes sulfuric acid in an amount of about 5 wt. % to about 6 wt. %, water in an amount of about 12 wt. % to about 16 wt. %., and balance leady oxide, all amounts based on total weight of sulfuric acid, water and leady oxide. The additive may be then be used in any of its dried or undried states.
[0024] In a second exemplary process, the PCA is produced as the reaction product formed by heating a battery paste to a temperature of about 70° C. to about 90° C. for about 10 min. to about 90 min., wherein the battery paste includes sulfuric acid in an amount of about 3 wt. % to about 10 wt. %, water in an amount of about 10 wt. % to about 20 wt. %., and balance leady oxide, all amounts based on total weight of sulfuric acid, water and leady oxide.
[0025] As mentioned above, starting-lighting-ignition (SLI) lead-acid batteries have as their major mission to provide high current to the starter motor, which crank the internal-combustion engines of motor vehicles until they start. There is a market need to improve cranking ability while simultaneously reducing size, weight and cost. Cranking requires a high current (hundreds of amperes) battery discharge over a short period (<1 min.) of time. This requires that the active materials of the battery have a large and intimate contact area: the larger the surface area, the greater the cranking performance, all other things being equal.
[0026] Lead-acid batteries contain three electrochemically active ingredients, two being sets of solid members forming numerous opposed pairs of oppositely polarized “plates” and the third being the sulfuric acid electrolyte, which is disposed within and between the plates. The plates are connected together in two groups; the positive polarity plates contain PbO 2 and the negative polarity plates contain sponge Pb. As mentioned above, and as further detailed below, plates typically comprise conductive lead alloy frames called “grids” which at manufacture are filled with a “paste” of the approximate consistency of a plastic dough mixed from leady oxide (i.e., flakes of solidified lead particles with a PbO coating), water and sulfuric acid, cured, and then electrochemically “formed” or charged. Pastes intended for positive and negative plates are generally similar, except that pastes for negative plates contain other ingredients called “expanders”. One assembly of two sets of opposite-polarity plates, along with electrically insulating but porous separators, the electrolyte, and the containment for all of these comprise a single cell. Two or more (usually 3 or 6) series-connected cells comprise a battery.
[0027] The surface of each plate, both positive and negative, formed by pasting as described above, consists of two intermeshed parts: a discontinuous solid phase formed of the various lead compounds described above, interspersed with a discontinuous void space, which will ultimately be filled with electrolyte. In order to provide adequate surface area, the solid phase should consist of moderately large crystals with a “fuzzy” surface, or more numerous smaller crystals. The latter approach has traditionally been used by battery manufacturers, where the small crystals (approximately 3 microns long) are tribasic lead sulfate (“3BS”) the chemical composition of which is 3PbO·PbSO 4 or, if hydrated, 3PbO·PbSO 4 ·H 2 O. 3BS can be produced during the mixing of the battery paste or during the subsequent recrystallization or “curing” step, typically carried out at <70° C. During mixing and curing, different basic lead sulfate salts can be produced under different conditions. These range from non-basic lead sulfate (0BS, PbSO 4 ) through 1BS (PbO·PbSO 4 ) and 2BS (2PbO·PbSO 4 ) to 3BS as above and ultimately to 4BS (4PbO·PbSO 4 ). 0BS, 1BS and 2BS are generally undesirable in cured battery plates. 4BS, which is nucleated at >70° C. but which can subsequently grow after nucleation at any temperature from nearly 0 C to 100° C. (below this range H 2 O freezes and above this range H 2 O boils, of course), is desirable for use in long-life deep-cycling applications such as fork lift truck batteries, and may be useful to some degree in SLI battery applications as well, if the 4BS crystals can be inhibited from growing overly large. Thus, there is a desire to provide as much 4BS in the battery paste as possible, especially for batteries intended for deep-cycle applications, if certain problems inherent in the use of 4BS as mentioned can be overcome.
[0028] More specifically, and as also noted above, while 3BS crystals stop growing at 3 microns, 4BS crystals can grow to become several hundred microns in length. This size is mechanically and electrically desirable, but as these large crystals provide comparatively little surface area, they are electrochemically undesirable. Accordingly, smaller 4BS crystals are desirable to maximize the ratio of surface area to weight.
[0029] Generally, one 4BS crystal grows from a single seed, the seed consisting of ground, macro-crystalline 4BS, as is now commercially available. To grow small 4BS crystals, one approach (for example in U.S. Pat. Nos. 7,118,830 and 7,517,370) is to use very finely ground (0.1 to 5 micron) 4BS seeds, but this finely ground material is difficult to handle and provides a significant dust hazard which is undesirable. Another approach is to use a larger quantity of seed (20% rather than the usual 1 to 2%), but seed is costly and larger amounts appear to be preferentially consumed before leady lead oxide in the paste mixing and/or curing processes.
[0030] Higher growth temperatures for the growth of 4BS, performed with or without 4BS seeds, impart secondary nucleation of 4BS (desirable) and also generally give better grid-paste adhesion (also desirable) by way of enhanced grid corrosion by the alkaline battery paste. Thus, curing the paste at higher temperatures will generally result in the formation of more 4BS, but manufacturers may not be able or willing to cure the paste at such elevated temperatures.
SUMMARY OF THE INVENTION
[0031] The approach taken by the present invention is to provide seed of relatively large size, e.g. 20-40 micron, or <325 mesh, to nucleate the growth of 4BS crystal, so as to avoid the problems inherent in use of extremely fine powders, but to take precautions to interfere with the growth of the 4BS crystals, so as to limit the size of these crystals. Even though the seed particles were 20 to 40 microns in size, in the course of being mixed into paste and/or cured, the particles disintegrated and the resultant 4BS was acicular and generally under 40 microns in length, even without other precautions to limit the size. As mentioned, finely powdered 4BS seeds, such as are described in U.S. Pat. Nos. 7,118,830 and 7,517,370, are costly to make and difficult to handle.
[0032] In order to prevent or limit growth of over-large crystals of 4BS, one could drastically change the curing conditions, but this would preferentially affect the outsides of each plate, and, worse, perhaps affect only the outside plates of a stack of pasted plates stacked up for curing in an oven.
[0033] The present invention recognizes that as crystal growth generally proceeds in the direction of a single preferred crystallographic plane of a seed, one possibility for limiting crystal growth might be to add materials to the paste that would tend to modify the “crystal habit”, i.e. activate or deactivate growth of crystals along various planes.
[0034] The literature, for example Perry's Chemical Engineer's Handbook, 7th edition (1997) at Table 18-4 contains several examples of the use of borax to modify the crystallization of soluble alkaline earth and transition metal sulfates such as MgSO 4 and ZnSO 4 . Borax in a quantity of 5% is reportedly used to aid growth of crystals of these salts, although the original papers show no insight as to how this is accomplished. As materials such as MgSO 4 and ZnSO 4 are very soluble in water whereas basic lead sulfates are nearly insoluble in water, such that the chemical behavior of the respective substances are generally nonanalogous, there is no reason to expect that borax would be helpful in controlling the growth of 4BS crystals. Neither borate ion nor sodium is deleterious to battery operation, but unfortunately even as little as 0.1% borax can make battery paste soupy and unprocessable. Other salts have various other problems. For solubility and minimal materials costs, sodium salts are preferred to Li, K, Sr, etc. Some other sodium salts could be used, such as acidic phosphates, silicates, fluoborates, etc. Soluble peroxysalts (perborate, persulfate, percarbonate) have been used in batteries, but here the salt additive is intended to provide the peroxy oxygen to oxidize some Pb(O) to Pb 2 O 3 , Pb 3 O 4 or PbO 2 . Even nonalkaline salts such as boric acid might be useful.
[0035] Assuming that borax or perhaps some other material would be useful in limiting 4BS crystal growth, the next concern is to find a way to convey such a crystal growth-modifying ingredient into a workable paste mix. Any organic carrier can degrade ultimately to acetic acid, which undesirably corrodes the positive grids. Any inorganic carrier would need to be extremely porous, such that the additive, e.g. borax, would slowly dissolve and diffuse from the carrier to the 4BS growth plane, would also need to be extremely inexpensive, and would also need to be inert so as not to interfere with the battery operating conditions. This precludes use of most materials except titania, that is, TiO 2 , and lead compounds. Titania, used widely as a white paint pigment, is much cheaper than various nonstoichiometric titanium oxides, which have rough surfaces, but has no significant internal porosity. Titania, if used, would remain inert within each plate, that is, would not participate in charge or discharge, and would thus add undesired weight. Therefore, no titanium-oxygen material is particularly suitable as a carrier.
[0036] Considering the possibility of making a porous lead compound to contain the borax or other crystal growth inhibitor, it would be difficult to create porosity by adding water, air, or a gas-producing salt, as most lead compounds are made by a pyrolytic process at temperatures above the melting point of Pb (327.46° C.) and the heat would drive off or decompose the additive. Soluble anions such as chloride, acetate, perchlorate, or nitrate are deleterious to battery operation because they enhance the undesirable grid corrosion if a lead-based carrier were to be attempted using a hydro (low temperature aqueous solution) process. SEM microscopy shows little if any porosity in 3BS, 4BS or any of the other basic lead sulfates made by any of the solution/slurry methods. It would seem that a highly porous lead-based carrier would be impossible.
[0037] The simplest selection criterion for high porosity of a lead material is low material density. Although lead and its compounds generally have densities >9 g/cc, the inventor has discovered a lead compound with density approximately one third of this and a corresponding increase in porosity. SEM micrographs show that each grain of this novel lead mixture (described in detail below, and hereinafter called “Fluff”) is microporous, and that the low density is not merely imparted by a rough surface. When the Fluff was mixed with a borax solution, the borax was absorbed in the pores of the Fluff, as shown by the unchanged golden color and by an increase in material density. Summarizing the process of producing a borax-containing Fluff, the process being further detailed below: in order to introduce the borax into grains of the porous Fluff lead material, the most soluble borax form, borax decahydrate, was dissolved in water, mixed with the Fluff, and dried, leaving borax within the pores of the Fluff, probably in the form of a lower, less soluble hydrate, e.g., borax·5H 2 O. The final product, in a batch consisting of 3 kg of Fluff lead material having been impregnated with 5 kg of borax decahydrate solid material, fits within a one gallon can after drying.
[0038] The improvements and advantages provided by using such a combination of borax with the novel Fluff microporous lead sulfate mixture carrier (the combination hereinafter being referred to as “BF”) include that it has no effect on the processing characteristics of battery paste containing this material, and that its use, like PCA, limits the size of the 4BS crystals formed to 40 to 60 microns, presumably by causing more crystals to form and thereby reduce their size. Other crystals of large surface area and fine crystal structure are also formed, as shown by SEM, also providing improved high rate battery performance. XRD analysis shows the crystal mixture consists of 4BS and some various lead borate salts. The greater alkalinity of paste containing a BF combination due to the presence of the sodium ion also improved grid-paste adhesion, as shown by pellet-puncture mechanical tests. Initial tests of experimental plates made with a paste containing 4BS nucleant seeds plus BF showed a 10% improvement in moderately fast discharges (20 minute, the “reserve capacity”) versus controls which did not include BF. The inventor extrapolated, based on the well-known Peukert law, that cranking performance should have been improved by at least 10%, but because of the design of the battery test cells, this was not tested in the intial experiments.
[0039] Subsequently, the use of BF in battery paste together with a 4BS nucleant was tested at a SLI battery factory. These tests revealed minimal effect on paste mixing (slight initial or final water addition), better/faster curing, and better crystallinity and porosity of the cured plates (as seen in SEM examination). The latter manifested as faster formation (i.e., initial battery charging), less gassing, less water loss and a 12% increase in cranking performance. A preferred process for using PCA and BF was developed, but the first and three subsequent companies where tests were performed were unwilling or unable to fully comply with the inventor's recommendations. Nonetheless, each of 8 factory tests to date have shown not only improved high-rate battery performance, but also the necessary development of fine-particle high-surface-area 4BS that would explain such improved performance. Data from these tests is summarized in Table 1, below.
[0040] In all the tests described in Table 1, a combination of PCA and BF gave improved high-rate battery performance: at companies 1, 2, and 3 this was shown as a >12% increase in CCA despite processing below the recommended values (especially for curing and drying, paste mix peak temperature and oxide quality). Company 4 found higher capacity using PCA and BF in golf car batteries. These have an unpredictable current draw and duty cycle, so that capacity cannot be measured easily, but these approximate a 75 amp discharge and a 90-100 minute discharge time. It was observed that the PCA/BF batteries need recharge only every 2 to 3 days compared with 1 to 2 days for controls.
[0041] The ability of the Fluff to convey a material that might otherwise be deleterious into a process so as to be gradually diffused or dispersed may be useful in other applications. For example, the Fluff might be useful to convey colorants into glasses and ceramics. The Fluff might also be useful to convey catalysts for fuel cells or other applications. In another possible battery application, the Fluff might carry barium into plates to act as an “expander” which enhances discharge capacity. In this application, the Fluff could be expected to disperse Ba slowly, during curing, so that any BaSO 4 produced would be minimal in size and would not undesirably enhance shedding. This might allow use of barium as an expander within positive as well as negative plates.
[0042] The microporous basic lead sulfate Fluff material of the invention is distinctly different from the high surface area lead oxide (HSAO) made by treating an aqueous suspension of lead oxide with ozone, as described by G. Anthony Parker in U.S. Pat. No. 4,388,210. First, the HSAO material is made without sulfate, i.e. merely from oxide., in an aqueous slurry which contains various sodium salts but not specifically sodium tetraborate, which is treated by addition of ozone to create a mixture of lead oxide and lead dioxide. Second, the HSAO material seen under SEM examination has merely a coarse surface texture: it does not have internal microporosity, and consequently cannot store any significant quantity of, for example, a habit-modifying ingredient. Such an ingredient would be coated at best only on the outside of the coarse HSAO, where it would act like bulk, unabsorbed habit-modifier, that is, would dissolve as quickly as habit-modifier without HSAO. Furthermore, the density of the Parker HSAO material is substantially more than 3.5 g/cc.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Manufacture of Lead Fluff
[0043] The Fluff material of the invention can be made in the same process as the PCA material. Fluff was initially identified as a nuisance and undesirable byproduct of the manufacture of PCA, as described in application Ser. No. 11/234,077, and its production was minimized in order to maximize the production of PCA. Any Fluff still produced was separated during the grinding operation and was scrapped out. The value of Fluff was recognized later.
[0044] As disclosed in Ser. No. 11/234,077, PCA can be made by using a range of processing steps carried out on a typical battery paste of, e.g., 5-6 wt % sulfuric acid, 12-16 wt % water, balance leady oxide. Typically this paste is heated to 80-90° C. for about 5-10 minutes. Other examples are given in Ser. No. 11/234,077. Those of skill in the art will recognize this range of temperatures in particular as being considerably higher than the usual ranges used to cure such a paste in the typical battery plate pasting process. If the mixture is mixed of pre-heated ingredients, and especially when the acid is rapidly added, the resultant PCA comprises 3BS and 4BS and also some low density material which is composed of a small residue of lead oxide, some various basic lead sulfate salts including lead sulfate hydroxide and lead sulfate carbonate. By comparison, a typical XRD analysis of Fluff is: 63.7% 4BS, 10.5% 3BS, 7.8% 1BS, 13.1% hydrocerrusite, 3.4% litharge form of PbO and 1.1% leadhillite.
[0045] If the paste mixing is continued, especially with continued external heating, so that the water is driven off the paste quickly (over on the order of 30 minutes), followed by grinding, the PCA paste breaks down to a powder with grains in the size range from 50 down to <500 mesh. The heating and mixing create drafts such that the finest and lowest-density portion is thrown off, and further fine particles are similarly created during grinding. This low-density material, which is the novel Fluff of the invention, can be collected, e.g., with a vacuum source discharging into a baghouse, in both the mixing and grinding steps, as desired. Fluff might also be collected in a known “dropout” system, or by an air classifier, known in the art for separating fine particles according to their relative sizes. The coarser particles can be returned to the grinder for further reduction, or can be used “as is” as PCA. The larger particles of PCA are primarily 3BS and unreacted lead oxide, with a small residue of free lead. As above, Fluff is a mixture of lead oxide with various basic lead sulfates and a smaller amount of free lead. More significantly, Fluff has a low density (<3.5 g/cc) and correspondingly high porosity, and is insoluble in and does not react with water.
[0046] Fluff, unlike PCA, will not by itself nucleate paste to grow 4BS, despite being substantially composed of 4BS. Hence, PCA is still preferably also used in making battery paste, together with BF. Without limiting the invention, it is theorized that the lack of free PbO probably is what prevents Fluff from acting like PCA to nucleate growth of 4BS. However, when Fluff is subsequently incorporated into battery paste, as described below, it is incorporated into the cured paste materials (3BS and/or 4BS) and structure, so that its lead content contributes to the battery function.
[0047] The heating, mixing, drying, crushing, and separation of Fluff from battery paste which has been formulated and treated to form PCA and Fluff can be performed over a wide range of conditions, to be optimized depending on starting oxide composition and paste processing characteristics. The yield of Fluff can be improved by modification of these conditions. The yield of Fluff also depends heavily on the processes and apparatus used to collect it.
[0048] In one example, starting with two paste mixes totaling 1999 lb of leady oxide, 100 lb of water and 128 lb of 50 wt % (1.400 sp.gr.) aqueous sulfuric acid, the leady oxide and acid were unheated and the water was preheated to 47.6 deg C. The ingredients were mixed, forming a paste which was subsequently dried in the mixer to a residual moisture content of <1%. At this moisture content, the PCA material can be ground readily; at >2% moisture content the grinding operation is less efficient. In the example, the dried powder was ground slowly (500 lb/hr) in a Pulva model B hammermill grinder, and there was no collection of dust during mixing; the yield was 2090 lb of the high-density PCA residue and 15 lb of Fluff. As the PCA passed through the grinder into a collection hopper, Fluff was ejected through the vent port at the top of the grinder into a dropout box which in turn was connected to a ventilation system.
[0049] Since the reaction stoichiometry provides a weight gain from oxidation of most of the free Pb in the Fluff, and from the sulfate in the aqueous sulfuric acid, the inventor calculates that a few lb of Fluff was lost but could have been collected if dust collection steps had been performed at the mixer. The goal of this experiment was to maximize the yield of the high-density PCA material for another application, and therefore was to minimize the yield of Fluff; it appears clear that the processing conditions can be optimized for the production of Fluff. More specifically, in previous experiments in making PCA that were carried out on a kilopound scale, hotter water, more rapid acid addition and more rapid grinding were used, and a greater yield of Fluff was achieved. Therefore, for any particular starting combination of oxide material, acid, and water, it is logical to presume that the yield of Fluff can be optimized or maximized responsive to variation in the mixing and/or grinding steps.
[0050] Neither the patent nor technical literature known to the applicant describes any method to produce a low density, highly porous form of any basic lead sulfate. Mere mixing of 3BS, 4BS and the other ingredients, even when in a water slurry dried using an open-flame gas heater to make hydrocerrusite and leadhillite in situ, does not yield a low density product, nor a particularly microporous product.
Manufacture of Slow-Dissolving Habit-Modifier/4BS Growth Inhibitor
[0051] Fluff will cake together when wet, but, upon drying, is readily crushed back to a fine dust. This can be done repeatedly, as shown by its unchanged color, density, and ability to absorb other materials. It appears that neither the 4BS nor 3BS are recrystallized in this process.
[0052] In use of Fluff for inhibiting growth of large 4BS crystals in battery manufacture, the study next turned to identification of a suitable material to be absorbed by the Fluff, which would diffuse slowly out of the Fluff carrier to modify crystal habits and growth, as discussed briefly above.
[0053] Organics are generally precluded for prevention of large 4BS crystal growth. Although organics are reported to prevent formation of 4BS, experiments with battery paste containing 4BS seeds and organics (such as the lignosulfonates used as negative plate expanders) show that 4BS can be grown. Therefore, the organics prevent nucleation, not growth.
[0054] Most inorganic salts (halides, oxyhalides, sulfates, nitrates, nitrites and transition metal oxyanions such as chromate, manganate, etc.) are too expensive, too insoluble, and/or are electrochemically incompatible with the battery reactions.
[0055] Carbon-containing anions (acetate, citrate, etc) and the usual organic habit-modifying materials (urea, surfactants, etc) can degrade to acetic acid which will rapidly and undesirably corrode battery grids after oxidation on the PbO 2 in the formed positive plates.
[0056] It being desired to provide the crystal growth inhibitor as a salt, so as to provide chemical neutrality, a few salts are left as possible candidates for use as inhibitors of growth of large 4BS crystals: hydroxides, borates, oxides, carbonates, bicarbonates, silicates, phosphates, and possibly fluoro-derivatives of these. The alkaline paste will readily dissolve most of these. The counterion (cation) of choice (which is needed so that a salt is added) is probably sodium, based on minimal cost (as compared to, e.g., Li, K, Rb, etc.). Of possible sodium compounds, NaO and NaOH react rapidly, and the carbonate and bicarbonate react more slowly with lead oxide to generate the blood red salt sodium plumbate, and change (reduce) the paste viscosity, so these are inappropriate choices.
[0057] This leaves as candidates sodium borates, silicates, and phosphates, and perhaps the peroxysalts mentioned above, although the latter are much more expensive and much less stable than their non-peroxygenated analogues. The literature referred to above shows that borax (this term being used loosely here, as generally in the art, to refer to, e.g., sodium borates of various specific compositions, such as anhydrous borax (Na 2 B 4 O 7 ), borax pentahydrate (Na 2 B 4 O 7 ·5H 2 O), and borax decahydrate (Na 2 B 4 O 7 ·10H 2 O)) has been used to modify the crystal habits of various soluble transition metal sulfate salts such as MgSO 4 and ZnSO 4 , when used in a concentration of 5 weight percent of the transition metal sulfate. Mixing 5 wt % borax with battery paste changed its characteristics rapidly from a useable paste to a low viscosity suspension. Even as little as 0.1 wt % borax caused the paste to liquefy. Hence, it appears that any direct addition of borax to paste renders the paste useless.
[0058] As above, the inventor has found that borax could be absorbed within lead Fluff, and that the resultant BF material would not affect paste characteristics. Moreover, the borax diffused out of the Fluff during curing, such that it eventually modified 4BS growth and reacted to form various lead borate salts which were small in size and high in surface area. The inventor briefly considered other possible microporous carriers for borax, such as TiO 2 and ZrO 2 , but these are generally more expensive than lead Fluff and would remain inert within the plates during the battery life, since these are electrochemically inactive in a lead-acid battery. By comparison, the lead in Fluff contributes to the battery's function. Furthermore, at end of life, these other carriers might cause issues with battery recycling.
[0059] Borax is commercially available cheaply in many different forms which vary in terms of amount of hydration from anhydrous borax through 2, 4, 5, and up to 10 waters of hydration. Borax decahydrate (−10 H 2 O) was chosen, although the pentahydrate works equally well. Manufacturer's literature shows the solubility of borax decahydrate is 170 grams per 100 cc H 2 O at 100° C. This was interpolated to an estimated 150 g/100 cc solubility at 80° C. In a first trial, 2 kg of the decahydrate was dissolved in 5 liters of water but this was insufficient since addition of the salt to the hot water cooled the water off, so that some material would not dissolve, or, worse, would crystallize out. 6 liters of water was sufficient to dissolve 2 kg of borax decahydrate. After the borax was dissolved, with the solution maintained at >90° C., Fluff was added. Heating was continued until all the air in the pores of the Fluff had been driven off and the borax solution fully penetrated the pores, and continued until the remaining free water had been boiled off. Although 2 kg of Fluff will absorb 6 liters of the borax solution, there is probably some on the outside of each Fluff grain, as seen by the difficulty in grinding this composition after it has been dried. 3 kg of Fluff fully absorbs the borax solution, forming the desired BF material, and is easy to dry and grind, so the preferred ratio of materials is 6 liters of water, 5 kg of borax decahydrate and 3 kg of Fluff.
[0060] The lab-scale production of BF described above was carried out in enameled steel or stainless steel cooking pots heated over electric hot plates, but it is obvious that this can be scaled up for quantity. The water was measured out and heated to >/90° C., and borax decahydrate was weighed out and was added in incremental portions to the pot, such that temperature was maintained above 90° C. so that no borax precipitated out of the solution. After all the borax had been dissolved, the Fluff was weighed out and also added in portions to the pot to maintain the temperature above 90° C., to maintain the complete solubility of the borax. Fluff does not dissolve, so the solution becomes a suspension of the Fluff in the aqueous borax solution. The suspension is heated with the pot partially uncovered such that the volume of the suspension is reduced 10-20%, and the suspension reaches the consistency of a thick mud. In order to control the subsequent drying of the mud, it was found convenient to transfer the mud to smaller, shallower stainless steel pans and then dry these in a laboratory oven at between 80 and 140° C. If the mud is dried too quickly, such that borax separates from the mud rather than being absorbed by the porosity of the Fluff carrier, the batch can be redissolved and drying can be repeated at a lower temperature or at a lower drying rate (for example, by providing less ventilation).
[0061] Other materials that might also be useful are compounds which, like borax, that is, sodium borate, include an alkaline anion or hydrogen ion with a suitable cation, such as sodium phosphates, acid phosphates, sulfates, acid sulfates, silicates, fluoborates, or peroxysalts such as perborate, persulfate or percarbonate.
Use of BF Material in Battery Paste
[0062] The efficacy of BF as an inhibitor of growth of 4BS crystals requires, first, that it be used with 4BS seed crystal materials, which are available from several commercial sources, and second, that both these seed crystals and the habit-modifier additive BF be mixed intimately into the battery paste. There is some advantage to dry mixing the 4BS seeds with the oxide, since these powders mix together rapidly if not wet, and the 4BS seeds can start growing 4BS crystals during the paste mixing. Less preferred is to mix by adding water first, then oxide and wet mixing this, then adding the 4BS seeds, then adding the acid and then final mixing. The BF material should be added after acid addition is complete, but before final mixing. It may be possible to add BF at an earlier point in the process, for example by absorbing borax onto the Fluff component in an unseparated PCA-Fluff mixture, but conditions for this have not yet been established. As mentioned above, PCA is still used, as described in prior application Ser. No. 11/234,077, as part of the battery paste. After pasting, the use of any 4BS nucleant will allow faster curing, or equal curing at lower temperature, either way requiring less thermal energy. During the cure, the borax dissolves slowly out of the Fluff carrier, reacts with some lead oxide or basic lead sulfate, and modifies the growth of 4BS. Further, the basic lead sulfate carrier (fluff) is incorporated into the crystalline matrix in the cured paste and is available for electrochemical utilization.
[0063] More specifically, at curing temperatures >70° C., secondary nucleation of 4BS can occur within the paste. Both primary and secondary nucleated 4BS crystals are limited in growth by the modifying additive. At curing temperatures <70° C., the primary nucleated 4BS crystals (that is, grown from seeds) are smaller in size and/or more numerous than would be grown without the microporous BF carrier and the contained growth modifying additive. Accordingly, the curing temperature can be selected to control the amount of 4BS grown, in accordance with the desired use of the battery; as above, SLI batteries generally are preferred to have more 3BS than 4BS, while the converse is true with deep-cycle batteries.
[0064] Laboratory processing tests have shown that less than the calculated 0.5-1 wt % may be effective, in that a residue of borax is found in the sump of the curing chamber after curing a batch of plates containing BF. No similar residue was observed in the plant trials, but may occur during factory production of plates using BF. If so, the amount of BF can be reduced or the residue can be discarded or recycled.
[0065] Those of skill in the art will recognize that batteries are typically “formed”, that is, initially charged, using either a “1-shot” or a “2-shot” formation technique. In 1-shot formation, the unformed battery is filled with a more concentrated aqueous sulfuric acid electrolyte; as the battery undergoes initial (formation) charge, the sulfates from the various basic lead sulfates in the plate increase the electrolyte concentration modestly.
[0066] For example, a filling acid added at a specific gravity of 1.220 to 1.250 is increased to the range 1.270 to 1.300, and the battery is shipped and sold at this concentration. 2-shot formation involves initial use of an electrolyte of very low concentration, 1.005 to perhaps 1.030, which after formation increases to the range 1.050 to 1.180. This acid is dumped out and the battery is refilled with a more concentrated electrolyte solution slightly higher in density than the desired final/shipping specific gravity. For example, a final specific gravity of 1.285 might be achieved by adding acid of specific gravity 1.290 to a residue inside the battery of 1.100. Most SLI batteries are formed using the 1-shot process, while most deep discharge batteries (truck/bus, golf cart, forklift, stationary) are formed by the 2-shot process.
[0067] Any further residual borax (or similar crystal-growth-modifying additive) within the plates will be retained within the cell if the battery had been formed by the 1-shot process, but neither borax, sodium nor any of the other anions will be deleterious to battery performance and life. Such further residue within the plates might be washed out during the acid-dumping step if the battery had been formed by the 2-shot process. The residue can be separated from the dumped acid, allowing its reuse.
[0068] There may be some application for using the growth-modifying additive, for example sodium borate in any of its commercial forms, to deliberately decrease the viscosity of a battery paste which is otherwise difficult to paste, and for which the paste formulation cannot be changed by adding more liquid.
[0069] Table I below summarizes the results of tests performed at four different battery manufacturer's facilities. The notes and column headings explain the test circumstances and conditions. For example, test 1-1 was carried out on Jun. 9, 2010; the grinding was done using a ball mill (BM); the paste mix included 550 kg of oxide, 12.5 kg of PCA, 7 kg of BF, 61 kg of water, and 53.5 kg of sulfuric acid; and an Oxmaster-type mixer was used. The curing conditions were that the plates were stacked, the curing temperature was <50° C., the relative humidity was >95%, and the cure time was 23.55 hours for plates containing PCA and the BF additive. In several cases, control plates were also made, using compositions without BF, and the data as to these is reported as well.
[0070] As indicated, where CCA values were applicable, improvements of typically 12-15% were noted where the BF was added to the paste mix.
[0000]
TABLE 1
SUMMARY OF PLANT TESTS
Paste mix composition: Kg
Company-test no.
Date
Oxide/PCA/BF/H 2 O/acid 1.400 sp.gr.
Mixer type
Recommendation - BP1000/22.7/12-18/104/128.8
Oxmaster
1-1
June 2009
BM 550/12.5/7/61/53.5
Oxmaster
1-2
July 2009
BM 500/12.5/7/61/53.5
Oxmaster
2-1
July 2010
BP1000/15/7/126/119
Oxmaster
3-1
April 2010
BM 550/11.5/8/65/50
Eirich
3-2
July 2010
BM 550/11.5/8/62.5/60.4
Eirich
Curing variables
(C)ure: temp/RH/Time
End of Cure/Dry
Co.-test no
(D)ry: paste H 2 O 5%-8% for >/= 4 hrs
% Pb
% H 2 O
Notes
Recommendation: racked, C > 80°C., >95% RH, </= 48 hrs
<2
<1
1-1
stacked, C < 50° C., >95% RH, 23.55 hrs BF, 39 hrs control
<2
<1
D not specified
1-2
same as 1-1
same as 1-1
2-1
stacked, C 70° C., 100% RH, 14 hrs
2.5
3.0
note 5
D 75° C., 0% RH 20 hrs
not measured
3-1
stacked C < 70° C.
3-2
stacked C/D profile NOTE 6
stacked >2
>2
Racked <2
>2
4-1
stacked C > 80° C., >95% RH, 48 hrs
<2
<1
D > 80° C. unknown decreasing RH
Co.-test no
CCA improvement
Other processing/performance
SEM/porosity/XRD
Recommendation: predicted >10%
Predict: notes 1, 2, 3, 4
>80% 4BS with >80%
Crystals <20 microns
1-1
12%
notes 1, 2, 3, 4
mostly 4BS, some large xtal
1-2
15%
notes 1, 2, 3, 4
BF: very good 3BS, 4BS,
Excellent porosity
Control: poor 3BS, unreacted oxide
Poor porosity
2-1
15%
not yet reported
BF: excellent 4BS < 15 microns
Excellent porosity
C: mostly 3BS, unreacted oxide
Poor porosity
3-1
>12%
not yet reported
BF: <10% large 4BS > 20 microns
Predominantly smaller 4BS
Excellent porosity
C: mostly unreacted oxide,
poor porosity
3-2
not yet reported
not yet reported
BF: not yet examined
C: see test 3-1
4-1
not applicable
Notes 1, 2, 3, 4
BF: small 4BS < 20 microns
Excellent porosity
C: (PCA but no BF) 4BS 10 to 40
microns, excellent porosity
NOTES:
Paste mix composition: oxide preparation BM = ball mill, BP = Barton pot
(1) faster formation: tests 1-1 and 1-2 28 hrs BF vs. 30 hrs control
(2) less gassing on formation
(3) less water loss on formation
(4) mechanically stronger plate: tests 1-1 and 1-2 mechanical drop test, test 4, puncture
(5) unknown procedures for % Pb, % H 2 O, poor equipment and technique, unknown calibration
(6) Profile: 80° C./95% RH/8 hrs but actual 70° C./93% RH/8 hrs, then 80° C./70% RH/2 hrs, then 80° C./50% RH/4 hrs, then 80° C./20% RH/2 hrs, then 80° C./0% RH/4hrs, then 50° C./0% RH/2 hrs, then 40° C./0% RH/2 hrs.
[0071] While several examples of the invention have been provided above, the invention is not to be limited thereto. | A microporous lead-containing solid material is produced, which can serve as a carrier for desired materials into a reaction for various desired purposes. For example, if the microporous solid is impregnated with borax it tends to inhibit the growth of unduly large crystals of tetrabasic lead, which is useful in producing batteries having improved functional qualities. | 2 |
RELATED APPLICATIONS
[0001] This application is a Continuation In Part Application of a prior filed application having Ser. No. 10/853,417 and filing date of May 24, 2004 and entitled: Baseboard Molding with Adaptive and Accommodating Surfaces.
BACKGROUND OF THE INVENTION
INCORPORATION BY REFERENCE
[0002] Applicant(s) hereby incorporate herein by reference, any and all U.S. patents and U.S. patent applications cited or referred to in this application.
FIELD OF THE INVENTION
[0003] This invention relates generally to decorative and utility molding strips especially of the type used in residential and commercial spaces for concealing the margins between floors, walls and ceilings.
DESCRIPTION OF RELATED ART
[0004] The following art defines the present state of this field:
[0005] Roberts et al., U.S. Pat. No. 5,112,548 describes an extrusion method and apparatus for producing a molding strip, which includes a decorative Mylar plastic strip located between a pair of interbonded plastic layers. The top plastic layer or topcoat is clear so that the decorative strip can be seen therethrough. A single die is utilized to produce the molding strip. The plastic layers are both preferably flexible PVC plastic which are interbonded by interfusion between adjacent surfaces while in a molten state within a bonding chamber of the die so that the plastic layers do not separate during use of the molding strip. The topcoat is interbonded with the other plastic layer or body without requiring the clear plastic to totally encapsulate the resulting molding strip. Also, preferably, a re-enforcement wire is embedded in the plastic body within the bonding chamber to give the molding strip additional strength.
[0006] Azzar et al., U.S. Pat. No. 5,157,886 describes an extruded, thermoplastic baseboard elastomeric molding strip having opposed generally flat front and rear surfaces is provided with a plurality of closely vertically, spaced horizontal, parallel ribs projecting outwardly of the flat front surface over the full surface area thereof. The strip is formed of front and rear surface layers of thermoplastic material of the same durometer hardness with the front surface layer forming at least the tips of the front surface ribs being of a low density thermoplastic material and the balance of the strip being of high density thermoplastic material. The front and rear surface layers may be of contrasting colors. The rear surface of the strip is preferably formed with concave grooves separated by a multiplicity of fine, vertically spaced horizontal, parallel rearwardly projecting ribs with a rear, center rib between adjacent fine ribs, of a larger diameter than adjacent fine ribs separating the rear surface grooves. The rear surface configuration facilitates removing of excess wet adhesive and maintenance of flush adhesive mounting of the molding strip to a building vertical wall.
[0007] Irrgang, U.S. Pat. No. 5,219,626 describes a molding strip, particularly for vehicles, with continuous ends formed thereon. The molding strip is a plastic injection molded part and has an integrated reinforcement, which consists of at least one metal strip. The metal strip has a plurality of cut out tongues in rows along one or both lateral edges, and which extend, in whole or in separate regions of the individual tongues, out of the plane of the metal strip. The metal strip can have shaped tongues and unshaped tongues. In a row of tongues which are arranged one behind the other, unshaped tongues alternate with tongues which extend out of the plane of the metal strip at the row of tongues.
[0008] Gross et al., U.S. Pat. No. 5,286,536 describes a decorative molding strip for automobiles and the like, consisting of a polymeric body member having a stabilizing layer imbedded therein. One surface of the strip is mounted on a portion of an auto, for example, such as a bumper or a side panel, and the opposite surface is exposed and subject to impact from an outside source. The layer is made of a woven fabric, preferably of glass fibers, and allows the surface, which has been impacted to recover from indentation, thus preserving the original smooth and unblemished appearance.
[0009] Logan, U.S. Pat. No. 5,398,469 describes a decorative molding for a corner formed by a ceiling and a vertical wall comprising a thin strip of flexible plastic that is secured to the wall by an attachment allowing the molding strip along its upper and lower edges to be flexible to conform with uneven surfaces in the ceiling and/or wall. In one form the strip is attached to the wall by an adhesive. In another form, a wall track and clip arrangement is utilized to provide easy removal from the wall for paint or wallpaper application. A corner element is provided in one form in which ends of the strips are adhesively secured thereto in overlapping engagement. In another embodiment, the strips are telescopically connected to the corner element.
[0010] Logan et al., U.S. Pat. No. 5,457,923 describes a decorative molding for a corner formed by a ceiling and a vertical wall comprising a thin strip of flexible plastic that is secured to the wall by an attachment allowing the molding strip along its upper and lower edges to be flexible to conform with uneven surfaces in the ceiling and/or wall. In one form the strip is attached to the wall by an adhesive. In another form, a wall track and clip arrangement is utilized to provide easy removal from the wall for paint or wallpaper application. A corner element is provided in one form in which ends of the strips are adhesively secured thereto in overlapping engagement. In another embodiment, the strips are telescopically connected to the corner element.
[0011] Gilmore et al., U.S. Pat. No. 5,525,384 describes a flexible ornamental or protective plastic molding strip having an inserted flexible decorative cord. The flexible molding strip, which serves as a base strip has an exposed outer surface that is usually smoothly contoured but can, if desired, be provided with longitudinally extending depressed or projecting surface decoration. In the exposed surface are one or more longitudinally extending grooves. Into each groove is inserted a flexible decorative cord, preferably of a color selected to provide an appealing visual effect, usually a color which contrasts with the color of the base strip itself. The decorative cord can be easily inserted into the groove by pressing it into place either at the factory or at the job site, to harmonize with the decor. The cord can be removed and replaced at any time desired, yet will be held securely in the groove by its contact with the walls of the groove during normal use.
[0012] Gilmore, et al., U.S. Pat. No. 5,688,569 describes a flexible ornamental or protective plastic molding strip having an inserted flexible decorative cord. The flexible molding strip, which serves as a base strip has an exposed outer surface that is usually smoothly contoured but can, if desired, be provided with longitudinally extending depressed or projecting surface decoration. In the exposed surface are one or more longitudinally extending grooves. Into each groove is inserted a flexible decorative cord, preferably of a color selected to provide an appealing visual effect, usually a color which contrasts with the color of the base strip itself. The decorative cord can be easily inserted into the groove by pressing it into place either at the factory or at the job site, to harmonize with the decor. The cord can be removed and replaced at any time desired, yet will be held securely in the groove by its contact with the walls of the groove during normal use.
[0013] Pallas et al., U.S. Pat. No. 6,604,331 describes an area between a wall and a floor of a building that can be covered by a baseboard-molding unit. The baseboard molding unit includes a wall-mounted track section that can be fixed to a wall by fasteners and which includes a dovetail joint element and a baseboard element that has a dovetail groove defined therein that is slidably, yet securely held on the dovetail joint element. Corner pieces are used for inside and for outside corners.
[0014] Our prior art search with abstracts described above teaches: an extrusion method and apparatus for producing a molding strip, an extruded elastomeric baseboard molding strip, a molding strip, particularly for vehicles, an indention-recoverable molding strip, several decorative molding strips, a flexible molding strip having inserted decorative cord and furniture provided with such strips, and a baseboard molding strip unit. The prior art teaches that molding strips may have plural horizontal recesses in a rear surface for improved adhesive flow and removal, and that such strips may have curved decorative front surfaces, and that such strips may have an integrated stiffener strip, and that the rear surface may be formed to accommodate a mounting strip, and that such strips may be made of thin material with plural separate parts cooperating especially where an inner portion supports and provides rigidity to an outer portion covering the inner portion, and that such strips may have front surface grooves for mounting decorative strips, and that a baseboard molding may have a dovetail slot on a rear surface for intimate engagement with a dovetail supporting and mounting strip engaged with a wall surface. The present invention, in contrast, fulfills these needs and provides further related advantages as described in the following summary.
SUMMARY OF THE INVENTION
[0015] The present invention teaches certain benefits in construction and use which give rise to the objectives described below.
[0016] In a best mode preferred embodiment of the present invention, a molding strip having a front face and a spaced apart rear face, the front and rear faces extend between parallel top and bottom edges. The front face is formed into a decorative curvature with a frontal groove running horizontally. An insert filler is adapted for press-fitting into the frontal groove. The bottom edge is indented from the front face such that with the body oriented uprightly, and in contact with a floor surface, a frontal space is formed between the floor surface and the front face. The rear surface comprises a plurality of parallel grooves separated by at least two parallel contact edges. A cutaway surface extends from the bottom surface to a medial position on the rear face, the cutaway surface sized for receiving a smaller, prior mounted, molding strip. A caulking relief is formed between the top edge of the molding and the rear surface. The molding strip can cover an existing molding strip to provide improvements to an existing construction without stripping existing moldings.
[0017] A primary objective of one embodiment of the present invention is to provide an apparatus and method of use of such apparatus that yields advantages not taught by the prior art.
[0018] Another objective is to assure that an embodiment of the invention is capable of covering a prior mounted molding.
[0019] A further objective is to assure that an embodiment of the invention is capable of being painted without masking a floor surface and without getting paint on the floor surface.
[0020] A still further objective is to assure that an embodiment of the invention is capable of receiving a decorative filler strip without the need to bond or fasten the strip while still achieving a secure mounting.
[0021] A still further objective is to assure that an embodiment of the invention is capable of being mounted to a wall surface with protruding imperfections without difficulty and yet capable too of being supported by a generous amount of adhesive bonding material.
[0022] A still further objective is to assure that an embodiment of the invention is capable of receiving a caulking compound along the visually critical edge in such manner that gaps do not show and wherein excessive caulk does not drip across the front face of the molding.
[0023] Other features and advantages of the embodiments of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of at least one of the possible embodiments of the invention.
[0000] BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The accompanying drawings illustrate at least one of the best mode embodiments of the present invention. In such drawings:
[0025] FIGS. 1-4 are perspective views of embodiments of the invention an elongate baseboard molding strip, wherein in each view only a short portion of such a strip is depicted and particularly showing a cross section in each view; and
[0026] FIG. 5 is an exploded perspective view of the embodiment of FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
[0027] The above described drawing figures illustrate the present invention in at least one of its preferred, best mode embodiments, which is further defined in detail in the following description. Those having ordinary skill in the art may be able to make alterations and modifications in the present invention without departing from its spirit and scope. Therefore, it must be understood that the illustrated embodiments have been set forth only for the purposes of example and that they should not be taken as limiting the invention as defined in the following.
[0028] In one aspect of a best mode embodiment of the present invention, a baseboard molding strip apparatus 10 (“strip”) distinguishes over the prior art in several ways. Such a strip 10 is normally made of wood or of extruded plastic, but may also be made of other common and inexpensive materials by milling, molding and other well known processes. The molding strip 10 is mounted to a building vertical wall surface 20 , with a bottom edge 30 ′ of the strip 10 in contact with a building horizontal floor surface 40 . Such moldings are very common and are used to provide a finished look to a building interior. The strip 10 has a front decorative surface 12 and an opposite rear, wall contacting surface 30 as is well known. Such strips 10 are mounted to walls by nailing or gluing or both. In improving over the prior art, the bottom edge 30 ′ of the present inventive strip 10 is indented to form a horizontal frontal space 50 between the strip 10 and the floor surface 40 as shown in FIGS. 1 and 5 . The advantage and reason for this indentation will be explained in due course.
[0029] A frontal horizontal slot 16 in the front decorative surface 12 has top 16 ′ and bottom 16 ″ slot edges. These edges 16 ′, 16 ″ diverge inwardly to better engaged a decorative insert filler strip 70 that may be used to provide a customized appearance to the strip 10 . The rear, wall contacting surface 30 comprises a plurality of horizontal, vertically spaced contact edges 14 ′ all of which align along a plane so as to commonly contact the wall surface 20 . These edges 14 ′ are interspersed by a plurality of horizontal, vertically spaced concave grooves 14 ″ for retaining an adhesive (not shown) used for mounting the strip 10 . Such grooves 14 ″ enable the surface 30 to avoid difficulties with minor wall protrusions such as pimples and also to hold a greater amount of adhesive for an improved engagement with the wall to which it is attached.
[0030] Preferably, the strip 10 has a cutaway surface 18 extending from the bottom edge 30 ′, upwardly to a medial position 60 on the rear surface 30 , such that with the rear, wall contacting edges 14 ′ abutting the building vertical wall surface 20 , and with the bottom edge 30 ′ abutting the building horizontal floor surface 40 , a lesser sized, existing molding strip 5 mounted to the building vertical wall surface 20 , is concealed within the cutaway surface 18 . This provides the great advantage of being able to install the strip 10 without removing prior mounted molding of a smaller size.
[0031] Preferably, the present invention further comprises the insert filler 70 which is adapted with divergent filler side edges 72 and 74 for positive engagement within the frontal horizontal slot 16 . This is accomplished by tapering the filler side edges 72 and 74 to correspond with edges 16 ′ and 16 ″. Such diverging edges are preferably at an angle of between 1 and 3 degrees so as to assure a positive lock of the filler 70 within the slot 16 while still enabling engagement by simply pushing the filler 70 into the slot 16 where it snaps into place and is held without adhesive or nails, etc.
[0032] The indented bottom edge 30 ′ of the strip 10 provides the advantage, when installing the strip 10 , of providing a solid footing to the strip 10 , while enabling the strip 10 to be finished by staining, painting, or other surface finishing, without such finishing material inadvertently coming into contact with the building horizontal floor surface 40 . Thus, a painter's barrier (not shown) such as a piece of cardboard or similar flat and stiff sheet stock material, may be held under the strip 10 during painting, etc. to assure that the floor surface 40 is not contacted. Such a barrier is moved along the strip 10 as finishing proceeds. This avoids the time and expense of using masking tape, which, of course, must be carefully placed and thereafter removed.
[0033] FIG. 1 shows an embodiment of the invention with filler 70 , with indent space 50 and with parallel grooves 14 ″. FIG. 2 shows a similar strip 10 having also cutout 18 . FIG. 3 shows a similar strip 10 with an alternate filler 70 showing that such a filler 70 may be made in various sizes and with varying decorative features. FIG. 4 shows the strip 10 of FIG. 3 with the cutout 18 showing that the cutout 18 may be included or not.
[0034] FIG. 4 shows a top edge 15 in positional opposition to the bottom edge 30 ′, the top edge 15 extending from the front decorative surface 12 to a relief 15 ′ formed between the top edge 15 and the wall contacting surface 30 . This relief 15 ′ receives a caulking compound (not shown) as part of the molding mounting and securing procedure. The relief 15 ′ is preferably a simple chamfer, i.e., an angled planar surface, but may also be a concave surface.
[0035] The enablements described in detail above are considered novel over the prior art of record and are considered critical to the operation of at least one embodiment of the instant invention and to the achievement of the above described objectives. The words used in this specification to describe the instant embodiments are to be understood not only in the sense of their commonly defined meanings, but to include by special definition in this specification: structure, material or acts beyond the scope of the commonly defined meanings. Thus if an element can be understood in the context of this specification as including more than one meaning, then its use must be understood as being generic to all possible meanings supported by the specification and by the word or words describing the element.
[0036] The definitions of the words or elements of the embodiments of the herein described invention and its related embodiments not described are, therefore, defined in this specification to include not only the combination of elements which are literally set forth, but all equivalent structure, material or acts for performing substantially the same function in substantially the same way to obtain substantially the same result. In this sense it is therefore contemplated that an equivalent substitution of two or more elements may be made for any one of the elements in the invention and its various embodiments or that a single element may be substituted for two or more elements in a claim.
[0037] Changes from the claimed subject matter as viewed by a person with ordinary skill in the art, now known or later devised, are expressly contemplated as being equivalents within the scope of the invention and its various embodiments. Therefore, obvious substitutions now or later known to one with ordinary skill in the art are defined to be within the scope of the defined elements. The invention and its various embodiments are thus to be understood to include what is specifically illustrated and described above, what is conceptually equivalent, what can be obviously substituted, and also what essentially incorporates the essential idea of the invention.
[0038] While the invention has been described with reference to at least one preferred embodiment, it is to be clearly understood by those skilled in the art that the invention is not limited thereto. Rather, the scope of the invention is to be interpreted only in conjunction with the appended claims and it is made clear, here, that the inventor(s) believe that the claimed subject matter is the invention. | A molding strip has a front surface and a spaced apart rear surface, the front and rear surfaces extending between parallel top and bottom edges. The front surface is decorative with a horizontal groove for accepting a decorative filler strip. The bottom surface is indented from the front surface to form a space between the molding strip and the floor below it. The rear surface comprises a plurality of parallel grooves separated by horizontal contact edges. A cutaway surface extends from the bottom edge to a medial position on the rear surface for concealing a lesser sized molding strip. | 4 |
BRIEF SUMMARY OF THE INVENTION
This invention relates to new organic compounds and, more particularly, is concerned with novel N'-[2,6-dichloro-4-(substituted-benzylamino)phenyl]-N,N-dimethylformamidines which may be represented by the following structural formula: ##STR1## wherein R 1 and R 2 are each individually selected from the group consisting of hydrogen, fluoro, chloro, bromo, methyl, methoxy and trifluoromethyl; R 4 and R 5 are each individually selected from the group consisting of hydrogen, chloro and methoxy; R 3 is selected from the group consisting of hydrogen, methoxy, phenyl, dimethylamino and diethylamino; and R 2 and R 3 taken together is methylenedioxy with the proviso that at least two of R 1 , R 2 , R 3 , R 4 and R 5 are hydrogen. A preferred embodiment of the present invention may be represented by the above structural formula wherein R 1 , R 2 , R 3 and R 4 are as hereinbefore defined and R 5 is hydrogen with the proviso that at least one of R 1 , R 2 , R 3 and R 4 is also hydrogen.
The organic bases of this invention form non-toxic acid-addition salts with a variety of pharmacologically acceptable organic and inorganic salt-forming reagents. Thus, acid-addition salts, formed by a mixture of the organic free base with one or more equivalents of an acid, suitably in a neutral solvent, are formed with such acids as sulfuric, phosphoric, hydrochloric, hydrobromic, sulfamic, citric, lactic, malic, succinic, tartaric, acetic, benzoic, gluconic, ascorbic, and the like. For purposes of this invention the free bases are equivalent to their non-toxic acid-addition salts. The acid-addition salts of the organic bases of the present invention are, in general, crystalline solids, relatively soluble in water, methanol and ethanol but relatively insoluble in non-polar organic solvents such as diethyl ether, benzene, toluene, and the like.
DETAILED DESCRIPTION OF THE INVENTION
The novel compounds of the present invention may be readily prepared as set forth in the following reaction scheme: ##STR2## wherein R 1 , R 2 , R 3 , R 4 and R 5 are as hereinabove defined. In accordance with the above reaction scheme, 2,6-dichloro-p-phenylenediamine (1) is reacted with a benzaldehyde of the general structure (2) to yield the intermediate 2,6-dichloro-N 4 -benzylidene-p-phenylenediamine compounds (3).
Thus, when 2,6-dichloro-1,4-phenylenediamine and a benzaldehyde of the general structure (2) are dissolved in a solvent such as ethanol or tetrahydrofuran and heated at the reflux temperature for one to 18 hours, with or without the removal of water, compounds of the general structure (3) are obtained. These products may be purified by crystallization from solvents such as ethanol or combinations of solvents such as ethanol and n-hexane.
When the compounds of general structure (3) are dissolved in a solvent such as ethanol or tetrahydrofuran and the solution is hydrogenated in the presence of a noble metal catalyst, preferably finely divided metallic palladium or other metals of the platinum family, the compounds of general structure (4) are obtained. The pure metal may be used or the catalyst may be supported on one of the common carriers such as finely divided alumina, activated charcoal, diatomaceous earth and the like. The hydrogenation may be carried out at temperatures ranging between 0°-50° C. and preferably at room temperature (i.e. 25° C.) and at a hydrogen pressure of about one atmosphere. Or, if compounds of the general structure (3) are dissolved in a solvent such as ethanol or tetrahydrofuran (preferably ethanol) and then treated with a reducing agent such as sodium borohydride, lithium borohydride or, preferably, sodium cyanoborohydride at 0°-50° C. (preferably 25° C.) for 10 minutes to 20 hours (preferably 4 hours) with the pH of the reaction maintained between 4 and 10, compounds of general structure (4) are obtained. When the compounds of general structure (4) are treated with a formamidine forming reagent such as N,N-dimethylformamide dimethylacetal neat, or in an inert solvent, by heating (usually at the reflux temperature) for 4-20 hours, the final products (5) are obtained. After evaporation of the solvents, the products (5) can be purified by crystallization from solvents such as ethanol, or a combination of solvents such as n-hexane and ethanol.
Alternatively, the novel compounds of the present invention may be prepared as set forth in the following reaction scheme: ##STR3## wherein R 1 , R 2 , R 3 , R 4 and R 5 are as hereinbefore defined. In accordance with the above reaction scheme, N'-(2,6-dichloro-4-aminophenyl)-N,N-dimethylformamidine (6) is dissolved in a solvent such as ethanol and treated at ambient temperature or at the reflux temperature for one to 18 hours, with or without the removal of water, with a benzaldehyde of the general structure (2) to yield the intermediate formamidine compounds (7). These intermediates may be purified by crystallization from common solvents such as ethanol or combinations of solvents such as ethanol and n-hexanes. Alternatively, the compounds (7) may be prepared from compounds of the general structure (3) with formamidine forming reagents such as N,N-dimethylformamide dimethylacetal as previously described.
When the intermediate compounds (7) are dissolved in a solvent such as ethanol or tetrahydrofuran and hydrogenated as previously described the novel compounds of formula (5) are obtained.
The novel compounds of the present invention are physiologically active and, therefore, useful in the pharmaceutical field. In particular, these compounds are useful as either diuretic and/or hypotensive agents.
The novel compounds of the present invention are potent diuretics, producing significant water diuresis and sodium (Na + ) loss, but with minimal loss of potassium (K + ), as determined in the following procedure.
One to three spontaneously hypertensive rats are dosed by gavage with a test compound at one to 100 mg./kg. of body weight and loaded with 0.9% sodium chloride at 25 ml./kg. of body weight at zero hour. The 0-5 hour urine is collected, its volume measured, and Na + and K + concentrations determined. The following compounds have been found to possess significant diuretic activity when tested as described above:
N'-(4-Amino-2,6-dichlorophenyl)-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(3,4,5-trimethoxybenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(2-chloro-4-dimethylaminobenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(m-fluorobenzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
N'-[2,6-Dichloro-4-(m-(trifluoromethyl)benzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
N'-[4-(m-Bromobenzylamino)-2,6-dichlorophenyl]-N,N-diylformamidine hydrochloride
N'-[2,6-Dichloro-4-(3,5-dichlorobenzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
N'-[2,6-Dichloro-4-(4-dimethylamino-2-methoxybenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(p-diethylaminobenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(4-dimethylamino-2-methylbenzylamino]phenyl)-N,N-dimethylformamidine
N'-[4-(2-Bromo-4-dimethylaminobenzylamino)-2,6-dichlorophenyl]-N,N-dimethylformamidine
N'-[4-(3-Bromo-4-dimethylaminobenzylamino)-2,6-dichlorophenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(4-dimethylamino-2-fluorobenzylamino)phenyl]-N,N-dimethylformamidine
The novel compounds of the present invention also possess anti-hypertensive activity at non-toxic doses and as such are useful as hypotensive agents. The hypotensive properties of the compounds of the present invention have been shown when orally administered to mammals, specifically warm-blooded animals as described below.
The novel compounds of the present invention were tested for anti-hypertensive activity in a procedure using spontaneously hypertensive rats (SHR) as follows: One male adult SHR (16-20 weeks old) weighing about 300 grams (Taconic Farms, Germantown, N.Y.) is dosed by gavage with the test compound at one to 100 mg./kg. with 0.9% sodium chloride loading at 25 ml./kg. at zero hour. A second identical dose is given at 24 hours without saline loading and the mean arterial blood pressure (MABP) of the conscious rat is measured directly by femoral artery puncture at 28 hours. A 2nd or 3rd SH rat may be needed depending on the results of the 1st rat [Chan, et al., Pharmacologist, 17, 253 (1975)]. The following representative compounds of the present invention have been shown to possess anti-hypertensive activity when tested as described above.
N'-(4-Amino-2,6-dichlorophenyl)-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(3,5-dimethoxybenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(3,4,5-trimethoxybenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(2-chloro-4-dimethylaminobenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(3-fluoro-4-methoxybenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(m-fluorobenzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
N'-[2,6-Dichloro-4-(p-phenylbenzylamino)phenyl]-N,N-dimethylformamidine
N'-[4-(m-Bromobenzylamino)-2,6-dichlorophenyl]-N,N-diylformamidine hydrochloride
N'-[2,6-Dichloro-4-(3,5-dichlorobenzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
N'-[2,6-Dichloro-4-(4-dimethylamino-2-methoxybenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(p-diethylaminobenzylamino)phenyl]-N,N-dimethylformamidine
N'-[2,6-Dichloro-4-(4-dimethylamino-2-methylbenzylamino)phenyl]-N,N-dimethylformamidine
N'-[4-(2-Bromo-4-dimethylaminobenzylamino)-2,6-dichlorophenyl]-N,N-dimethylformamidine
The novel compounds of the present invention have thus been shown to be valuable diuretic agents of low toxicity when administered orally. The amount of a single dose or of a daily dose will vary but should be such as to give a proportionate dosage of from about one mg. to about 1000 mg. per day for a subject of about 70 kg. body weight. The dosage regimen may be adjusted to provide the optimum therapeutic response, for example, doses of 25-250 mg. may be administered on a four times per day regimen, or the dose may be proportionately increased as indicated by the exigencies of the therapeutic situation.
The novel compounds of the present invention have also been found to be highly useful for lowering elevated blood pressure in mammals when administered in amounts ranging from about 0.4 mg. to about 10.0 mg. per kg. of body weight per day. A preferred dosage regimen for optimum results would be from about 7.0 mg. to about 175 mg. per dose. Such dosage units are employed that a total of from about 28 mg. to about 700 mg. of active compound for a subject of about 70 kg. of body weight are administered in a 24 hour period. The dosage regimen may be adjusted to provide the optimum therapeutic response. For example, several divided doses may be administered daily or the dose may be proportionally reduced as indicated by the exigencies of the therapeutic situation. The compounds of this invention are preferably administered orally but may be administered in any convenient manner such as the intravenous route.
The compounds of the present invention may be administered as active components of compositions in unit dosage form such as tablets, pills, capsules, powders, granules, oral or parenteral solutions or suspensions and the like. For preparing solid compositions such as tablets, the active compound is mixed with conventional tableting ingredients such as starch, lactose, sucrose, sorbitol, talc, stearic acid, magnesium stearate, dicalcium phosphate, gums and functionally similar materials as pharmaceutical diluents or carriers. The tablets or pills can be laminated or otherwise compounded to provide a dosage form affording the advantage of prolonged or delayed action, or predetermined successive action of the enclosed medication. For example, the tablet or pill can comprise an inner dosage and an outer dosage component, the latter being in the form of an envelope over the former. The two components can be separated by an enteric layer which serves to resist disintegration in the stomach and permits the inner component to pass intact into the duodenum or to be delayed in release. A variety of materials can be used for such enteric layers or coatings, such materials including a number of polymeric acids or mixtures of polymeric acids with such materials as shellac, shellac and cetyl alcohol, cellulose acetate, and the like. A particularly advantageous enteric coating comprises a styrene maleic acid copolyment together with known materials contributing to the enteric properties of the coating.
Compositions according to the present invention having the desired clarity, stability and adaptability for parenteral use are obtained by dissolving from 0.01% to 10.0% by weight of active compound in a vehicle consisting of a polyhydric aliphatic alcohol or mixtures thereof. Especially satisfactory are glycerin, propylene glycol, and polyethylene glycols. The polyethylene glycols consist of a mixture of non-volatile, normally liquid, polyethylene glycols which are soluble in both water and organic liquids and which have molecular weights of from about 200 to 1500. Although the amount of active compound dissolved in the above vehicle may vary from 0.10% to 10.0% by weight, it is preferred that the amount of active compound employed be from about 3.0% to about 9.0% by weight. Although various mixtures of the aforementioned non-volatile polyethylene glycols may be employed, it is preferred to use a mixture having an average molecular weight of from about 200 to about 400.
In addition to the active compound, the parenteral solutions may also contain various preservatives which may be used to prevent bacterial and fungal contamination. The preservatives which may be used for these purposes, are for example, myristyl-gamma-picolinium chloride, benzalkonium chloride, phenethyl alcohol, p-chlorphenyl-α-glycerol ether, methyl and propyl parabens, and thimerosal. As a practical matter, it is also convenient to employ antioxidants. Suitable antioxidants include, for example, sodium bisulfite, sodium metabisulfite, and sodium formaldehyde sulfoxylate. Generally, from about 0.05% to about 0.2% concentrations of antioxidant are employed.
The novel compounds of the present invention are adapted to intravenous administration when diluted with water or diluents employed in intravenous therapy such as isotonic glucose in appropriate quantities. For intravenous use, initial concentrations down to about 0.05 to 0.25 mg./ml. of active ingredient are satisfactory.
The liquid forms in which the compounds of the present invention may be incorporated for administration include aqueous solutions, suitably flavored syrups, aqueous or oil suspensions, flavored emulsions with edible oils such as cottonseed oil, sesame oil, coconut oil, peanut oil, and the like, as well as elixirs and similar pharmaceutical vehicles. Suitable dispersing or suspending agents for aqueous suspensions include synthetic and natural gums such as tragacanth, acacia, alginic acid, dextran, sodium carboxymethylcellulose, methylcellulose, polyvinylpyrrolidone, gelatin and the like.
The term unit dosage form refers to physically discrete units suitable as unitary dosages, each unit containing a predetermined quantity of active material calculated to produce the desired therapeutic effect in association with the required pharmaceutical diluent, carrier or vehicle. The specifications for the unit dosage forms of this invention are dictated by and are directly dependent on (a) the unique characteristic of the active material and the particular therapeutic effect to be achieved, and (b) the limitations inherent in the art of compounding such an active material for therapeutic use, as disclosed in detail in this specification, these being features of the present invention.
The invention will be described in greater detail in conjunction with the following specific examples.
EXAMPLE 1
N'-(4-Amino-2,6-dichlorophenyl)-N,N-dimethylformamidine
A mixture of 20.7 g. of 2,6-dichloro-p-nitroaniline and 15 ml. of N,N-dimethylformamide dimethylacetal in 125 ml. of dimethylformamide is heated on a steam bath for 4 hours. The reaction mixture is cooled at -10° C. and the precipitate is collected by filtration. The product is washed with isopropyl alcohol and dried to give 21.5 g. of N'-(2,6-dichloro-4-nitrophenyl)-N,N-dimethylformamidine, m.p. 164°-166° C.
A 540 g. amount of stannous chloride is dissolved in 450 ml. of concentrated hydrochloric acid with stirring. The solution is cooled to 10° C. in an ice bath and 155 g. of N'-(2,6-dichloro-4-nitrophenyl)-N,N-dimethylformamidine (prepared as described above) is added portionwise, with stirring, at a rate to maintain the reaction temperature at 75° C. The reaction mixture is allowed to stand at room temperature for 18 hours, then is filtered. The filter cake is suspended in 200 ml. of ice water and concentrated sodium hydroxide is added until the reaction mixture is alkaline. The reaction mixture is filtered and the insolubles are collected and extracted with chloroform. The chloroform extracts are evaporated in vacuo to yield 102 g. of the product of the Example as pale yellow crystals, m.p. 121°-126° C.
EXAMPLE 2
N'-[2,6-Dichloro-4-(3,5-dimethoxybenzylamino)phenyl]-N,N-dimethylformamidine
A mixture of 5.3 g. of 2,6-dichloro-p-phenylenediamine and 4.98 g. of 3,5-dimethoxybenzaldehyde in 100 ml. of ethanol is heated on a steam bath, solution occurs, followed by crystallization. Warming is continued on the steam bath for 16 hours. The reaction mixture is cooled, 50 ml. of glacial acetic acid and 500 mg. of platinum oxide are added and the mixture is hydrogenated in a Parr apparatus at 40 p.s.i. for 15 minutes. The mixture is filtered and washed with ethanol, then the combined filtrate and washings are evaporated to dryness. The residue is treated with 200 ml. of saturated sodium carbonate then is extracted twice with 200 ml. of ethyl acetate. The combined extract is evaporated to dryness. The residue is dissolved in methanol and the solution is cooled at 5° C. to provide crystals. The crystals are collected by filtration and washed with methanol to give 7.8 g. of product. This product is heated at reflux with 20 ml. of N,N-dimethylformamide dimethylacetal for 18 hours. The resulting solution is evaporated to an amber syrup. The syrup is treated with ether/hexane to crystallize 7.1 g. of the product of the Example as colorless needles, m.p. 124°-125° C.
EXAMPLE 3
N'-[2,6-Dichloro-4-(3,4,5-trimethoxybenzylamino)-phenyl]-N,N-dimethylformamidine
A mixture of 5.3 g. of 2,6-dichloro-p-phenylenediamine in 50 ml. of warm ethanol and 5.9 g. of 3,4,5-trimethoxybenzaldehyde in 50 ml. of warm ethanol is stirred for 2 hours, then filtered. The filter cake, dissolved in 50 ml. of tetrahydrofuran containing 500 mg. of platinum oxide, is hydrogenated in a Parr apparatus at 47 p.s.i. until no more hydrogen is absorbed. The reaction mixture is filtered and washed with ethanol. The filtrate is evaporated to a syrup which is dissolved in 25 ml. of methanol. The product is crystallized, collected by filtration and washed with cold methanol to give 7.0 g. of 2,6-dichloro-N 4 -(3,4,5-trimethoxybenzyl)-p-phenylenediamine as yellow crystals, m.p. 96°-97° C.
A 5.0 g. amount of the preceding compound and 20 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 18 hours. The reaction mixture is evaporated to give an amber syrup. The syrup is dissolved in 50 ml. of methanol and water is added until turbid. The mixture is chilled at 5° C. to provide crystals. The crystals are collected and washed with chilled 50% methanol/water to yield 5.84 g. of the product of the Example, m.p. 137°-138.5° C.
EXAMPLE 4
N'-[2,6-Dichloro-4-(2-chloro-4-dimethylaminobenzyl-amino)phenyl]-N,N-dimethylformamidine
A mixture of 18.3 g. of 2-chloro-4-dimethylaminobenzaldehyde and 17.7 g. of 2,6-dichlorophenylenediamine in 200 ml. of ethanol is refluxed for 18 hours. The reaction mixture is evaporated to dryness. The residue is crystallized from a mixture of ethanol and water. The product is collected by filtration and washed with ethanol/water, then dried to give 3.7 g. of 2,6-dichloro-N 4 -(2-chloro-4-dimethylaminobenzylidene)-p-phenylenediamine as mustard colored crystals, m.p. 139°-140° C.
An 8.0 g. amount of the preceding compound (prepared as described above) is dissolved in 200 ml. of tetrahydrofuran with stirring, then several grams of lithium borohydride are added over a one hour period and the mixture is allowed to stand at room temperature for 16 hours. The mixture is evaporated to an oil, water and chloroform are added and the layers are separated after decomposition of the excess hydride is complete. The chloroform layer is dried over magnesium sulfate, filtered and evaporated in vacuo to give a syrup which is crystallized from a mixture of ethyl ether and n-hexane. The crystals are collected by filtration and washed with n-hexane to give 6.5 g. of 2,6-dichloro-N 4 -(2-chloro-4-dimethylaminobenzyl)-p-phenylenediamine as yellow crystals, m.p. 91°-94° C.
A 4.0 g. amount of the above compound in 25 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 18 hours. The reaction mixture solvent is evaporated to give a crystalline residue. The residue is dissolved in 125 ml. of boiling ethanol then is allowed to stand at 5° C. The crystallized material is collected by filtration and washed with ethanol to yield 2.5 g. of the product of the Example as yellow crystals, m.p. 177°-178° C.
EXAMPLE 5
N'-[2,6-Dichloro-4-(3-fluoro-4-methoxybenzylamino)phenyl]-N,N-dimethylformamidine
A 7.0 g. amount of N'-(4-amino-2,6-dichlorophenyl)-N,N-dimethylformamidine (Example 1) and 4.6 g. of 3-fluoro-p-anisaldehyde are each dissolved separately in 25 ml. of warm methanol and then combined. The mixture is cooled at 5° C. The crystallized product is collected and washed with ether to provide 8.2 g. of N'-[2,6-dichloro-4-[(3-fluoro-4-methoxybenzylidene)amino]phenyl]-N,N-dimethylformamidine as yellow crystals, m.p. 139°-141° C.
A 4.0 g. amount of N'-[2,6-dichloro-4-[(3-fluoro-4-methoxybenzylidene)amino]phenyl]-N,N-dimethylformamidine is dissolved in 100 ml. of warm tetrahydrofuran, then 500 mg. of platinum oxide that has been wetted with water is added and the mixture is hydrogenated in a Parr apparatus for 15 minutes. The reaction mixture is filtered and washed with tetrahydrofuran. The clear yellow solution is evaporated in vacuo to crystallize a solid. The solid is recrystallized from ethanol, filtered and washed with a small amount of ether to provide 2.0 g. of the desired product as granular yellow crystals, m.p. 138°-140° C.
EXAMPLE 6
N'-[2,6-Dichloro-4-(m-fluorobenzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
A 10.6 g. amount of 2,6-dichloro-p-phenylenediamine and 7.4 g. of m-fluorobenzaldehyde are dissolved in 100 ml. of absolute ethanol. The solution is refluxed for 5 hours then cooled in an ice bath at 5° C. for 18 hours. The mixture is filtered and the precipitate is washed with ether to give 11.8 g. of 2,6-dichloro-N 4 -m-fluorobenzylidene-p-phenylenediamine as grey crystals, m.p. 102°-103° C.
The above filtrate and washings are combined and evaporated to provide additional crystalline product. This material is dissolved in 100 ml. of anhydrous tetrahydrofuran, then over a one hour period there is added 1-2 g. of lithium borohydride with stirring. Stirring is continued for 18 hours then the solution is evaporated to dryness and 100 ml. of chloroform and 50 ml. of water is added to the residue. The mixture is stirred for one hour and the layers are separated. The chloroform layer is dried over magnesium sulfate and the solvent is evaporated to yield 1.0 g. of 2,6-dichloro-N 4 -m-fluorobenzyl-p-phenylenediamine as bright yellow crystals, m.p. 60°-61° C.
The entire 1.0 g. amount of the preceding product and 15 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 18 hours. The reaction mixture is evaporated to a pale yellow syrup, the syrup is redissolved in 3 ml. of ethanol, then ether is added followed by 3 ml. of 3.6 N ethanolic hydrochloric acid. The solvents are evaporated and the residue is recrystallized from ethanol to give 1.0 g. of the product of the Example as colorless granular crystals, m.p. 239°-241° C. (dec.).
Alternatively, the preparation of the title compound can be achieved by the reaction of the above 2,6-dichloro-N 4 -m-fluorobenzylidene-p-phenylenediamine with excess dimethylformamide dimethylacetal at the reflux point for 18 hours, removal of excess reagent to yield the crude N'-[2,6-dichloro-4-(m-fluorobenzylideneamino)phenyl]-N,N-dimethylformamidine as a yellow solid, and reduction with lithium borohydride in tetrahydrofuran solution.
EXAMPLE 7
N'-[2,6-Dichloro-4-[m-(trifluoromethyl)benzylamino]phenyl]-N,N-dimethylformamidine hydrochloride
A mixture of 8.9 g. of 2,6-dichloro-p-phenylenediamine and 8.7 g. of m-trifluoromethylbenzaldehyde in 50 ml. of absolute ethanol is refluxed for 5 hours. The solvent is evaporated, then ethanol is added to the solid cake followed by n-hexane. The mixture is filtered and the precipitate is washed with n-hexane until the wash is clear to give 11.5 g. of 2,6-dichloro-N 4 -α,α,α-trifluoro-m-benzylidene-p-phenylenediamine as tan needles, m.p. 124°-125° C.
A mixture of 10.0 g. of the preceding compound and 500 mg. of 10% palladium-on-carbon catalyst in 100 ml. of tetrahydrofuran is hydrogenated in a Parr shaker at room temperature for 3 hours with a pressure drop from 48 p.s.i. to 22 p.s.i. The mixture is filtered and washed with tetrahydrofuran. The dark filtrate is evaporated to a syrup. The syrup is dissolved in ethanol then n-hexane is added until turbid. The mixture is cooled and 20 ml. of 4.1 N ethanolic hydrochloric acid is added. The crude product is recrystallized from ethanol to give 5.3 g. of 2,6-dichloro-N 4 -[m-(trifluoromethyl)benzyl]-p-phenylenediamine hydrochloride as colorless crystals, m.p. >210° C. (dec.).
A mixture of 5.0 g. of the above product and 25 ml. of N sodium hydroxide is extracted with 100 ml. of chloroform and 50 ml. of methylene chloride. The extracts are dried over magnesium sulfate and evaporated in vacuo to give a syrup, then 25 ml. of N,N-dimethylformamide dimethylacetal is added and the mixture is refluxed for 18 hours. The reaction solution is evaporated to a clear yellow syrup. The syrup is dissolved in 10 ml. of ethanol and n-hexane is added until turbid, then 15 ml. of 4.1 N ethanolic hydrochloric acid is added, the product collected, to provide 5.6 g. of the product of the Example as pink crystals, m.p. 214°-217° C. (dec.).
EXAMPLE 8
N'-[2,6-Dichloro-4-(p-phenylbenzylamino)phenyl]-N,N-dimethylformamidine
A 17.7 g. amount of 2,6-dichloro-1,4-phenylenediamine is dissolved in 50 ml. of refluxing ethanol and 18.2 g. of 4-biphenylcarboxaldehyde is dissolved in 15 ml. of hot ethanol and added to the above solution. The orange-yellow solution is refluxed for 18 hours, then is cooled and filtered. The product is washed with n-hexane to provide 35.0 g. of 2,6-dichloro-N 4 -p-phenylbenzylidene-p-phenylenediamine as bright yellow needles, m.p. 108°-110° C.
A mixture of 13.6 g. of 2,6-dichloro-N 4 -p-phenylbenzylidene-p-phenylenediamine and 1.0 g. of 10% palladium-on-carbon catalyst in 100 ml. of tetrahydrofuran is hydrogenated in a Parr shaker at room temperature with a pressure drop from 44 p.s.i. to 15 p.s.i. The mixture is filtered and washed with tetrahydrofuran. The filtrate is evaporated to a syrup which is treated with ethanol/hexane to crystallize the product. The product is collected and washed with n-hexane to give 9.4 g. of 2,6-dichloro-N 4 -p-phenylbenzyl-p-phenylenediamine as pale yellow crystals, m.p. 110°-111° C.
A 6.9 g. amount of the above product in 21 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 5 hours then is allowed to stand at room temperature. The solvent is evaporated in vacuo and the solid is dissolved in 300 ml. of refluxing ethanol. The ethanol solution is evaporated to 100 ml. and cooled at 5° C. The crystallized product is collected by filtration and washed with ethanol/n-hexane to yield 4.4 g. of the product of the Example as pale yellow crystals, m.p. 165°-168° C.
EXAMPLE 9
N'-[4-(m-Bromobenzylamino)-2,6-dichlorophenyl]-N,N-dimethylformamidine hydrochloride
A 17.7 g. amount of 2,6-dichloro-1,4-phenylenediamine is dissolved in 50 ml. of absolute ethanol, then 18.5 g. of m-bromobenzaldehyde is added. Crystallization of a product takes place within one minute, then n-hexane is added. The product is collected by filtration to give 31.0 g. of N 4 -m-bromobenzylidene-2,6-dichloro-p-phenylenediamine as pale yellow crystals, m.p. 136°-138° C.
A 17.3 g. amount of N 4 -m-bromobenzylidene-2,6-dichloro-p-phenylenediamine is dissolved in 100 ml. of warm tetrahydrofuran, then 1.0 g. of platinum oxide is added and the mixture is hydrogenated in a Parr apparatus. Reduction is complete after 5 minutes with 4.5 p.s.i. consumed. The reaction mixture is filtered and washed with tetrahydrofuran. The pale yellow filtrate is evaporated to a syrup. The syrup is dissolved in ethanol, then hexane is added and the solution is treated with 25 ml. of 4.1 N ethanolic hydrochloric acid. The product is collected by filtration and washed with n-hexane to give 21.8 g. of N 4 -m-bromobenzyl-2,6-dichloro-p-phenylenediamine hydrochloride as orange crystals, m.p. 192°-195° C. (dec.).
A mixture of 10.0 g. of the preceding compound, 20 ml. of water, and 10 ml. of 10 N sodium hydroxide is extracted with two 50 ml. portions of chloroform. The combined extract is dried over magnesium sulfate and evaporated to a syrup. The syrup is refluxed with 25 ml. of N,N-dimethylformamide dimethylacetal for 18 hours. The reaction mixture solvent is removed in vacuo to give an amber syrup which is dissolved in 20 ml. of warm ethanol. The addition of 20 ml. of 4.1 N ethanolic hydrochloric acid gives 10.0 g. of the product of the Example as colorless crystals, m.p. 217°-219° C.
EXAMPLE 10
N'-[2,6-Dichloro-4-(3,5-dichlorobenzylamino)phenyl]-N,N-dimethylformamidine hydrochloride
A mixture of 13.3 g. of 2,6-dichloro-p-phenylenediamine and 13.1 g. of 3,5-dichlorobenzaldehyde in 100 ml. of absolute ethanol is refluxed for 18 hours. The mixture is cooled and hexane is added. The product is collected by filtration and is washed with hexane until the wash is clear to give 24.3 g. of 2,6-dichloro-N 4 -3,5-dichlorobenzylidene-p-phenylenediamine as mustard colored crystals, m.p. 194°-195° C.
A mixture of 13.8 g. of 2,6-dichloro-N 4 -3,5-dichlorobenzylidene-p-phenylenediamine, 150 ml. of warm tetrahydrofuran and 1.0 g. of 10% palladium-on-carbon catalyst is hydrogenated in a Parr shaker at room temperature for 3 hours. The reaction mixture is cooled, filtered, and evaporated in vacuo to give a dark syrup. The addition of ethanol and n-hexane gives 8.3 g. of crude product. Recrystallization from heptane gives 4.7 g. of 2,6-dichloro-N 4 -3,5-dichlorobenzyl-p-phenylenediamine as crystals, m.p. 133°-135° C.
A 3.0 g. amount of the preceding product in 20 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 5 hours. The mixture is evaporated in vacuo to give a syrup. The syrup is dissolved in 10 ml. of ethanol and 30 ml. of 4.1 N ethanolic hydrochloric acid is added. After the addition of ether the crystals are collected by filtration and washed with ethanol/ether then ether to give 1.6 g. of the desired product as off-white crystals, m.p. 240°-242° C. (dec.).
EXAMPLE 11
N'-[2,6-Dichloro-4-[(4-dimethylamino-2-methoxybenzyl)-amino]phenyl]-N,N-dimethylformamidine
An 8.0 g. amount of 2,6-dichloro-p-phenylenediamine is dissolved in 50 ml. of warm ethanol then 8.1 g. of 4-dimethylamino-2-methoxybenzaldehyde is added and the mixture is heated at reflux for 5 hours. The solution is cooled to room temperature and crystallization is induced by the addition of several drops of n-hexane. Filtration gives 9.2 g. of 2,6-dichloro-N 4 -(4-dimethylamino-2-methoxybenzylidene)-p-phenylenediamine as bright yellow crystals, m.p. 137°-139° C.
A 5.0 g. amount of 2,6-dichloro-N 4 -(4-dimethylamino-2-methoxybenzylidene)-p-phenylenediamine is slurried in 100 ml. of methanol. To this mixture is added, with stirring, over a 30 minute period, 1.2 g. of sodium borohydride. After an additional 30 minutes of stirring, 3.6 g. of 2,6-dichloro-N'-(4-dimethylamino-2-methoxybenzyl)-p-phenylenediamine is collected by filtration as yellow crystals, m.p. 111°-113° C.
A 3.0 g. amount of the above material in 15 ml. of N,N-dimethylformamide dimethylacetal is heated at the reflux temperature for 6 hours. The mixture is evaporated in vacuo to a crystalline residue. Recrystallization from 15 ml. of ethanol gives 1.7 g. of N'-[2,6-dichloro-4-[(4-dimethylamino-2-methoxybenzyl)amino]phenyl]-N,N-dimethylformamidine as granular, yellow crystals, m.p. 160°-162° C.
EXAMPLE 12
N'-[2,6-Dichloro-4-(p-diethylaminobenzylamino)-phenyl]-N,N-dimethylformamidine
A 10.8 g. amount of 2,6-dichloro-p-phenylenediamine is dissolved in 75 ml. of warm ethanol, then 10.8 g. of p-diethylaminobenzaldehyde is added and the mixture is refluxed for 18 hours. The reaction mixture is diluted to one liter with n-hexane. The solution is evaporated to a dark amber syrup and crystallized from a mixture of toluene and hexane, to give 3.7 g. of 2,6-dichloro-N 4 -(p-diethylaminobenzylidene)-p-phenylenediamine as light yellow crystals, m.p. 56°-57° C.
A 6.7 g. amount of 2,6-dichloro-N 4 -(p-diethylaminobenzylidene)-p-phenylenediamine (prepared as described above) is dissolved in 50 ml. of dry tetrahydrofuran (dried over 3 A molecular sieves). Then over a 5 minute period with stirring is added 1.0 g. of lithium borohydride. The mixture is covered and stirred for 18 hours.
The reaction mixture is filtered through diatomaceous earth and evaporated to a syrup. Water and chloroform are added to the syrup and the mixture is stirred for 2 hours. The chloroform layer is evaporated in vacuo to give a syrup which is crystallized from ethanol to give 1.2 g. of 2,6-dichloro-N 4 -(p-diethylaminobenzyl)-p-phenylenediamine as colorless crystals, m.p. 120° C. (dec.).
A 5.6 g. amount of 2,6-dichloro-N 4 -(p-diethylaminobenzyl)-p-phenylenediamine (prepared as described above) and 15 ml. of N,N-dimethylformamide dimethylacetal are refluxed for 18 hours. The reaction mixture is evaporated to a pale yellow syrup. The syrup is dissolved in 20 ml. of ethanol, treated with activated carbon and filtered. The filtrate is diluted to 250 ml. with n-hexane to provide 4.1 g. of the product of the Example as colorless needles, m.p. 98°-99° C.
EXAMPLE 13
N'-[2,6-Dichloro-4-(4-dimethylamino-2-methylbenzylamino)phenyl]-N,N-dimethylformamidine
A 25.0 g. amount of N,N-dimethyl-m-toluidine is formulated with Vilsmeier reagent (N,N-dimethylformamide-phosphorus oxychloride) to give 19.0 of 4-dimethylamino-o-tolualdehyde as pale yellow crystals, m.p. 64°-65° C. A 10.6 g. amount of recrystallized 2,6-dichloro-p-phenylenediamine is dissolved in 50 ml. of warm ethanol, then 9.8 g. of 4-dimethylamino-o-tolualdehyde is added and the mixture is heated at a simmer for 3 hours. The mixture is allowed to stand at room temperature for 16 hours, then is evaporated to dryness. The residue is recrystallized from ethanol/n-hexane, filtered and washed with ethanol/hexane to yield 12.0 g. of 2,6-dichloro-N 4 -(4-dimethylamino-2-methylbenzylidene)-p-phenylenediamine as mustard colored needles, m.p. 92°-93° C.
A 6.4 g. amount of 2,6-dichloro-N 4 -(4-dimethylamino-2-methylbenzylidene)-p-phenylenediamine is slurried in 100 ml. of methanol. To this mixture is added, with stirring, over a 2 hour period 2.0 g. of sodium borohydride. Solution occurs and the mixture is stirred at room temperature for 18 hours. The solution is evaporated to dryness. The residue is extracted from water with two 100 ml. portions of chloroform. The combined extracts are dried over magnesium sulfate and evaporated to a syrup which is crystallized in the presence of ethanol to give 5.3 g. of 2,6-dichloro-N 4 -(4-dimethylamino-2-methylbenzyl)-p-phenylenediamine as tan plates, m.p. 108°-109° C.
A 3.0 g. amount of the preceding compound in 15 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 6 hours. The mixture is cooled and evaporated in vacuo to a dark amber syrup. Crystallization from ethanol and n-hexane gives 2.4 g. of the product of the Example as golden plates, m.p. 166°-168° C.
EXAMPLE 14
N'-[4-(2-Bromo-4-dimethylaminobenzylamino)-2,6-dichlorophenyl]-N,N-dimethylformamidine
A 31.0 g. amount of 3-bromo-dimethylaniline and 20 ml. of dry N,N-dimethylformamide is added over a 20 minute period to a cold stirred solution of Vilsmeier reagent (N,N-dimethylformamide-phosphorus oxychloride) to give 28.5 g. of pale yellow crystals. The product is recrystallized from hexane, filtered and washed with hexane to give 20.3 g. of 2-bromo-4-dimethylaminobenzaldehyde as colorless needles, m.p. 86°-88° C.
A 10.6 g. amount of 2,6-dichloro-p-phenylenediamine is dissolved in 50 ml. of warm ethanol and 13.7 g. of the preceding aldehyde is added. The reaction mixture is refluxed for one hour then is allowed to stand at room temperature. The solid is collected by filtration to yield 21 g. of N 4 -(2-bromo-4-dimethylaminobenzylidene)-2,6-dichloro-p-phenylenediamine as mustard colored crystals, m.p. 152°-153° C.
An 8.1 g. amount of N 4 -(2-bromo-4-dimethylamino-benzylidene)-2,6-dichloro-p-phenylenediamine is stirred in 125 ml. of methanol. To this suspension is added with stirring, portionwise, over a one hour period 1.3 g. of sodium borohydride. The reaction mixture sets to a solid and is filtered and washed with water. The aqueous phase is extracted with 200 ml. of chloroform which is dried over magnesium sulfate and evaporated to give an oil. Crystallization from ethanol gives 2.7 g. of N 4 -(2-bromo-4-dimethylaminobenzyl)-2,6-dichloro-p-phenylenediamine as bright yellow crystals, m.p. 133°-135° C.
The preceding product (2.7 g.) is refluxed for 5 hours in 25 ml. of N,N-dimethylformamide dimethylacetal. The reaction solution is evaporated in vacuo to yield yellow crystals. The material is recrystallized from ethanol/n-hexane to give 2.5 g. of the desired product as yellow crystals, m.p. 135°-137° C.
EXAMPLE 15
N'-[4-(3-Bromo-4-dimethylaminobenzylamino)-2,6-dichlorophenyl]-N,N-dimethylformamidine
An 8.8 g. amount of 2,6-dichloro-p-phenylenediamine is dissolved in 40 ml. of ethanol by refluxing, then 11.4 g. of 3-bromo-4-dimethylaminobenzaldehyde [prepared by the method of Brady and Truszkowske, J. Chem. Soc., 123, 2438 (1923)] in 10 ml. of ethanol is added. The mixture is refluxed for 6 hours, then cooled to give crystals. Washing with n-hexane gives 17.3 g. of N 4 -(3-bromo-4-dimethylaminobenzylidene)-2,6-dichloro-p-phenylenediamine as pale yellow crystals, m.p. 138°-140° C.
A 3.9 g. amount of N 4 -(3-bromo-4-dimethylaminobenzylidene)-2,6-dichloro-p-phenylenediamine is stirred as a slurry in 100 ml. of methanol. To the slurry is added with stirring, portionwise over a one hour period, 1.0 g. of sodium borohydride. The resulting solution is covered and stirred at room temperature for 18 hours. The reaction mixture is evaporated to dryness, water is added and the mixture extracted twice with 75 ml. of chloroform. Evaporation of the chloroform yields an amber syrup which crystallizes from ethanol to give 3.0 g. of N 4 -(3-bromo-4-dimethylaminobenzyl)-2,6-dichloro-p-phenylenediamine as pale yellow needles, m.p. 98°-99° C.
A 2.5 g. amount of the preceding product in 15 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 18 hours. The solution is evaporated to an amber syrup. The syrup is treated with hexane and ether to give 1.4 g. of the product of the Example as pale yellow rosettes, m.p. 109°-110° C.
EXAMPLE 16
N'-[2,6-Dichloro-4-[(4-dimethylamino-2-fluorobenzyl)-amino]phenyl]-N,N-dimethylformamidine
An 8.8 g. amount of 2,6-dichloro-p-phenylenediamine is dissolved in 100 ml. of refluxing ethanol. Then 8.4 g. of 4-dimethylamino-2-fluorobenzaldehyde [prepared by the method of J. Org. Chem., 25, 2053 (1960)] is added, the mixture is refluxed for 4 hours, cooled, filtered and washed with cold ethanol, ethanol-hexane then hexane to give 12.0 g. of 2,6-dichloro-N 4 -(4-dimethylamino-2-fluorobenzylidene)-p-phenylenediamine as crystals, m.p. 127°-128° C.
To a stirred slurry of 5.0 g. of 2,6-dichloro-N 4 -(4-dimethylamino-2-fluorobenzylidene-p-phenylenediamine is added one g. of sodium borohydride, portionwise, over a 30 minute period. The reaction mixture is evaporated to a dryness after stirring at room temperature for 18 hours. Water is added and the mixture is extracted with chloroform. The chloroform extract is evaporated to give a tan solid which is crystallized from a mixture of ether and n-hexane to give 3.9 g. of 2,6-dichloro-N 4 -(4-dimethylamino-2-fluorobenzyl)-p-phenylenediamine as pale yellow crystals, m.p. 114°-115° C.
A 3.5 g. amount of the preceding product in 15 ml. of N,N-dimethylformamide dimethylacetal is refluxed for 6 hours. The mixture is evaporated to a syrup. The syrup is crystallized from ethanol/n-hexane/ether to give 2.2 g. of the desired product, m.p. 118°-120° C. | This disclosure describes novel N'-[2,6-dichloro-4-(substituted-benzylamino)phenyl]-N,N-dimethyl-formamidines which possess activity as hypotensive agents and as diuretics. | 2 |
FIELD OF THE INVENTION
The present invention is in the field of implantable medical devices and prosthesis, particularly, devices useful as both a structural prosthetic for articular tissue and an in vivo scaffold for the regeneration of articular tissue, including tendons for rotator cuff repair, and methods of making and using the devices.
BACKGROUND OF THE INVENTION
Proper functioning of the human shoulder is in part governed by the rotator cuff muscles. These muscles originate from scapula (one of the three shoulder bones) and attach to the humerus via fibrous tendons as they approach the outer aspect of the shoulder thereby surrounding the anterior, superior and posterior of the shoulder joint. The motion of the shoulder is facilitated by the contraction of rotator cuff muscles which pull the rotator cuff tendons. Thus the rotator cuff allows movement of the upper arm for activities such as reaching and throwing.
Disorders of the rotator cuff, particularly tears of the rotator cuff tendons, can cause significant shoulder pain and disability. Young athletes, middle-aged workers, and a substantial portion of the elderly population can suffer a rotator cuff injury which prevents them from working, playing sports, enjoying hobbies or performing routine daily activities. Active people, including athletes, are highly susceptible to rotator cuff problems, particularly as they get older. It has been estimated that more than 100,000 rotator cuff surgeries are performed in the United States each year. Rotator cuff lesions are one of the most common causes of upper extremity disability.
A serious concern with a rotator cuff tear is that the rotator cuff has limited healing potential after tears. The non-surgical treatment for rotator cuff tears includes some combination of anti-inflammatory medication, limiting overhead activity, steroid injections, and strengthening exercises often in association with physical therapy. Surgery to repair the rotator cuff is often advised when a rotator-cuff tear causes severe shoulder weakness or when there has been no improvement following non-surgical treatment. Repair of a torn rotator cuff generally consists of reapproximating the tendon edge to a bony trough through the cortical surface of the greater tuberosity.
Traditionally, surgeons use suture and suture anchors to repair weak, frayed and damaged tissue. Several surgical procedures have been performed to cover massive irreparable rotator cuff tears, including tendon transfer, tendon mobilization and tendon autografts patch grafts using biological or synthetic materials [Aoki et al., 1996 J Bone Joint Surg Br. 1996 September; 78(5):761-6; Gerber 1992 Clin Orthop Relat Res. 1992 February; (275):152-60; Kimura et al., 2003 J Bone Joint Surg Br. 2003 March; 85(2):282-7]. Suture anchors were found to be useful in rotator cuff repair because they could be placed with less surgical dissection and allowed for the “mini-open” technique to become popularized. There are two major disadvantages to using bioresorbable suture anchors that are currently available and used in arthroscopic rotator cuff repair. Passing the suture through the rotator cuff can often be challenging due to the limited amount of working area in the subacromial space. While knots can be tied arthroscopically in a secure fashion, the process is very time-consuming and clearly has a long learning curve. Arthroscopic repair has been suggested for rotator cuff repair, however is burdened by a percentage of recurrences that is greater than the repair carried out when an open technique is used [Bungaro et al., 2005 Chir Organi Mov. 2005 April-June; 90(2):113-9]. It has been found that when an open technique is used, good hold can be guaranteed by using reinforced stitches such as the modified Mason-Allen suture.
The clinical results of all current rotator cuff repair techniques are often sub-optimal and often pre-injury functional levels are not obtained. Augmentation devices have not provided a satisfactory alternative. Several factors limit the extensive use of biological grafts including donor site morbidity, limited availability of autografts material the risk of disease transmission from allografts and patch grafts become mechanically weaker over time as they cause adverse reactions. Extracellular matrices are widely employed by sports-medicine and orthopedic surgeons for augmenting the torn rotator cuff and are intended to strengthen the tendon and enhance biological healing. More recently, synthetic bioabsorbable meshes have been commercialized for repair of soft tissues, including the rotator cuff.
Several extracellular matrix products (ECMs) are commercially available and include GraftJacket (Wright Medical Technology), CuffPatch (Organogenesis, licensed to Arthrotek), Restore (Depuy), Zimmer Collagen Repair (Permacol) patch (licensed by Tissue Science Laboratories), TissueMend (TEI Biosciences, licensed to Stryker), OrthoADAPT (Pegasus Biologics), and BioBlanket (Kensey Nash). These products are fabricated from human, cow, or pig skin, equine pericardium, human fascia latta, or porcine small intestine submuccosa. The manufacturers use various methods of decellularization, cross-linking, and sterilization; the end products possess varying properties of strength, stiffness, and suture-failure load. While there are many products available and many thousands of rotator cuff repairs being performed annually with extracellular matrices, little is known about clinical outcomes. One published study by Iannofti et al found that porcine small intestine mucosa (DePuy's Restore patch) did not improve the rate of tendon-healing or the clinical outcome scores of patients with massive and chronic rotator cuff tears. The relatively low resistance to suture pull-out and potential for immunological response (perceived or real) of ECMs has limited widespread use of ECMs for rotator cuff repair.
Depuy Orthopedics Inc, Warsaw, Ind. has developed SIS (intenstinal submucosa) for augmentation of rotator cuff tendon tears. The SIS materials have sold well, but have the disadvantage of originating from a contaminated animal source, necessitating a variety of cleaning steps. Some patients have sustained swelling, and what appears to be a graft versus host reaction to the SIS Material. GraftJacket is a product by Wright medical using cross banked human cadaver skin. While response levels are lower with this product, the material is very poorly degradable.
Some of the recent studies have indicated some advantages of using synthetic augmentation devices to support the healing of torn rotator cuff. Two synthetic, bioabsorbable products were recently 510 k cleared by the FDA, and both indications for use statements include rotator cuff repair. One of these products is SportMesh (marketed by Biomet) which is made from woven Artelon fibers. Artelon is a biodegradable poly(urethaneurea) material. SportMesh is currently under evaluation for treatment of rotator cuff tears at one or more US-based centers. A second synthetic product recently cleared by the FDA is the X-Repair (marketed by Synthasome) which is made from woven bioabsorbable poly(L-lactic acid) (PLLA) fibers. The X-Repair product was evaluated in a canine model and found to improve biomechanical function at 12 weeks. Another product of interest that was cleared by the FDA is Serica's SeriScaffold, a long-term bioabsorbable woven mesh of silk fibers. Two PLLA devices have been evaluated for rotator cuff repair; one study in sheep reported in 2000 showed a 25% increase in strength of the repair and a second study in goats reported in 2006 showed no significant difference in load to failure of the repair. One study by Koh et al. demonstrated the better biomechanical performance of damaged rotator cuff tendon while healing when the tear was augmented with woven polylactic acid structures [Koh et al., 2002 Am J Sports Med. 2002 May-June; 30(3):410-3]. See, for example, U.S. published application 2008/0051888.
There is a need for an alternative strategy to develop an augmentation device for rotator cuff repair and regeneration due to several reasons. First it has recently been found that up to 60 percent of rotator cuff tendon repairs are failing after repair, even in the hands of good surgeons. While some patients do well after surgery even with the re-torn rotator cuff tear, many do not, and in fact a re-torn rotator cuff is a negative predictor of outcome for a patient. Second, is the fact that traditional outcomes of rotator cuff repair are limited by biology. It takes four weeks to heal a rotator cuff repair, during which patients are not allowed to have significant mobilization of the shoulder. However, the decreased mobility of the joint can lead to significant shoulder stiffness which is a serious disadvantage. This clearly shows the importance of an augmentation device that would allow shoulder mobility while healing. Third, often there are gap areas that cannot be closed with rotator cuff tears. An augmentation device when employed could satisfactorily address this concern.
It is an object of the present invention to provide a biocompatible device for augmentation and repair of rotator cuff injuries.
It is still another object of the present invention to provide a method for producing a device for repair or augmentation of rotator cuff injury which results in improved strength retention and ingrowth of new tissue.
SUMMARY OF THE INVENTION
A braided rather than woven device has been developed to augment the rotator cuff tendon tissue as it proceeds in healing. The device has two purposes: to provide initial stability to the rotator cuff repair site to allow early mobilization of the upper extremity of the patient, and to allow for reinforcement of rotator cuff tendon repairs to increase the likelihood of successful rotator cuff tendon repairs. The device consists of an inter-connected, open pore structure that enables even and random distribution and in-growth of tendon cells. The braided structure allows for distribution of mechanical forces over a larger area of tissue at the fixation point(s).
The device can be formed of a degradable polymer. The degradable material is designed to degrade after a period of about nine to twelve months, to allow for repair or augmentation of the tendon prior to the device losing the structural and mechanical support provided by the degradable material.
The device is manufactured using 3-D braiding to create the proper porosity for tendon cell ingrowth and in conjunction with the degradable polymer, provides augmentation strength.
The device is implanted at the site of injury preferably during open surgery although it may be possible to implant arthroscopically, by securing the device using interference screws, rivets, or other attachment devices such as sutures. Torn or damaged tendons, or allograft tissue, may be sutured to or placed adjacent to the device to enhance healing or augmentation.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view of a three dimensional (3-D) braid prepared using standard 3-D braiding techniques with final dimensions of 12 mm wide, 0.8 mm thick, cut to length.
DETAILED DESCRIPTION OF THE INVENTION
When developing an augmentation device, a bioresorbable device is highly preferred as it could prevent the need for a second surgery and at the same time significantly prevent long term biocompatibility issues found with permanent metallic, ceramic or polymeric implants.
The resorbable augmentation device needs to closely mimic the biomechanical properties of the tissue to be regenerated for a short span of time during the new tissue formation, until the regenerated tissue could satisfactorily perform the required functions. In addition to these requirements the resorbable augmentation device should present a favorable structure for cell infiltration and matrix deposition for neo-tissue formation. These facts points to the need for the development of a temporary augmentation device that closely mimics the structural features of the native tissue.
I. Tendon Rotator Cuff Augmentation Device
A polymeric fibrous structure that exhibits similar mechanical properties of human fibrous soft tissue, such as tendon, and is fabricated using standard 3-D braiding techniques. The mechanical properties of soft tissue and/or the fibrous structures can be determined by the placing a sample in a spring loaded clamp attached to the mechanical testing device and subjecting the sample to constant rate extension (5 mm/min) while measuring load and displacement and recording the resulting strain-stress curve. In particularly useful embodiments, the polymeric braided structure exhibits a stiffness in the range of stiffness exhibited by fibrous soft tissue. Typically, suitable stiffness will be in the range of about 10 to about 500 Newtons per millimeter (N/mm), and suitable tensile strength will be in the range of about 20 to about 1000 Newtons (N). In some embodiments, the stiffness of the polymeric fibrous structure will be in the range of about 20 to about 80 N/mm. The fibrous structure can be prepared using standard techniques for making a 3-D braided structure. The width and length dimensions of the device can vary within those ranges conventionally used for a specific application and delivery device. For example, dimensions of about 10 mm by 10 mm to about 100 mm by 100 mm. The device can be dimensioned to allow it to be rolled or otherwise folded to fit within a cannula having a small diameter to allow arthroscopic or laparoscopic implantation, fitting within openings on the order of about 0.5 mm to about 10 mm. In some embodiments, the fibrous structure defines openings on the order of about 0.5 mm to about 10 mm. In certain embodiments, the fibrous structure is braided using multifilament PLLA fibers that are plied to create a yarn bundle. Each 60 to 100 denier PLLA fiber is made up of 20-40 individual filaments. In particularly useful embodiments, the 3-D braided fibrous structure includes about twenty four 75 denier PLLA fibers made up of 30 individual filaments. The diameter of a 75 denier PLLA fiber is about 80-100 microns while the diameter of an individual filament is about 15-20 microns. In some embodiments, the fibers have a diameter ranging from about 50 microns to about 150 microns. In particularly useful embodiments, the fibers have a diameter ranging from about 80 microns to about 100 microns. In one embodiment, the device is formed using a braiding mechanism with 75 denier degradable polymer such as PLLA, having a relaxed width of between 10 mm and 14 mm and tensioned width of between 8 mm and 12 mm; relaxed thickness of between 0.8 mm and 1.2 mm and a tensioned thickness of between 0.6 mm 1.0 mm.
The braided structure can be packaged and sterilized in accordance with any of the techniques within the purview of those skilled in the art. The package in which the implant or plurality of implants are maintained in sterile condition until use can take a variety of forms known to the art. The packaging material itself can be bacteria and fluid or vapor impermeable, such as film, sheet, or tube, polyethylene, polypropylene, poly(vinylchloride), and poly(ethylene terephthalate), with seams, joints, and seals made by conventional techniques, such as, for example, heat sealing and adhesive bonding. Examples of heat sealing include sealing through use of heated rollers, sealing through use of heated bars, radio frequency sealing, and ultrasonic sealing. Peelable seals based on pressure sensitive adhesives may also be used.
The braided structures described herein can be used to repair, support, and/or reconstruct fibrous soft issue. The braided structures may rapidly restore mechanical functionality to the fibrous soft tissue. The braided structures may be implanted using conventional surgical or laparoscopic/arthroscopic techniques. The braided structure can be affixed to the soft tissue or to bone adjacent to or associated with the soft tissue to be repaired. In particularly useful embodiments, the braided structure is affixed to muscle, bone, ligament, tendon, to or fragments thereof. Affixing the braided structure can be achieved using techniques within the purview of those skilled in the art using, for example, sutures, staples and the like, with or without the use of appropriate anchors, pledgets, etc.
A. Polymeric Materials
Suitable degradable polymers include polyhydroxy acids such as polylactic and polyglycolic acids and copolymers thereof, polyanhydrides, polyorthoesters, polyphosphazenes, polycaprolactones, biodegradable polyurethanes, polyanhydride-co-imides, polypropylene fumarates, polydiaxonane polycaprolactone, and polyhydroxyalkanoates such as poly4-hydroxy butyrate, and/or combinations of these. Natural biodegradable polymers such as proteins and polysaccharides, for example, extracellular matrix components, hyaluronic acids, alginates, collagen, fibrin, polysaccharide, celluloses, silk, or chitosan, may also be used.
Preferred biodegradable polymers are lactic acid polymers such as poly(L-lactic acid) (PLLA), poly(lactic acid) (PLA), and poly(lactic-co-glycolic acid) (PLGA). The co-monomer (lactide-glycolide) ratios of the poly(lactic-co-glycolic acid) are preferably between 100:0 and 50:50. Most preferably, the co-monomer ratios are between 85:15 (PLGA 85:15) and 50:50 (PLGA 50:50). Blends of PLLA with PLGA, preferably PLGA 85:15 and PLGA 50:50 can also be used. The preferred polymer for the non-degradable region is a polyester and the preferred polymer for the degradable region is PLLA.
Material may be applied to the fibers to increase adhesion or biocompatibility, for example, extracellular matrix molecules such as fibronectin and laminin, growth factors such as EGF, FGF, PDGF, BMP, and VEGF, hyaluronic acid, collagens, and glycosaminoglycans.
B. Cell Seeding
The devices can optionally be seeded with cells, preferably mammalian cells, more preferably human cells. Alternatively, they are implanted and cells may attach to and proliferate on and within the devices. Various cell types can be used for seeding. In a preferred embodiment, for ligament and tendon replacement, the cells are either mesenchymal in origin or capable of generating mesenchymal cells. Accordingly, preferred cell types are those of the connective tissue, as well as multipotent or pluripotent adult or embryonic stem cells, preferably pluripotent stem cells. However, the scaffolds can be seeded with any cell type which exhibits attachment and ingrowth and is suitable for the intended purpose of the braided scaffold. Some exemplary cell types which can be seeded into these scaffolds when used for repair, regeneration or augmentation of connective tissue or other tissue types such as parenchymal tissues, include, but are not limited to, osteoblast and osteoblast-like cells, endocrine cells, fibroblasts, endothelial cells, genitourinary cells, lymphatic vessel cells, pancreatic islet cells, hepatocytes, muscle cells, intestinal cells, kidney cells, blood vessel cells, thyroid cells, parathyroid cells, cells of the adrenal-hypothalamic pituitary axis, bile duct cells, ovarian or testicular cells, salivary secretory cells, renal cells, chondrocytes, epithelial cells, nerve cells and progenitor cells such as myoblast or stem cells, particularly pluripotent stem cells.
Cells that could be used can be first harvested, grown and passaged in tissue cultures. The cultured cells are then seeded onto the three dimensional braided scaffold to produce a graft material composed of living cells and a degradable matrix. This graft material can then be surgically implanted into a patient at the site of ligament or tendon injury to promote healing and repair of the damaged ligament or tendon.
Growth factors and other bioactive agents may be added to the graft material. In a preferred embodiment, these include fibroblast growth factor (FGF), vascular endothelial growth factor (VEGF), epidermal growth factor (EGF), and bone morphogenic proteins (BMPs). Adhesive materials such as fibronectin and vimentin can also be added. These are preferably added in amount ranging from 0.1 nanogram to 1 micrograms. Cell isolates (for example, from marrow cells) or biological factors isolated from blood can also be added to the graft or placed with the graft.
II. Methods of Manufacture
The device is prepared using standard 3-D braiding techniques and equipment. The device is 3-D braided so that the structure has the desired combination of the fiber properties and porosity resulting from the 3-D braided structure
The geometric parameters which determine the shape and fiber architecture of three-dimensional braids includes braiding angle distribution, fiber volume fraction, number of carriers, and braiding width. The braiding pattern can depend on braiding machinery/technique used. The device peak load strength range is from 20 to 1000 N, with an initial stiffness range of 20 to 500 N/mm. The devices are typically provided in a sterile kit, such as a foil or TYVEX® package.
III. Methods of Use
The device is used for repair or augmentation of articular injury, by implanting the device at a site in need of articular repair or augmentation.
In use, the devices are implanted to match the biomechanical properties of the tissue being repaired. This permits an early return to normal function post-operatively. The implanted device bears applied loads and tissue in-growth commences. The mechanical properties of the biodegradable material of the implant slowly decay following implantation, to permit a gradual transfer of load to the ingrown fibrous tissue. In a preferred embodiment, the degradation of the biodegradable material occurs after about 9-12 months. Additional in-growth continues into the space provided by the biodegradable material of the implant as it is absorbed. This process continues until the biodegradable material is completely absorbed and only the newly formed tissue remains.
Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims. | A device has been developed to augment the rotator cuff tendon tissue as it proceeds in healing. The device has two purposes: to provide initial stability to the rotator cuff repair site to allow early mobilization of the upper extremity of the patient, and to allow for reinforcement of rotator cuff tendon repairs to increase the likelihood of successful rotator cuff tendon repairs. The device consists of an inter-connected, open pore structure that enables even and random distribution and in-growth of tendon cells. The braided structure allows for distribution of mechanical forces over a larger area of tissue at the fixation point(s). | 3 |
BACKGROUND OF THE INVENTION
This invention relates to a new and improved apparatus for wrapping individual and similarly shaped confectionery and non-confectionery items, and more particularly, to wrapping mints and the like.
The prior art apparatus is known from the present assignee's previously assigned U.S. Pat. Nos. 2,757,499 and 3,391,520; and this invention provides an improved and simplified arrangement for accomplishing the automatic and continuous individual wrapping of each item.
The referenced U.S. Pat. No. 2,757,499 is directed in general to a machine wherein the individual articles are pushed through a stuffing tunnel to shape a planar sheet fragment into the form of a bag surrounding the entering end and peripheral portion of the article leaving a skirt. Thereafter, the skirt is twisted and crimped in order to form about the opposite end of the article a complete wrap to substantially seal each article or unit in a tightly wrapped manner. Specifically, the machine of this patent is associated with a conventional article conveyor line and includes a receiving chamber for delivering the articles in a predetermined position. A machine mechanism intermittently projects the free end of a strip of flexible wrapping material into a planar position above or in front of the article. The machine thereafter severs the outer portion of the strip into a wrapping fragment and brings the article with the severed fragment into a stuffer tunnel to cover the forward end and periphery of the article in a bag formation within the wrapper. Thereafter, the twist and skirt portion is formed tightly about the article completing the wrapping operation, all of which is operatively synchronized in the successive operations for wrapping the individual articles.
An improved appparatus for wrapping the individual confectionery products was disclosed in U.S. Pat. No. 3,391,520 in which the machine retained a piece of confectionery product adjacent a continuous web of wrapping material. While the piece was retained by the conveyor mechanism, the web was severed and pushed with the piece to fold the wrapper about the piece to complete the fold. This apparatus included a drum mechanism for individually indexing each head with a mint through a number of angular locations while the material was retained adjacent one surface of the pieces for each head severing the web to form a wrapper. A plunger mechanism forwarded the confectionery piece out of the drum assembly and moved the stationary piece to partially fold the wrapper about said piece, and the folding was completed at the wrapping station. A severing mechanism was included for feeding a sheet of wrapping material from the web to form individual wrappers for movement into the wrapping station. In the wrapping station, the mint is pushed out of the drum assembly aperture and against the severed wrapper to build the outer parametric portions of the wrapper and to fold the outer parametric portions of the wrapper to complete the wrapping of the confectionery piece which was accomplished in the wrapping head. The wrapping head included a series of folders for each drum assembly to complete the wrapping operation, each series of elements being synchronized to complete the folding of the paper to completely wrap the confectionery piece.
Insofar as the referenced patents are necessary for an understanding and to enable practicing the instant invention, the patents are hereby incorporated by reference. The improved apparatus according to the present invention provides a simplified arrangement for feeding and conveying the individual items to be wrapped into the wrapping head. The improvements include a simplified plunger and infeed drive so that the overall operation is simpler. A number of features are incorporated to provide a mint wrapper having simple construction and operation; this results in a lower cost and easier to maintain machine as will become evident by reference to the following specification.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an improved article wrapping machine which is comparatively simple, compact and efficient.
Another object of the invention is to provide an improved wrapping machine for wrapping mints and similarly shaped products in a continuous manner and without all the complexity required by the previous automatic equipment.
According to the broader aspects of the invention, there is provided a means to accomplish wrapping of a mint confectionery product by properly displacing a product into a receiving yoke, and means for pushing the product with a sheet of wrapping material into a wrapping head.
A feature of the invention is an improved plunger and infeed drive mechanism wherein an indexing means is timed with a plunger so that the displaced mint product is synchronously pushed with the sheet of wrapping material into the wrapping head in a continuous manner.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing objects and features and advantages of the present invention will be more easily understood with reference to the following description made in connection with the accompanying drawings, in which:
FIG. 1 is an illustrative perspective view showing the essential elements of the invention; and
FIG. 2 is an illustrative perspective view showing the essential mechanisms for providing the plunger and infeed drive for the novel elements of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, the apparatus of the invention will be disclosed with reference to wrapping mints and it being understood that it can be utilized to wrap other similarly shaped confectionery and non-confectionery products. In FIG. 1, an infeed belt 10 carries the mint 11 in the direction of arrow 12 and into the product entry point of vibrator infeed 13 of vibrator drive 14. The vibrator drive may be of the type as supplied by Syntron, type BF-01-C Feeder, Homer City, Pa. The vibrator infeed 13 has mounted thereon channeling guides 15, 16 into which are cut slots 15', 16' to enable operation of an electric eye means 17. This permits counting of the mints as they are carried forward by the vibrating infeed in the direction of arrow 18, or shutting down the machine when no mints are present. The vibrator 14 is mounted by support extension 19 on machine frame 20. Also mounted on the machine frame 20 is a drive unit 21 and a drive mechanism within housing 22 as more particularly described in connection with FIG. 2.
A timing and indexing wheel 23 moving in the direction of arrow 24 engages individual ones of the mints 11 and carries the mints forward, one at a time, as shown in FIG. 2, and in a timed relationship onto dual chain conveyor 25. The mints are carried forward in a continuous manner by the chain conveyor and displaced onto drop guide 26 to be caught by receiving yokes 27 in its U-shaped portion 28.
In the meantime, a web of paper wrap 30 shown in dashed lines is fed from a roll moving in the direction of arrow 31. The paper wrap is comprised of aluminum foil and wax paper, and is cut and fed into the paper stop portion 29 of yoke members 27. The paper roll is rotatably mounted and held by hub means 32, and the paper web passes over paper guides 33, 34, 35 mounted on support 36. The paper web 30 is fed between paper infeed rollers 37 driven in the direction of arrows 38 and between cutting knives 39. The cut sheet of paper is fed between feed belts 40 and stationary guides behind belts and yoke members 27 to stop 29. The paper is cut by repeated closing of the cutters in time sequence with the timing wheel 23 or the plunger 41 in a standard manner as known by the prior referenced patents.
In time relationship with indexing of timing wheel 23, a plunger 41 pushes the mint held within U-shaped portion 28 of yoke members 27 and forces the paper sheet and the mint through forming cone 42 into the wrapping head 43. The cone 42 and wrapping head 43 are shown centered on dashed lines 43' in an isometric displaced projection for clarity, whereas in reality they are positioned as indicated by dotted lines 43'. The wrapping head includes a wrapped product outlet 44 and four wrapping tuckers 45 which are operated to individually wrap the mints with the paper as known from the cross-referenced prior art applications. The operation of the wrapping tuckers, paper feed and cutters is not shown in further detail since they are well known and adequately demonstrated in the prior art patents and do not require further disclosure to enable understanding of the inventive features for this new wrapping machine. The handwheel 46 is positioned outside housing 22 to enable hand operation of the plunger mechanism for adjustment and clearance of an item when desired.
Referring now to FIG. 2, the novel feature of the plunger and infeed drive mechanism for this improved wrapping machine is illustrated in greater detail. A motor 50 is coupled by drive belt 51 to gear box 52 which is coupled to drive main angle gear 53 via drive sprockets and chain 54. One output shaft 55 from main angle gear 53 is coupled to the product infeed shaft 56 by a 2:1 ratio sprockets and chain 57. Shaft 56 drives the drive sprocket wheels 57 of dual chain conveyor 25 also rotatably mounted about sprocket wheels 58. Coupled to product infeed shaft 56 is an angle gear drive shaft 59 by means of a 2:1 ratio drive sprockets and chain 60. The angle gear drive shaft 59 drives a 2:1 ratio angle gear 61 to rotate timing wheel 23 shaped to engage the mints 11.
The vibrator 14 is infeeding the mints 11 to timing wheel 23 by means of the vibrating infeed 13. The mints 11 are received in a spaced relationship 11' on dual chain conveyor 25 which displaces the mints on drop guide 26 and into the U-shaped portion of the yoke. Plunger 41 then pushes the mint into the forming cone for wrapping as described in connection with FIG. 1. The synchronized operation is accomplished in the following manner. Another output shaft 62 from main angle gear 53 is coupled by drive sprockets and chain 63 to drive main cam shaft 64. The main cam shaft 64 is also coupled to handwheel 46 of FIG. 1. Mounted on the main cam shaft 64 is a plunger cam 65 having a camming surface 66 to effect movement of cam plunger follower 67 which is mounted at one end by bracket 68 and at the other end to linkage member 69. This enables movement of the follower 67 in the direction of arrow 70 in accordance with the movement of camming surface 66. Linkage 69 is coupled by pivot and linkage element 71 to translate the up and down motion represented by arrow 70 to the plunger in and out motion represented by arrows 74. The timing wheel 23 can be rotated 360° and locked in any position. The mint patties are timed out by the timing wheel 23 onto dual chain conveyor 25, such that when the foremost mint patty 11 drops into receiving yoke 27 in its U-shaped portion 28, the plunger 41 at that time has just reached the fully backward stroke.
In summary, the improved wrapping machine enables confectionery mints moving on a conveyor feed belt to be captured and fed by a vibrating infeed into a timing wheel. The timing wheel then engages the mint patties to feed them in a spaced manner onto a dual chain conveyor which displaces and drops them into a receiving yoke. Wrapping paper is fed from a roll through infeed rollers and cut into equal lengths with reciprocating knives in a standard manner. The cut paper sheet is then fed down by two paper feed belts onto paper stops of the receiving yoke. A plunger moves forward in timed and sequenced relationship with the timing wheel and pushes the paper sheet and mint patty through a forming cone into a wrapping head where tuckers move in and out to fold and close the paper on the rear side of the patty to complete the wrap.
Although the apparatus has been disclosed with reference to wrapping mints, it can be used to wrap other similarly shaped confectionery and non-confectionery products. It is further understood that the specific operation of the cam assemblies may be varied relative to specific angular positions of the gearing and drive coupling without changing the basic operating sequence and inventive features of the invention. A number of wrapping materials and different types of cutting edges may be utilized than described in connection with the particular enabling disclosure. This is particularly true since various products require different type wrapping material and cutting edges for cutting the wrapping material at the wrapping point of the apparatus.
While we have described above the principles of our invention in connection with specific apparatus, it is to be clearly understood that this description is made only by way of example and not as a limitation to the scope of our invention as set forth in the objects thereof and in the accompanying claims. | The products to be wrapped are moved from an input conveyor belt onto a vibrating infeed and proceed through a timing wheel which predeterminedly spaces the products. The products are dropped into a receiving yoke, and a sheet of wrapping paper is positioned such that a reciprocating plunger moves the paper and product through a forming cone and into a wrapping head which folds and closes the paper on the product. | 1 |
CROSS-REFERENCES
This application is a 371 National Phase of International Patent Application Ser. No. PCT/AU2005/001570 filed Oct. 12, 2005 which claims the benefit of priority to Australian Patent Application Serial No. 2004905923 filed Oct. 13, 2004, both of which are incorporated herein by reference in their entirety noting that the current application controls to the extent there is any contradiction with any earlier applications and to which applications we claim priority.
FIELD OF THE INVENTION
This invention relates to an apparatus for protecting cables, water lines and the like (hereinafter referred to as lines or service lines), particularly, but not exclusively, in underground workings.
BACKGROUND OF THE INVENTION
During mining operations it is necessary to protect a variety of electrical cables, water hoses and other service lines from damage. One particular area where line protecting apparatus is required, is in the area of coal mining, particularly in longwall coal mining in which a coal cutter traverses back and forth across a coal face depositing coal cut from the coal face into a conveyor disposed behind the coal cutter. In order to operate, the coal cutter requires a supply of water and electricity, which are provided by service lies. The service lines are located in a trough which is typically disposed on the opposite side of the conveyor from the coal cutter and the lines travel up and down the trough as the coal cutter moves up and down the coal face. It should be noted however, that whilst the type of apparatus envisaged by the present invention is particularly suitable for use in handling and protecting service lines for longwall coal mining, other applications of the apparatus are possible.
In order to protect such service lines, it is known to enclose, or at least partially enclose them in a protective articulated cable handler formed from a plurality of interconnected links. U.S. Pat. No. 4,988,838 discloses one such cable handler formed from a plurality of interconnected links. Each link has a central web forming a common base for a pair of laterally open channels on respective sides of the central web. For at least some of the links, each channel is formed with a inwardly extending nib so that the entrance to the channel is narrower than the width of the channel. Each link is formed from a plastics material, typically nylon, so that the channel sides are resiliently flexible and a service line can be inserted into a respective one of the channels by deflecting walls of the channel and the nibs apart. After a service line is passed through the channel entrance, the channel sides return back to regain their original position and thus prevent the line from inadvertently moving out of the channel. The links are joined by linking the central web of one link to adjacent links hence such cable handlers are referred to as “centre pull” cable handlers. Centre pull cable handlers also preferred because the water hose is kept separate from the electric cable for safety & reliability reasons.
PCT/GB95/00384 discloses a development of the apparatus shown in U.S. Pat. No. 4,988,838 in which the web is located to one side of the link instead of being centrally located, and the channel is approximately twice the depth of the centre pull design. This type of cable handler is referred to as a “side pull” cable handler, as the links are articulated via the side web and are pulled along one side only.
One problem which is common to the cable handlers of both U.S. Pat. No. 4,988,838 and PCT/GB95/00384 results from the presence of stones, flints and the like in the trough along which the cable handler runs. These flints and stones are often narrower than the channel entrance and they can enter the channel and may puncture the water hose or electric cable, thus interrupting the supply of power or water to the coat cutter and disrupting production. Further, the type of heavy duty cables used in underground mining are expensive, particularly the electric cables. The cost of replacing any damaged cables, is high, such that in some environments, mining operators will not use cable handlers of the type described in U.S. Pat. No. 4,988,838 because of the potential for damage to the service lies.
To avoid this problem twin pull cable handlers have been developed and are currently used at many longwall operations, particularly in the USA, Australia and the UK. In a twin pull cable handler, each link defines a generally rectangular shaped box in which the electric cable and water line are located. The water hose is not kept separate from the electric cable as with the centre pull design. A removable plate or plates are bolted or otherwise fixed to the tops of the side walls of the rectangle, thereby locking the cables in the U shaped link. The base, side walls, and plate are all solid providing all round protection for the electric cable and water line. The links may be linked/pulled from either or both sides, and are typically pulled from both sides, hence the name “twin pull”. However, whilst such a twin pull design provides a high degree of protection for cables, it will be appreciated that it is an extremely lengthy, tedious and time consuming process to install a pair of lines in a twin pull cable handler compared to a centre pull cable handler such as in U.S. Pat. No. 4,988,838 or a side pull cable handler, because of the need to attach a plate to each link in turn. For a typical longwall mine which might require a cable handler which is many metres long, this may take many hours, even days, and will result in loss of operating time. There is also the risk of the bolts, clips or the like securing the plates to the channels, becoming loose and separating from the channel. It will also be appreciated that, because the links have to be articulated to allow the cable to fold back upon itself, as the coal cutter traverses up and down the coal face, however the cable handler is designed, it is impossible to totally enclose the cables In a cable handler which is made of articulated rigid protective elements, as gaps are required between links to allow articulation.
International Patent Application publication number WO 03/095797 discloses one attempted solution to this problem. The links of the cable handler disclosed in that publication define a channel having an end wall and flexible side walls for receiving at least one, and typically two service lines. Engaging formations are defined on the free ends of the side walls and a second end wall plate defining engaging formations adapted to engage with the engaging formations of the side wall is provided. Engagement between engaging formations is enabled by flexing of the side walls to securely engage the second end wall between the side arms thus preventing movement of the second end wall relative to the side walls, absent flexure of the side walls. At least one, and preferably both, of the end walls is provided with pivotal formations to enable the chain link to be pivotally connected to a similar link to form a chain. Although, in theory, the design of WO 03/095797 should provide good protection for cables against a the presence of stones, flints and like in the trough, in practice it has been found that the end wall plates are not securely retained in the line of maximum parting force between the side walls in all conditions, and the end wall could possibly disengage from the rest of the link, in use. Further in the design shown in WO 03/095797, the water hose is not kept separate from the electric cable.
Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.
SUMMARY OF THE INVENTION
In a first aspect there is provided a link of a chain link for protecting cables, service lines and the like comprising:
a body portion having a first wall and two opposed side arms integral with the first end wall extending away from one side of the first wall and defining at least one channel for receiving at least one service line, the side arms having free ends and being capable of being deflected, the end walls defining first engaging formations; and
a closure means defining an end wall, the end wall defining complementary engaging formations to the first engaging formations for interlocking the end wall to the first component characterised in that the engaging formations are such the side arms of the body portion are deflected towards each other to disengage the closure means from the body portion.
The closure means may comprise an end wall from which extend relatively shorter side arms on which the complementary engaging formations are defined.
Typically the engaging formations include a rebate defined in the free end of each side arm and a key or tenon defined at the free end of each relatively shorter side arm. The rebate and key are preferably slightly inwardly tapered. The key and rebate prevent relative transverse movement of the components, which is also the direction in which the link is towed, in use.
The engaging formations may also include a channel extending transversely across the width of one of the shorter side arms or the longer side arms and a depending rib extending transversely across the width of the other of the shorter side arms or the side walls. Preferably the channel is defined on the side walls adjacent the rebate.
In one preferred embodiment the body portion defines two channels extending from opposite sides of the first wall. In this embodiment, the two channels each define engaging formations for receiving a respective closure means defining shorter side arms on which complementary engaging formations are defined. Both the first wall of the body portion and both end walls of the two closure means typically include linkage means so that the links may be connected in the centre and at both sides.
For twin pull or side pull links where the water and electrical cables would ordinarily be carried in the same channel a separator may be provided which snap-fits into the channel to separate the two cables. The separator may have a hour glass like cross-section being narrower at its middle than its top and bottom.
BRIEF DESCRIPTION OF THE DRAWINGS
A specific embodiment of the present invention will now be described by way of example only with reference to the accompanying drawings in which:
FIG. 1 is a schematic top plan view of a first embodiment of a chain link for a line protecting apparatus embodying the present invention comprising first and second interlocked components;
FIG. 2 is a schematic side view of the chain link of FIG. 1 showing the link holding two cables;
FIG. 3 is a schematic top plan view of the chain link of FIG. 1 with the first and second components separated to illustrate engaging formations on the components, and showing one end only of the first component;
FIG. 4 is a schematic side view of the chain link of FIG. 1 with the first and second components separated to illustrate engaging formations on the components, showing one end only of the first component;
FIG. 5 is a schematic top plan view of a second embodiment of a chain link for a line protecting apparatus embodying the present invention;
FIG. 6 is a schematic side view of the embodiment of chain link of FIG. 5 showing the link holding two cables;
FIG. 7 is a general assembly of a third embodiment of a chain link for a rifle protecting apparatus, embodying the present invention;
FIG. 8 is a perspective view of a fourth embodiment of a chain link for a line protecting apparatus embodying the present invention;
FIG. 9 is a side view of a cable separator for use with the fourth embodiment show in FIG. 8 ; and
FIG. 10 is an end view of the cable separator of FIG. 9 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, FIGS. 1 to 4 show a first embodiment of a line protecting apparatus or chain link 10 which forms one link of an articulated chain. The chain link comprises two parts: a body portion in the form of a generally U-shaped channel element 12 ; and a detachable closure means 14 which defines an end wall 15 from which extend a pair of short side arms 16 , 17 . The U-shaped channel element 12 includes a first or end wall 18 and two identical opposed side arms or walls 20 , 22 , integral with the end wall and defining free ends 20 a, 22 a (best seen in FIG. 4 ).
The body portion 12 is formed from a moulded plastics material such as high viscosity nylon incorporating a steel insert 24 to provide additional strength and to provide linkage means. The side walls 20 , 22 are not reinforced and are generally flexible.
The steel insert 24 , which is not ordinarily visible being largely encased in nylon, but is best seen in FIG. 1 , comprises two parallel cranked linkage elements. At one end 30 , it defines a through aperture 32 and at the other end 34 defines two parallel arms 36 which define coaxial apertures 38 . The relatively narrower portion 30 of one insert 24 can be inserted between the arms 36 of an adjacent insert and the inserts may be linked together with a bolt or other suitable means passing through the apertures 32 and 38 .
The closure means 14 is similar in design to the end wall of the U-shaped channel element 12 in that it is formed from a moulded plastics material, again typically high viscosity nylon incorporating a steel insert 40 of substantially the same shape and design as the insert 22 of the end wall 18 , to provide additional strength and additional linkage means. Thus when the closure means 14 is attached to the channel means, as illustrated in FIGS. 1 and 2 , a twin pull chain link is defined. The means by which the closure means 14 and the U-shaped channel element 12 are interlocked can be seen more clearly with reference to FIGS. 3 and 4 .
The side walls 20 , 22 of the channel element extend away from the end wall 18 in a longitudinal direction and define a generally rectangular cross-section transverse to their longitudinal extent. The side walls 20 , 22 are parallel to one another and symmetrical about a longitudinally extending plane L extending between and parallel to the side walls. Typically they will be about 6 mm deep, although this depth may be varied. A channel 50 is defied in the outer face of each side wall 20 , 22 adjacent each end 20 a, 22 a. Since the engagement means defined by the ends of the side walls are identical, one only on sidewall 22 will be described.
The channel 50 extends in a transverse direction from one side of the side wall 22 to the other. As is best seen in FIG. 4 , the channel is defined in a U/J shaped thickened portion 52 defined at the end 22 a of the arm in which the underside of the arm 22 is thickened to provide an increased depth of material underneath the channel 50 . The base 52 of the channel 50 is typically about 8 mm deep relative to the outer surface of the side wall 20 . This allows for wear of the top and bottom faces of the link, in use.
As is best seen in FIG. 3 (and shown in phantom in FIG. 4 ), a generally rectangular slot or rebate 60 with slightly tapered walls is defined in the end of the side wall 22 . The rebate extends from tie middle of the side wall of the channel 50 , in the direction of the end wall 18 . The walls taper gently towards each other in the direction of the end wall 18 .
Complementary engaging formations which mate with the channel 50 and rebate 60 are defined on the end element 14 . There is preferably zero tolerance/clearance between the inter-engaging formations to ensure a tight fit.
In particular, with reference to FIGS. 3 and 4 , the short side arms 16 , 17 of the closure means 14 each define a generally rectangular key or tenon element 62 with gently tapering sides which locates in the rebate 60 and prevents movement of the detachable end wall 14 in a transverse direction relative to the U-shaped channel element 12 .
As is best seen in FIG. 4 each short side arm 16 , 17 also defines an projecting rib 70 which, in use, locates in the channel 52 of the channel element 12 (see FIG. 2 ).
When the two components are interlocked as shown in FIGS. 1 and 2 , the dovetail-type joint formed by the key 62 and rebate 60 prevents relative movement of the components in a transverse direction T. The channel 50 and rib prevents relative movement in a longitudinal direction L.
In order to engage the U-shaped element 12 and end element 14 together, the two elements 12 and 14 are pressed together with the rebate 60 and key 62 aligned. The flexible side walls 20 , 22 flex towards each other, or may be pushed towards each other to facilitate inter-engagement. In use the link will carry service lines 80 and 90 , for water and electricity, respectively shown in FIG. 2 .
In order to disengage the detachable end wall 14 from the U-shaped channel element 12 the side arms 20 , 22 of the U-shaped channel element are simply flexed towards each other and the two components 12 , 14 , separate relatively easily.
Advantageously however, because of the design of the engaging means, the engaging means are strongest in the direction of greatest magnitude of force which occurs during use of the chain link that the direction in which the links are pulled along. In use there is little tendency for forces to be applied pushing the side walls 20 , 22 together hence little likelihood of the detachable end wall accidentally disengaging.
FIGS. 5 and 6 show a variant 10 a of the link of FIGS. 1 to 4 . The link 12 is the same as that of FIGS. 1 to 4 . The closure means 14 a, is slightly different from closure 14 as it includes only a single ranked like 40 a rather than two parallel cranked linkage elements.
Although the above describes a link for a twin pull line protector, it will be appreciated that the same principals may be applied to produce side pull, centre pull or triple pull chain links. For a centre pull, side arms will extend out from both sides of the end wall 18 , defining a channel for a water line, and a channel for a cable separated by the end wall, and the ends of those channels may be closed with end walls 14 which do not define linkage means.
FIG. 7 illustrates a triple or tri pull link 100 . In this embodiment there is a central wall 101 and two pairs of parallel side arms 102 , 104 extending away from either side of the central wall 101 . Again a steel insert 24 which is not ordinarily visible being largely encased in nylon which comprises two parallel cranked linkage elements is embedded in the wall 101 . The free ends 102 a and 104 a of the side arms are configured the same as the free ends 120 a and 122 a of the first and second embodiments and define engaging formations in the form of a channel and rebate. These engage closure means 114 a, 114 b which are substantially identical to the closure 14 a of the embodiment of FIG. 5 although one is a mirror of the other. A single cranked linkage 140 a, 140 b is embedded in the end wall of each detachable closure 114 a, 114 b respectively. Using single shear cranked plates keeps the width of the link to an minimum.
In a yet further variant a side pull link can be provided by using the body portion 12 of the twin pull described above but with an end wall which does not define any linkage means.
FIGS. 8 to 10 illustrate a yet further variant incorporating a cable separator. FIG. 8 shows a perspective view of a body portion 212 of a twin pull separator of the type shown in FIGS. 1 and 2 but which differs from the body portion of FIGS. 1 and 2 in that a notch or cut-out 214 is formed in each outer edges of each side arms 220 and 222 approximately midway between the end wall 218 and the free ends 220 a and 222 a of the body portion. A cable separator 230 shown in FIGS. 9 and 10 is provided. The cable separator has a main body portion 232 which has a height h equal to the vertical gap between the side arms 220 and 222 and relatively higher ends 234 which define protrusions 236 from the body portion and extend above and depend below the main body portion. The protrusions snap or push fit into the notches 214 to secure the cable separator extending transversely across the link. As is best seen in FIG. 10 in cross-section the cable separator is thicker at its top and bottom and tapers towards its centre, in an hour glass like shape. Typically the link will be 20 mm thick or so at its top and bottom, and as little as 2 mm thick at its middle. In this way the strength and rigidity of the separator and link are maintained whilst keeping the overall width of the link measured from the end wall 218 of the body portion to the end wall of the closure mean (not shown) as small as possible. This provides an arrangement in which the electrical cable and water line can be separated, which is desirable, in a relatively easy operation by flexing the side arms 220 and 222 and inserting the separator. No fiddly nuts or bolts, which may become loose and damage cables are required. The overall width of the link is not increased significantly, indeed, the link is thinner than the tri-pull shown in FIG. 7 , which is important as there is limited space in the channels in which such chain links run.
It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the invention as shown in the specific embodiments without departing from the spirit or scope of the invention as broadly described. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. | A cable handler link ( 10 ) includes a body portion ( 12 ) having a first wall and two opposed side arms integral with and extending generally perpendicular to the first wall defining a first channel for receiving one or more service lines. The side arms define free ends, arc capable of being deflected and each defines a first engaging formation in the form of a rebate ( 60 ). A closure means ( 14 ) includes an end wall ( 14 ) from which extend two relatively shorter side arms ( 16, 17 ) defining complementary engaging formations including a tenon ( 62 ) for interlocking the closure means to the side arms of the body portion ( 12 ). The side arms deflect towards each other to disengage the closure means from the body portion ( 12 ). The rebate ( 60 ) and tenon ( 62 ) are preferably slightly inwardly tapered and prevent relative transverse movement of the components, which is also the direction in which the link is towed, in use. | 4 |
FIELD OF THE INVENTION
This invention relates generally to embodiments of a passenger seat food tray.
BACKGROUND OF THE INVENTION
Existing food trays for airplanes are stowed in a recess of a seatback of an airplane. When stowed, a top surface of the tray faces inwardly toward the seatback. Thus, the top surface of the tray is inaccessible to airline personnel who clean airplanes. To clean a tray, airline personnel must unhinge the tray, lower the tray, clean the tray, and re-stow the tray. This cycle of unhinging, lowering, cleaning, and re-stowing each tray decreases efficiency of an airplane cleaning operation. These inefficient cleaning operations cost airlines time and money when turning an airplane around for receiving a next set of passengers.
Thus, there is an unmet need in the art for a food tray that can be rapidly wiped down and cleaned while the tray is stowed, thereby avoiding unnecessary steps and lost time spent unhinging and lowering the food tray for cleaning and re-stowing the food tray after it has been cleaned.
SUMMARY OF THE INVENTION
According to an aspect of the invention, a table is stowable and deployable from a seatback of a passenger seat. The table includes a substantially planar food tray with a first surface and a second surface substantially parallel to the first surface. The tray is stowed in the seatback in a substantially vertical position with the first surface facing outward towards a seated passenger, thereby permitting easy access cleaning of the first surface while in the stowed position. The vertically stowed tray is held in position with a moveable switch engaged against the first surface. A positioning means is mounted on the second surface which operates in stowing and deploying the tray. A pair of legs is attached to the positioning means, each leg having a first attached to the positioning means, and a second end attached to the seat. Upon turning the moveable switch clear of the first surface, the positioning means slidably urges the first surface from its stowed, substantially vertical position, to a deployed, substantially horizontal position, with the first surface facing upwards.
According to another aspect of the invention, a table is fitted with a means for rapidly detaching the tray for maintenance or replacement. A table is stowable and deployable from a seatback of a passenger seat. The table includes a substantially planar food tray with a first surface and a second surface substantially parallel to the first surface. The tray is stowed in the seatback in a substantially vertical position with the first surface facing outward towards a seated passenger, thereby permitting easy access for cleaning the first surface while in the stowed position. The vertically stowed tray is held in position with a moveable switch engaged against the first surface. A positioning means which operates in stowing and deploying the tray is mounted on the second surface. A pair of legs to the positioning means is attached a pair of legs, each leg having a first end attached to the positioning means, and a second end attached to the seat. Upon turning the moveable switch clear of the first surface, the positioning means slidably urges the first surface from its stowed, substantially vertical position, to a deployed, substantially horizontal position, with the first surface facing upwards. The means to rapidly detach the tray for maintenance or replacement includes a quick release mechanism that detaches the tray from and reattaches the tray to the pair of legs.
According to another aspect of the invention a table is substantially unaffected by seatback tilting caused by a forward seated passenger. A table is stowable and deployable from the seatback of the passenger seat. The table includes a substantially planar food tray with a first surface and a second surface substantially parallel to the first surface. The tray is stowed in the seatback in a substantially vertical position with the first surface facing outward towards a seated passenger, thereby permitting easy access for cleaning the first surface while in the stowed position. The vertically stowed tray is held in position with a moveable switch engaged against the first surface. To the second surface is mounted a positioning means which operates in stowing and deploying the tray. A positioning means which operates in stowing and deploying the tray is mounted on the second surface. A pair of legs, each leg having a first end attached to the positioning means, and a second end attached to a stationary region of the seat, is attached to the positioning means. Upon turning the moveable switch clear of the first surface, the positioning means slidably urges the first surface from its stowed, substantially vertical position to a deployed, substantially horizontal position, with the first surface facing upwards. The deployed, substantially horizontal position is substantially unaffected by tilting caused by the forward seated passenger. A means for rapidly detaching the tray for maintenance or replacement is provided, and includes a quick release mechanism. The quick release mechanism detaches the tray from and reattaches the tray to the pair of legs.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred and alternative embodiments of the invention are described in detail below with reference to the following drawings.
FIG. 1 is the invention in a stowed position of a seat back wherein the food-serving surface is facing outward;
FIG. 2 is the invention in a deployed position;
FIG. 3 is the inner working mechanisms of the invention;
FIG. 4A is a side view of the planetary transport mechanism moving the invention between a stowed position to a deployed position;
FIG. 4B is an angled view of the timing belt and gearing mechanism;
FIG. 5 is an expanded view of the timing belt components of the invention;
FIG. 6A depicts the cable and spring mechanism during invention deployment; and
FIG. 6B shows the cable and spring mechanism during invention stowage.
DETAILED DESCRIPTION OF THE INVENTION
A tray 14 is shown in FIG. 1. A food-serving surface 17 of the tray 14 faces outward when vertically stowed in the recess of a seatback in seat 10 . A toggle 11 is turned upwards in an engaged position against latch 16 . Beneath the food-serving surface 17 resides a housing panel 15 that contains the mechanical components and assemblies of a positioning mechanism that deploys and stows the tray. The housing panel 15 is attached to tray legs 13 which are held in position to seat 10 via pivot pins 12 .
The tray 14 in a deployed position is shown in FIG. 2 . After the food service tray toggle 11 is rotated clear of the latch 16 , the tray 14 migrates in an incrementally sliding motion to a substantially level position toward a passenger's lap. The incremental sliding motion is achieved with the positioning mechanism (not shown) located within the housing panel 15 . The incremental sliding motion occurs about the tray legs 13 that are connected to the seat 10 via the pivot pins 12 mounted through a hole (not shown) in each tray leg 13 .
FIG. 3 is an exploded view that shows the interior view of the housing panel 15 removed from the bottom of tray 14 . The structural relationship of the toggle 11 is shown in relation to a side underneath the latch 16 . Several of the components visible in the positioning mechanism include two timing belts 43 located on each underside of tray 14 . Each timing belt 43 meshes with a fixed timing pulley 41 that is secured to tray leg 13 , and then meshes with a planetary timing pulley 42 . Planetary timing pulleys are rotationally connected to wrist sheave 64 and tray slide arm 68 . The spring (not shown) and cable components (not shown) interact with arm 51 . A shaft (not shown) of pulley 41 and an axle (not shown) of pulley 42 are engaged with elbow pivot (not shown) and wrist pivot (not shown), respectively, of arm 51 . The engagement of the shaft and axles of pulleys 41 and 42 with elbow and wrist pivots of arm 51 maintains a constant inter-pulley distance between pulleys 41 and 42 . A hole 30 is shown in tray leg 13 in which the pivot pins (not shown) are mounted.
Incremental sliding motion imparted by the positioning mechanism is depicted in FIGS. 4A and 4B. Referring to FIG. 4A, fixed timing pulley 41 keeps timing belt 43 fixed, and, together with arm 51 (not shown), establishes planetary pulley 42 to maintain a substantially constant inter-pulley distance from timing pulley 41 . As toggle 11 turns clear of its latch, tray 14 is gravitationally urged downward and causes timing belt 43 to partially wrap around timing pulley 41 , thereby changing the pivot point of timing belt 43 . Planetary pulley 42 is then gravitationally urged downward from the changing pivot point, but a substantially constant inter-pulley distance is maintained. Thus, planetary pulley 42 rotates around the fixed timing pulley and fixed timing belt 43 , but from a changing pivot point. The wrapping movement of timing belt 43 is transmitted to the fixed pulley 41 and the planetary pulley 42 , wherein meshing of each pulley's teeth with the belt's slots imparts an incremental sliding motion to the sliding tray 14 as it is urged gravitationally downward. This in turn causes a ratcheting action of the planetary timing pulley 42 as timing pulley 42 migrates within the fixed loop path of timing belt 43 . The resultant action is the transit of the tray 14 from a substantially vertical position to a substantially horizontal position as indicated in the angle depictions, and is determined by the gearing ratios of timing pulley 41 and planetary pulley 43 . The end of the horizontal transit is controlled by a fitting 59 , such as a stop pin, that is attached to the fixed timing pulley 41 as tray 14 pivots towards a horizontal position about tray leg 13 . When downward travel of tray 14 stops, the food serving surface 17 of tray 14 is in a substantially horizontal position and faces upwardly.
Other components of the positioning mechanism are shown in FIG. 4 B. Timing pulley 41 is attached to tray legs 13 . Timing belt 43 wraps about fixed timing pulley 41 with the fitting 59 . The timing belt, in turn, causes the planetary timing pulley 42 to rotate. The rotation of the planetary timing pulley 42 is transmitted to a planetary axle 69 . Axle 69 has a plurality of stepped, smooth surfaces and a splined end. The splined end of axle 69 meshes with a wrist spline hole 72 of tray slide arm 68 . Rotation of the axle 69 results in the circular rotation of tray slide arm 68 from an approximately 0 degree parallel position to the timing belt 43 (wherein the end of tray arm 68 is substantially even with fixed pulley 41 ) to an approximately 180 degree parallel position to timing belt 43 (wherein the end of tray arm 68 is located in a linear configuration with pulley 42 and pulley 41 ). As the rotation of tray slide arm 68 occurs about timing belt 43 , arm 68 migrates from a substantially vertical position to a substantially horizontal position in relation to the upper end of tray arm 13 . The angle that results between the deployed position and the stowed position is determined by the gearing ratio between the fixed turning pulley 41 and the planetary timing pulley 42 .
FIG. 5 shows in greater detail the positioning mechanism. The fixed pulley 41 and the planetary timing pulley 42 are shown in relation to arm 51 that is mounted to the underside of tray 14 via bolts placed through arm mounting holes 54 . Fixed timing pulley 41 has a double-D shaft 56 that is inserted through elbow pivot 52 , then to a cam-shaped fixed sheave 58 having a shaft aperture 57 , followed by washer 76 , which are all secured via bolt 77 . The fitting 59 of pulley 41 runs in the track provided by cutout 75 in arm 51 . The fitting 59 migrates between a lower extreme edge 90 and an upper extreme edge 92 of cutout 75 . Tray level adjust bolt 55 adjusts the lap-level placement of the tray 14 .
Inserted into wrist spline hole 72 is the splined end of axle 69 that is attached to planetary timing pulley 42 . The internal multi-stepped smooth surfaces of axle 69 mesh with the sliding surfaces of bushings in wrist pivot 53 and cable sheave 64 . The planetary timing pulley 42 has an external flip groove 70 that aids in its engagement with wrist pivot 53 . The multi-stepped smooth surfaces of axle 69 provide matches with the smooth surfaces provided by the bushings of wrist pivot 53 and wrist sheave 64 of arm 51 . The multi-stepped surface of the axle 69 meshes with the wrist sheave bushing 64 , then to the wrist splines 72 of tray slide arm 68 . The planetary timing pulley assembly is then secured to tray slide arm 68 with a washer 80 and C-clip 71 .
Tray slide arm 68 contains a tray slide arm end 66 upon which a spring anchor pin fitting 67 is attached. Fitting 67 is connected to a spring 65 that in turn is connected to a draw cable 61 via cable loop 62 . The draw cable 61 is routed over the outer groove of wrist sheave 64 , thence back to fitting 59 that is attached via cable attachment catch 60 . Cable slide fitting 63 is able to migrate along cable 61 . Tray slide arm 68 is mounted in a tray slot 74 located beneath tray 14 . Attached to the tray slot 74 is a tray draw fitting 73 attached. Fitting 73 engages with the moveable cable slide fitting 63 as the cable and spring are subjected to decreasing tension as the tray 14 is deployed or increasing tension during use and storing of tray 14 .
When tray 14 is in a stowed position, the spring 65 is stretched more than when tray 14 is in a deployed position. When tray 14 is deployed, the incremental sliding motion results in rotation of the fixed timing pulley 41 within confines imposed by cutout 75 of arm 51 . Arm 51 's rotary movement is limited by fitting 59 that limits pivotal motion to the extreme edges of cutout 75 of arm 51 . During deployment of the tray 14 , arm 51 's lower rotation movement is limited as edge 90 meets fitting 59 . During stowage of the tray 14 , arm 51 's upper rotation movement is limited as edge 92 meets fitting 59 .
Referring to FIG. 6A, tray 14 deployment causes cutout 75 to migrate about fitting 59 as tensile forces are exerted through draw cable 61 , thence to cable attachment catch 60 . This results in cable slackening as cable 61 unwraps from sheave 58 . Cable slackening is then transmitted around wrist sheave 64 to spring 65 . Spring 65 is depicted in a lightly stretched state as cable slide fitting 63 is caught between draw fitting 73 and cable loop 62 . A light spring tension is sufficient to keep cable slide fitting 63 captured within draw fitting 73 and to stretch the spring lightly as the cable 61 pulls from spring anchor 67 of tray slide arm 68 .
In contrast to deployment of the tray 14 , stowage of the tray 14 , as depicted in FIG. 6B, results in a maximally tensioned spring as tray slide arm 68 pivots away from draw fitting 73 mounted to the underside of tray 14 . Spring 65 is depicted in a highly stretched state as cable slide fitting 63 is caught between draw fitting 73 and cable loop 62 . Pushing of tray 14 in a more forward position results in an increased distance between the cable sheave 64 and the double D shaft 56 that is inserted into the aperture 57 depicted in the foreground of arm 51 shown in phantom. The spring 65 is stretched more between draw fitting 73 , which has captured tray slide fitting 63 , and spring anchor 67 .
When a passenger moves the tray 14 forward for stowage, the spring 65 is subjected to increased tension. Cam 58 and arm 51 co-rotate within aperture 57 about pin 59 and double D shaft 56 of the fixed timing pulley 41 , limited to the edge 92 . More of the circumference cam engages the sheave 58 through aperture 57 . Simultaneously, both sheave 58 and arm 51 co-rotate clockwise about pin 59 inserted through cable attachment catch 60 . More of the sheave's curved path is committed to the draw cable 61 . Increased tension of draw cable 61 results and is transmitted around wrist sheave 64 , then to the cable slide fitting 63 . Clockwise tensioning rotation is limited to the upper cutout edge 92 . Spring 65 is depicted in a more stretched condition for the stowed tray 14 .
While the preferred embodiment of the invention has been illustrated and described, as noted above, many changes can be made without departing from the spirit and scope of the invention. For example, the tray 14 may be readily detachable and reattachable to tray legs 13 via a quick release device. The quick release device may be a snap insert fitting, a bayonet breech fitting, a lever release fitting, or any equivalently functional quick release mechanism.
In another alternate embodiment, tray 14 , though deployed from a moveable seatback, suitably includes tray legs 13 that are attached to a stationary section of the seat. Such a configuration matches the deployed food tray not susceptible to tilting that occurs when a seat in front of the passenger is reclined.
Accordingly, the scope of the invention is not limited by the disclosure of the preferred embodiments. Instead, the invention should be determined entirely by reference to the claims that follow. | A table that is stowable and deployable from a seatback of a passenger seat includes a substantially planar food tray with a first surface and a second surface substantially parallel to the first surface. The tray is stowed in a substantially vertical position with the first surface facing a seated passenger. The stowed tray is held in position with a moveable switch engaged against the first surface. A device for stowing and deploying the tray is mounted on the second surface. A pair of legs is mounted to the device. Each leg has a first end attached to the device and a second end attached to the seat. Upon turning the switch clear of the first surface, the device slidably urges the first surface from its stowed position to a deployed, substantially horizontal position, with the first surface facing upwards. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains to air quenching systems for heated parts characterized by its ability to uniformly cool the heated part throughout its configuration and regulate the rate of cooling during air quenching.
2. Description of the Related Art
Metal parts, usually formed of steel alloys, are commonly heat treated to improve the wear and strength characteristics of the part. The heat treating of metals is highly complex with the resultant wear and strength characteristics being determined by the percentages of carbon and other materials within the steel, or other metal, the rate of cooling, and the composition of the cooling medium. It is common to cool heated parts by the use of an oil bath quench wherein the part is rapidly cooled and the heat treatment characteristics are determined by the variables mentioned above.
While oil bath quenching is commonly used for heat treatment purposes, it is also common to use an air quench or cooling chamber utilizing moving air, to cool the heated part. Air quenching has the advantage of producing a slower cooling of the part than achieved with an oil bath quench, or the like, but, henceforth, it has been difficult to control air quenching procedures other than varying the length of time that the heated part remains in the cooling air stream.
When heat treating certain steels, particularly forgings, to produce critical parts, such as the connecting rods of internal combustion engines, in order to achieve the desired strength and wear characteristics, the selection of the steel composition is important, as is the heat treatment. The durability and strength of a part such as an engine connecting rod depends on the formation of carbon or carbide into a fine grain whose particles are rounded. Grain formation is achieved by elevating the steel temperature above 2200° F. wherein the carbide readily disburses throughout the steel, followed by slow cooling to atmospheric temperature. Slow cooling such as produced in air quenching systems produces the required pearlite grain structure necessary to achieve the desired connecting rod characteristics. To rapidly quench engine connecting rods in an oil bath produces a martensite grain which is significantly harder and more brittle than the pearlite grain structure desired.
Previously, air quenching systems have not been available wherein the heated part can be uniformly cooled by air, and wherein the rate of cooling during the cooling process could be closely controlled to consistently achieve the desired metal grain structure.
OBJECTS OF THE INVENTION
It is an object of the invention to produce an air quenching system wherein the heated part is simultaneously cooled on opposite sides to produce a uniform cooling of the part mass to achieve uniform grain structure throughout the part.
An additional object of the invention is to produce an air quenching system for heated parts wherein cooling air is simultaneously ejected upon opposite sides of the heated part and is quickly exhausted to minimize errant airflow currents in the air quenching chamber and cooling may be accurately regulated and controlled.
A further object of the invention is to provide an air quenching system for uniformly cooling heated parts throughout their mass and wherein the rate of cooling while in the quenching chamber may be regulated by controlling the rate of air flow upon the part.
Yet another object of the invention is to provide an air quenching system utilizing a conveyor belt supporting the heated part to be cooled which moves through a cooling chamber and the chamber is divided into zones having various cooling rates wherein movement of the heated part through the chamber zones closely controls the rate of cooling, and hence, the heat treat characteristics of the heated part.
SUMMARY OF THE INVENTION
An air quenching system in accord with the invention basically consists of similar upper and lower portions, the upper portion being vertically superimposed above the lower portion in a spaced relationship. A movable conveyor belt extends between the upper and lower portions for supporting the heated part to be cooled as it moves between the chamber portions during cooling.
The upper portion of the upper chamber portion and the lower portion of the lower chamber portion constitute air supply manifolds, and the lower chamber portion of the upper portion and the upper chamber portion of the lower portion constitute exhaust air manifolds. The lower surface of the upper chamber portion and the upper surface of the lower chamber portion have orifices defined therein wherein some of the orifices receive air supply tubes having an end in communication with the associated air supply chamber manifold and an inner end extending through the associated lower surface of the upper portion and the upper surface of the lower portion. Nozzles located within the inner ends of the air supply tubes form the air flowing through the tubes as it is injected in the spacing between the upper and lower chamber portions and upon the part to be cooled. Preferably, the exhaust air orifices are defined intermediate the air supply tubes.
The air supply chamber portions are supplied with pressurized air through a conduit system which, in the disclosed embodiment, utilizes three air supply branches each having an air pump in the form of a fan controlled by a variable frequency drive. The air supply branches communicate with the air supply manifolds by ports, and two ports are associated with each air supply duct branch. In this manner, six air supply ports are spaced along the length of the air quenching chamber in the direction of the heated part movement and by controlling the rate of the fan operation, and by the use of dampers, the rate of air supply into the air supply manifolds can be varied along the length of the air quench chamber to produce zones permitting a higher volume of air to be initially ejected upon the heated part, and a lower volume of air can be ejected on the heated part as it approaches the quenching chamber exit. In this manner, the rate of cooling of the part can be controlled to regulate the grain structure of the cooled part.
In a similar manner, the air exhaust system includes three branches each having a variable frequency drive fan located therein, and the exhaust branches communicate with the exhaust manifold through ports spaced along the manifold length. The exhaust system fans create a vacuum within the exhaust chamber manifolds drawing the air ejected from the air tubes into the orifices defined in the air chamber surfaces quickly removing the air which has been heated by the heated part and thereby maintaining an accurate control of the flow and temperature of the exhaust air. The exhaust air rate may also be controlled by zones throughout the length of the air quenching system by regulating the fan speed and by the use of dampers controlling the air through the air exhaust ports communicating between the air exhaust manifolds and branches.
The conveyor extending between the upper and lower chamber portions includes many openings as to be freely air pervious. Preferably, the conveyor belt is formed of an open chain link metal configuration, or the like, which is flexible for passing around the conveyor rollers, and permits air to flow therethrough with no resistance. In this manner, the air being ejected through air tubes and nozzles of both the upper and lower chamber portions will directly engage the upper and lower sides, respectively, of the heated part permitting the heated part to be quickly and uniformly cooled.
The zone control of the cooling air, and the injecting of the cooling air upon opposite sides of the heat part produce a degree of control in an air quenching system not previously attainable, and the rapid removal of the heated exhaust air from adjacent the part being cooled permits a control of the rate of air quenching not previously known.
BRIEF DESCRIPTION OF THE DRAWINGS
The aforementioned objects and advantages of the invention will be appreciated from the following description and accompanying drawings wherein:
FIG. 1 is an elevational view of a cooling chamber in accord with the invention as taken from the exit end of the chamber,
FIG. 2 is a side elevational view of an air quench cooling chamber in accord with the invention illustrating the air exhaust duct system as taken from the left of FIG. 1,
FIG. 3 is a schematic view taken transversely through the length of the cooling chamber, and
FIG. 4 is an enlarged elevational detail sectional view taken through the upper chamber portion illustrating the air supply and air exhaust manifold and air tubes.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The air quenching chamber in accord with the invention is usually mounted within an enclosure or housing generally represented at 10, and the air quench chamber 12 is located within this housing. The air quench chamber 12 requires a cooling air supply system generally indicated at 14 and an air exhaust system generally indicated at 16, FIGS. 1 and 2. The upper end of the air supply and air exhaust systems 14 and 16 will normally extend through the roof of the building enclosing the housing 10, and the upper end of the system 14 normally includes a baffle or air guide which prevents the entrance of rain, while the upper end of the exhaust system 16 may include a dust collector or filter to comply with environmental regulations.
As best illustrated in FIG. 3, the air quenching chamber 12 consists of identical upper and lower chamber portions 18 and 20, respectively. The portions 18 and 20 are vertically related, with the portion 18 being directly above the portion 20 wherein a vertical spacing 22 exists between the upper and lower chamber portions. Within the spacing 22, an endless conveyor 24 is located upon which the heated part to be cooled, indicated at 26, is supported. The conveyor 24 is supported upon rollers 28, FIG. 2, and the conveyor is driven by a conventional motor drive system, not shown. The conveyor 24 is air pervious as the cooling air from the lower chamber portion 20 must pass therethrough, and the conveyor 24 may include a plurality of openings, or may be formed of an open flexible material such as chain link or the like.
Both the upper chamber portion 18 and the lower chamber portion 20 are horizontally divided by plates 30, FIG. 3, wherein approximately one-half of the volume of a chamber portion exists on each side of the associated plate 30.
With reference to FIG. 3, the chamber portions located the greatest distance from the conveyor 24 constitute air supply manifolds 32, while the portion of the chambers closest to the conveyor 24 constitute air exhaust manifolds 34. The air supply conduits 36 include a variable speed fan insert 38, FIG. 3, and pressurized air from the air supply system 14 passes through conduit branches 40 and volume control dampers 42 through ports 44 whereby the air supply manifolds 32 will be pressurized by the fan 38.
The air exhaust conduit 46, FIG. 3, includes a variable speed drive fan 48, and the exhaust air passes through the air exhaust manifolds 34 through conduit branches 50 whose volume may be controlled by dampers 52. The ports 54 defined in the air exhaust manifolds 34 establish communication between the exhaust manifolds and the air exhaust system 16.
The innermost surface of the air quench chamber upper portion 18 and innermost surface of lower portion 20, i.e. the surfaces closest to the conveyor 24, is defined by inner plates 56 which define the lower surface of the upper chamber portion 18 and the upper surface of the lower chamber portion 20.
The inner plates 30 separating the upper and lower chamber portions 18.and 20 into air supply and air exhaust manifolds each include a plurality of circular holes 58, FIG. 4, and the inner plates 56 of the chamber portions include a plurality of exhaust air orifices 60. Additionally, the plates 56 include a plurality of circular holes 62 in vertical alignment with the holes 58 as will be appreciated from FIG. 4.
A plurality of cylindrical air tubes 64 are interposed between the plates 30 and 56. The air tube inlet end 66 is received within the plate holes 58, while the air tube exit end 68 is received within the holes 62 defined in the plates 56. A conical nozzle 70 is located within the air tube exit ends 68 for shaping and constricting the air flowing through the tubes 64.
As will be appreciated from FIG. 4, the air tube inlet ends 66 are in communication with the air supply manifold 32 of the associated air quench chamber portion, and the air tube exit 68 and nozzle 70 communicates with the spacing 22 located between the upper and lower chamber portions 18 and 20 for directing air toward both the upper and lower portions of the conveyor 24 and the heated part 26 supported upon the conveyor. The general air flow paths are indicated by arrows in FIGS. 3 and 4.
In the disclosed embodiment, cooling air is introduced into the air supply manifolds 32 at six separate locations spaced along the length of the air quench chamber 12, and the exhaust air is removed from the air exhaust manifolds 34 at six locations longitudinally spaced along the air quench chamber. The distribution of the air to and from the air quench chamber is best illustrated in FIG. 2 wherein the air quench chamber air exhaust system 16 is illustrated in elevation. The air exhaust system 16 branches into three exhaust duct branches 72, 74 and 76, and these branches, in turn, each branch into a pair of lower ducts 77 disposed adjacent the sides of the air quench chamber 12 wherein the lower duct 77 communicate with the exhaust manifolds 34 through short duct branches as schematically represented at 50 in FIG. 3 through volume dampers schematically represented at 52 whereby the air within the lower ducts 77 is introduced into the exhaust manifolds 34 throughout the air chamber length through the ports 54 illustrated in dotted lines in FIG. 2.
Each of the vertical duct branches 72, 74 and 76 includes a fan insert 78 in which an electric fan is located having a variable frequency drive wherein the speed of the fan can be regulated and between the fan speed control, and the volume dampers 52, the rate of exhausting of air through each of the duct branches 77 and 72, and 76 can be closely regulated.
The air supply system 14 duct system is similar to that previously described with respect to the air exhaust system. The vertical air supply duct 80, FIG. 1, branches into three duct branches which, in turn, separate into lower duct branches 81 similar to the lower ducts 77 in the exhaust system.
The air supply for the system 14 is provided by a fan insert 82, FIG. 1, containing a variable frequency drive motor wherein each of the primary three branches of the air supply system 14 can be closely controlled,. and in conjunction with the dampers 42, the air flow into the air supply manifolds 32 through the ports 44 can be closely regulated.
In operation, the air flow characteristics into the air supply manifolds 32 will be determined by adjusting the rate of air moved by the fan inserts 82, three in number, and the setting of the volume dampers 42. Similarly, the rate of air exhausting from the air exhaust manifolds 34 will be determined by the rate of air flow as pre-selected through the fan inserts 78 and the dampers 52. Usually, in air quenching processes, it is desirable to, initially, produce a more rapid rate of cooling of the heated part, and thereafter reduce the rate of cooling to closely control the grain growth within the heated part 26 during cooling. This regulation of the rate of cooling is determined by the rate of flow of cooling air through the system 14 and the exhausting of the air through the exhaust system 16 as adjusted by the fans within inserts 82 and 78, and the adjustment of the dampers 42 and 52. In effect, the air supply manifolds 32 and air exhaust manifolds 34 will be divided into zones along the length of the air quench chamber 12, such zones being determined by the rate the air is forced into the air supply manifolds 32 and removed from the air exhaust manifolds 34. It is desirable that the rate of air introduced and removed into each zone be substantially the same in order to eliminate "back pressure"0 or cause excessive air to flow longitudinally within the spacing 22. With the embodiment shown in FIG. 2, it is possible to create as many as six "zones" in view of the six duct branches 77.
As will be appreciated from FIGS. 3 and 4, the air exhaust orifices 60 are located intermediate the air tubes 64, and the preferred air flow from the air tubes and through the orifices 60 will be as indicated by the arrows in FIGS. 3 and 4. Preferably, air injected into the spacing 22 and upon the heated part 26 is quickly removed from the proximity of the heated part, and in this manner, the rate of cooling can be closely regulated.
With reference to FIG. 2, the air quench chamber 12 includes an inlet 86 defined in the housing 10 at the conveyor 24 whereby the heated part 26 may be placed upon the conveyor 24. Upon the part passing through the air quench chamber 12, the heated part is discharged through the exit 88. Accordingly, the rate of air flow through the duct 72 will usually be greater than the rate of air flow through the duct 74, and the air flow through duct 74 will usually be greater than that through duct 76 whereby a progressively slower rate of cooling of the heated part occurs as the part moves from inlet 86 to exit 88.
Because the conveyor 24 permits the cooling air from portion 20 to freely pass therethrough, both the upper and lower sides of the heated part 26 are simultaneously cooled and this bi-directional flow of cooling air upon the heated part permits better control of the cooling rate than is achievable with the usual monodirectional air flow utilized in conventional air quenching systems. As shown in FIG. 3, the cooling air directly flowing upon the upper and lower sides of the heated part 26 is quickly removed through the exhaust manifold orifices 60 and cooling due to uncontrolled air flow within the spacing 22 is minimized which adds to the close regulation of the rate of cooling achieved by the invention.
While the various zones of the rate of cooling through the chamber 12 can be produced solely by regulating the air flow through the air supply ports 44 and the exhaust ports 54, a more definite separation between zones can be achieved by using zone partitions 84, FIG. 4, between air supply and air exhaust components. The zone partitions 84 are vertically oriented and located within both the air supply manifolds 32 and the air exhaust manifolds 34 and prevent the air flowing through the ducts 72, 74 and 76, and the equivalent air supply ducts, from intermixing.
It is appreciated that various modifications to the inventive concepts may be apparent to those skilled in the art without departing from the spirit and scope of the invention. | An air quenching system for cooling heated parts under controlled conditions having cooling air ejection nozzles located in opposed relation on opposite sides of the heated part and air exhaust orifices adjacent the air supply nozzles for quickly removing the cooling air after engagement with the heated part. The cooling air, and exhausting thereof, may be controlled in various zones spaced along the length of the air quenching system for controlling air flow and the rate of cooling. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a stylus, in particular, to a stylus for a coordinate-measuring machine and having a stem with a break-off point. The present invention also relates to a method of forming a stylus with a break-off point, and to a coordinate-measuring machine having a stylus with a break-off point.
[0003] 2. Description of the Prior Art
[0004] As known, styluses are used in coordinate-measuring machines which perform different measuring tasks from a simple measurement of a distance between two spaced from each other objects to a measurement of the three-dimensional surfaces.
[0005] A stylus, which is usually used in coordinate-measuring machines, usually has a cylindrical stem formed of steel or ceramics and at one end of which, a mechanical touch element is attached, mostly, in a form of a ground ruby ball having a predetermined radius. The touch element is used for taking measurements of a specimen. The other end of the stem is connected with the touch probe which, on one hand, provides for displacement of the stylus and, on the other hand, contain sensors for determining the stylus displacements.
[0006] Coordinate-measuring machines can be divided in different groups. The first group includes linear measuring systems which output a position of a stylus, which is displaced in a measuring direction, as a measurement value.
[0007] The linear measurement systems permit to conduct simple distance measurements or obtain a height profile of a workpiece movable relative to the stylus.
[0008] The second group includes coordinate-measuring machines having a resiliently biased stylus that can be deflected in any direction. These so-called three-dimensional measurement systems function based on different principles.
[0009] Three-dimensional systems can include linear and rotary encoders which completely determine the deviation of the stylus and, thereby, provide for determination of coordinates of the touch element. These machines are designated as measuring touch systems. They insure determination of measurement values with a statical or dynamic operation, i.e., specimen and the touch element can, at the time of the acquisition of a measurement value, remain stationary with respect to each other or displace relative to each other.
[0010] Also known are so-called switching touch systems. With these systems, a trigger signal is generated at a predetermined deviation of the stylus. The signal is transmitted to a control unit which then receives coordinates from an available measuring system, e.g., of a machine tool. The switching systems operate only dynamically. After generation of the measurement signal, the displacement of the specimen or the touch system should be stopped in order that the maximum allowable deviation of the stylus is not exceeded.
[0011] It is not a trivial object to determine, in all cases, based on a position of the stylus, with a touch probe, the coordinates of the measurement point, i.e., the contact point of the touch element with the specimen. For the determination of coordinates, the measurement direction, deflection of the stylus, geometry of the touch element, and direction of the surface perpendicular of the specimen in the measurement point, all need be considered. The discussion of the coordinate determination can be found in an article of T. Pfeifer and A vom Hemdt “Berechung der Basiselemente und die Tasterkompensation in der koordinatenmesstechnik (Calculation of Basic Elements and Stylus Compensation)” published in a magazine “Technisches Messen (Technical Measurements)” 5/90, published by R. Oldenbourg Verlag.
[0012] Flexural characteristics, i.e., flexural strength of the stylus, also play an important role in the quality of the measurement with a coordinate-measuring machine.
[0013] In order to prevent damage of the sensitive mechanics or of the measuring system in the touch probe in case of an uncontrolled collision of the stylus with the specimen or other parts, it is desirable to provide the stylus with a predetermined break-off region that would prevent transmission of a large force.
[0014] German Publication DE 33 14 318 discloses a coordinate-measuring machine including an inductive measurement system that can determine a position of a stylus in one direction. The predetermined break-off region is obtained by a noticeable reduction of the cross-section of the stylus stem. The predetermined break-off region should protect this unidimensional measuring system against a large load acting transverse to the measurement direction. In this case, a particularly high flexural strength of the stylus is not required as bending of the stylus in a direction transverse to the measuring direction only slightly influences the measurement.
[0015] An object of the present invention is to provide a stylus having a predetermined break-off region and which can be economically produced and the flexural strength of which is not reduced at all or is reduced only insignificantly by the break-off region.
[0016] Another object of the present invention is to provide a cost-effective method of producing a stylus having a predetermined break-off region and which would not affect or affect only insignificantly the flexural strength of the stylus.
[0017] A further object of the present invention is to provide a coordinate-measuring machine having a stylus with a break-off region and which can be economically produced and the flexural strength of which is not affected or is affected only insignificantly by the manufacturing process of forming the break-off region.
SUMMARY OF THE INVENTION
[0018] These and other objects of the present invention, which will become apparent hereinafter are achieved by providing a stylus having a stem with a break-off region consisting of a changed structure of the stem material, by providing a method with which the break-off region is formed and according to which the changing of the structure of the stem material in a stem region in which the break-off region is to be formed, is effected by heating the respective stem region without any substantial removal of the material, and by providing a coordinate-measuring machine having a stylus the break-off region of which is formed by a changed structure of the stylus stem material.
[0019] According to the present invention, the stylus stem includes, as it has been discussed above, a region with a changed structure in which in case of application of mechanical load, local stresses are generated which lead to breaking of the stylus with a reduced force.
[0020] Advantageously, the changing of the structure in the break-off region is effected with heating the predetermined stem region with a laser beam. The finess of the obtained structure and the fact that no or almost no material is removed insure that the flexural characteristics of the stylus, and thereby, the measurement characteristics remain unchanged or are changed only insignificantly.
[0021] The novel features of the present invention, which are considered as characteristic for the invention, are set forth in the appended claims. The invention itself, however, both as to is construction and its mode of operation, together with additional advantages and objects thereof, will be best understood from the following detailed description of preferred embodiments, when read with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The drawings show:
[0023] [0023]FIG. 1 a schematic view of a coordinate-measuring machine; and
[0024] [0024]FIG. 2 a front elevational view of a stylus with a predetermined breaking point.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] A coordinate-measuring machine 1 , which is shown in FIG. 1, has a stylus 2 , and a touch probe 3 . The stylus 2 has a stem 4 , which is formed of a hard metal, and a touch element 5 in a form of a ruby ball. The stem 4 has a predetermined break-off point 6 that consists of a region the structure of material of which has been changed by heat treatment of the hard metal the stem 4 is made of. The touch probe 3 includes a device that provides for movement of the touch element 5 in all directions and permits to calculate a measurement point 7 between the touch element 5 and a specimen 8 based on a measurement direction X and a position of the stylus 2 .
[0026] [0026]FIG. 2, as discussed above, shows the stylus 2 according to the present invention for use with a coordinate-measuring machine. The inventive stylus 2 includes a stem 4 , a touch element 5 , a predetermined break-off point 6 , and a thread 9 with which the stylus 2 is secured in the touch probe.
[0027] The predetermined break-off point 6 is obtained when the stem 4 of the stylus 2 is subjected to a local heating with a tunable nd-yag (neodym-yttrium-aluminum-granat) laser 10 . The diameter of a laser beam 11 is, e.g., so selected that the heating region of the stem 4 has a width of about 0.25 mm. As the measurement characteristic of the cylindrical stylus 2 transverse to a measurement direction should be the same in all directions, the stem 4 is irradiated along its entire circumference. The intensity of the laser beam 11 and the irradiation duration should be such that, e.g., a structural change up to a depth of about 0.2 mm in the volume of the stem 4 is achieved. Because no removal of material or a minimal removal of material occurs, the diameter of the stem would not change or would change only insignificantly. E.g., for the stem 4 formed of a hard metal and having a diameter 2 mm and a distance between the predetermined break-off point 6 and the touch element 5 of about 30 mm, the break-off force F is reduced to about 20N in comparison with the breaking force of 60N for an identical stylus but without a predetermined break-off point. With application of a load in the direction of the stylus, the predetermined break-off point 6 permits to reduce the break-off force from about 900N to about 650N.
[0028] The reduction of the break-off force F results from the local tension in the changed material structure in the region of the predetermined break-off point. Upon application of the break-off force F, the local tension, which is produced in the region of the predetermined break-off point, is noticeably greater than the tension in the material without a break-off point.
[0029] The advantage of the present invention, as described above, consists in that the break-off point is clearly visible, and clear differences between styluses with and without a break-off point exist.
[0030] According to a further embodiment of the present invention, it is possible to provide an adaptation member with a predetermined break-off point of the type described above. Such an adaptation member is generally screwed in between the stylus and the touch probe or between the touch element and the stem.
[0031] For the heat treatment and for changing the material structure of the stem 4 , not only laser irradiation can be used. Rather, all forms of high-energy irradiation, which have the necessary intensity and focusing, can be used. The stem 4 can be made not only of a hard metal. Also, the shape of the predetermined break-off point 6 can be adapted to existing conditions. Thus, when appropriate, instead of irradiation of the entire circumference of the stem 4 in the region of the predetermined break-off point 6 , only separate regions of the circumference can be irradiated. Alternatively, components, which have a preferential break-off direction, can be used.
[0032] Though the present invention was shown and described with references to the preferred embodiments, such are merely illustrative of the present invention and are not to be construed as a limitation thereof, and various modifications of the present invention will be apparent to those skilled in the art. It is, therefore, not intended that the present invention be limited to the disclosed embodiments or details thereof, and the present invention includes all variations and/or alternative embodiments within the spirit and scope of the present invention as defined by the appended claims. | A stylus including a stem, and a break-off region provided in the stem and consisting of a changed structure of a stem material, and a method of forming the stylus according to which the change of the structure of a stem material is effected by heat treatment of a region of the stem in which the break-off region is to be provided. | 6 |
RELATED APPLICATIONS
[0001] This application is a continuation-in-part of application Ser. No. 07/834,345 filed Feb. 12, 1992 (now U.S. Pat. No. ______ issued ______), which is a division of application Ser. No. 07/210,520 filed Jun. 23, 1988 (now U.S. Pat. No. 5,091,576 issued Feb. 25, 1992), which is a continuation-in-part of application Ser. No. 07/066,227 filed Jun. 25, 1987 (now abandoned), which is a continuation-in-part of application Ser. No. 06/936,835 filed Dec. 2, 1986 (now abandoned).
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0002] The present invention relates to novel polyamines having anti-neoplastic, anti-diarrheal, anti-peristaltic, gastrointestinal anti-spasmodic, anti-viral, anti-retroviral, anti-psoriasis and insecticidal activities, as well as pharmaceutical compositions and methods of treatment based thereon and methods for their preparation.
[0003] In recent years, a great deal of attention has been focussed on the polyamines, e.g., spermidine, norspermidine, homospermidine, 1,4-diaminobutane (putrescine) and spermine. These studies have been largely directed at the biological properties of the polyamines probably because of the role they play in proliferative processes. It was shown early on that the polyamine levels in dividing cells, e.g., cancer cells, are much higher than in resting cells. See Janne et al, A. Biochim. Biophys. Acta., Vol. 473, p. 241 (1978); Fillingame et al, Proc. Natl. Acad. Sci. U.S.A., Vol. 72, p. 4042 (1975); Metcalf et al, J. Am. Chem. Soc., Vol. 100, p. 2551 (1978); Flink et al, Nature (London), Vol. 253, p. 62 (1975); and Pegg et al, Polyamine Metabolism and Function, Am. J. Cell. Physiol., Vol. 243, pp. 212-221 (1982).
[0004] Several lines of evidence indicate that polyamines, particularly spermidine, are required for cell proliferation: (i) they are found in greater amounts in growing than in non-growing tissues; (ii) prokaryotic and eukaryotic mutants deficient in polyamine biosynthesis are auxotrophic for polyamines; and (iii) inhibitors specific for polyamine biosynthesis also inhibit cell growth. Despite this evidence, the precise biological role of polyamines in cell proliferation is uncertain. It has been suggested that polyamines, by virtue of their charged nature under physiological conditions and their conformational flexibility, might serve to stabilize macromolecules such as nucleic acids by anion neutralization. See Dkystra et al, Science, Vol. 149, p. 48 (1965); Russell et al, Polyamines as Biochemical Markers of Normal and Malignant Growth (Raven, New York, 1978); Hirschfield et al, J. Bacteriol., Vol. 101, p. 725 (1970); Hafner et al, J. Biol. Chem., Vol. 254, p. 12419 (1979); Cohn et al, J. Bacteriol., Vol. 134, p. 208 (1978); Pohjatipelto et al, Nature (London), Vol. 293, p. 475 (1981); Mamont et al, Biochem. Biophys. Res. Commun., Vol. 81, p. 58 (1978); Bloomfield et al, Polyamines in Biology and Medicine (D. R. Morris and L. J. Morton, eds., Dekker, New York, 1981), pp. 183-205; Gosule et al, Nature, Vol. 259, p. 333 (1976); Gabbay et al, Ann. N.Y. Acad. Sci., Vol. 171, p. 810 (1970); Suwalsky et al, J. Mol. Biol., Vol. 42, p. 363 (1969); and Liquori et al, J. Mol. Biol., Vol. 24, p. 113 (1968).
[0005] However, regardless of the reason for increased polyamine levels, the phenomenon can be and has been exploited in chemotherapy. See Sjoerdsma et al, Butter-worths Int. Med. Rev.: Clin. Pharmacol. Thera., Vol. 35, p. 287 (1984); Israel et al, J. Med. Chem., Vol. 16, p. 1 (1973); Morris et al, Polyamines in Biology and Medicine; Dekker, New York, p. 223 (1981); and Wang et al, Biochem. Biophys. Res. Commun., Vol. 94, p. 85 (1980).
[0006] It is an object of the present invention to provide novel polyamines having a wide variety of biological activities.
[0007] It is another object of the present invention to provide novel compositions and methods of treatment and application based on the biological activities of the polyamines of the invention.
[0008] It is an additional object of the invention to provide novel methods for preparing the polyamines of the invention.
BRIEF DESCRIPTION OF THE DRAWING
[0009] [0009]FIG. 1 is a diagram of a reaction scheme for preparing the polyamines of the invention.
SUMMARY OF THE INVENTION
[0010] The above and other objects are realized by the present invention, one embodiment of which comprises a polyamine having the formula:
[0011] wherein R 1 and R 2 are alkyl, aralkyl or aryl having up to lo carbon atoms; and
[0012] a and b may be the same or different and are integers from 1 to 8; or
[0013] a salt thereof with a pharmaceutically acceptable acid.
[0014] Further embodiments of the invention relate to anti-neoplastic, anti-diarrheal, anti-peristaltic, gastro-intestinal anti-spasmodic, anti-viral, anti-retroviral, anti-psoriasis and insecticidal compositions comprising biologically effective amounts of the above-described amines and biologically acceptable carriers therefor.
[0015] Still further embodiments of the invention comprise methods of treatment, administration or application of biologically effective amounts of the polyamines of the invention.
[0016] Final embodiments of the invention relate to methods for preparing the polyamines described above comprising:
[0017] 1. reacting a compound having the formula:
[0018] with a compound having the formula:
X—(CH 2 ) b —X
[0019] wherein Q is an amine protective group, e.g., tosyl, mesitylene sulfonyl, and the like,
[0020] X is a leaving group, e.g., Cl, Br, I, O-tosyl, and the like, which can be displaced with the
[0021] anion of compound (III), and
[0022] R 1 , R 2 and a have the meanings ascribed above to produce a compound of the formula:
[0023] and
[0024] 2. deprotecting compound (IV) to remove said Q groups to produce the polyamines of the invention.
[0025] The above method may optionally include the preliminary steps of:
[0026] 3. reducing a compound of the formula:
[0027] to produce a compound of the formula:
[0028] and
[0029] 4. reacting the amino groups of compound (II) with a reagent to produce a compound having the formula of compound (III).
DETAILED DESCRIPTION OF THE INVENTION
[0030] The polyamines of the present invention possess virtually the same biological activities as the corresponding polyamines described in U.S. patent application Ser. Nos. 07/834,345 filed Feb. 12, 1992; 07/066,227 filed Jun. 25, 1987; and 06/936,835 filed Dec. 2, 1986.
[0031] Polyamines corresponding to those of the invention wherein R 1 and R 2 are hydrogen are metabolized by the body when administered to human and non-human patients. The metabolic products of these polyamines are more toxic than the parent compounds.
[0032] The steric hindrance provided by the R 2 groups renders the polyamines of the present invention difficult to metabolize, thereby extending the half-life of the polyamine drug in the body and reducing the potential toxic side effects accompanying the metabolic products thereof.
[0033] Referring to FIG. 1, the polyamines of the present invention are prepared by the novel method described below.
[0034] Compound (I) is prepared by the conjugate addition of an alkyl amine with an appropriate unsaturated nitrile to produce an intermediate nitrile amine according to the reaction scheme:
[0035] An alternate synthesis of compound (I) is found in Kurihara et al, J. Pharm. Soc. Japan, Vol. 75, pages 1267-1269 (1955); and Chem. Abs., Vol. 50:8636b (1956).
[0036] The cyano group of the intermediate is then reduced (e.g., H 2 , Raney nickel in methanolic NH 3 ) to produce the intermediate:
[0037] The latter is reacted with a suitable reagent which provides an amine protective group on the nitrogen atoms thereof [e.g., tosyl (Ts) chloride, mesitylene sulfonyl chloride, and the like], thereby producing a compound of the formula:
[0038] A compound having termini which can N-alkylate the anion of compound (III),
[0039] e.g., dibromobutane, is then reacted with compound (III) (in NaH, DMF) to produce a tetratosyl polyamine having the formula:
[0040] The protective tosyl (Ts) groups are removed (e.g., Na, NH 3 , THF) to yield the polyamine:
[0041] The polyamines are preferably utilized as their acid addition salts with pharmaceutically acceptable acids, e.g., HCl, p-toluene sulfonic acid, methylene sulfonic acid, and the like.
[0042] In the structural formulae set forth herein, the terms “aryl” and “aralkyl” are intended to embrace any aromatic group whose chemical and physical properties do not adversely affect the biological activities of the polyamines and which do not adversely affect the efficacy and safety of the polyamines for therapeutic applications.
[0043] The anti-neoplastic activity (L1210) of the polyamines of the present invention was compared with that of the corresponding N 1 , N 4 -unsubstituted polyamines according to the following method and was found to be of about equal quality.
[0044] Murine L1210 leukemia cells were maintained in logarithmic growth as a suspension culture in RPMI 1640 containing 2% HEPES-MOPS buffer and 10% fetal calf serum as described by Porter et al, Science, Vol. 219, pages 1083-1085 (1983). Cultures were treated while in logarithmic growth (0.5 to 1×10 5 cells/mL) with the test compounds at concentrations ranging from 10 −6 to 10 −2 M. After 48 and 96 hours, cells were counted by electronic particle analysis and viability determinations with trypan blue.
[0045] The results are set forth in Table 1 below.
TABLE 1 L1210 Polyamine Analogue IC 50 (μM) 48 h 96 h K i (μM) 30 0.18 1.6 DESPM 50 0.1 — “crotyl” DESPM, or 1,12-diMe DESPM (4)
[0046] The invention is illustrated by the following non-limiting examples, wherein silica gel 60 (70-230 mesh) was used for column chromatography. Proton NMR spectra were recorded on a Varian EM-390 instrument and were run in CHCl 3 or D 2 O with chemical shifts given in parts per million down-field from an internal tetramethylsilane or HOD (δ4.7) standard, respectively (coupling constants are in hertz).
EXAMPLE 1
3-(N-Ethylamino)butanenitrile (I)
[0047] 50% NaOH (w/w, 32 mL) was cautiously added to ethylamine hydrochloride (44.13 g, 0.54 mol) at 0° C. Crotononitrile (cis and trans, 25 mL, 0.31 mol) was added to the cold suspension over 3 min., and the mixture was stirred for 18 hours (0° C. to room temperature). The reaction was heated on a boiling water bath for 1 hour 20 min. and allowed to cool. Ether (100 mL) was added, and then 1 N NaOH (50 mL) was added. The layers were separated, and the aqueous phase was further extracted with ether (2×100 mL). The combined organic portion was washed with brine (50 mL). The brine was extracted with ether (4 ×50 mL) and all of the organic extracts were evaporated in vacuo. A short path distillation of the crude product afforded 19.25 g (55%) of I bp 38-45.5° C./0.06 mm. NMR δ1.00-1.32 (m, 7 H), 2.42 (d, 2 H, J=6), 2.63 (q, 2 H, J=7), 3.03 (sextet, 1 H, J=6).
N-Ethyl-1-methyl-1,3-diaminopropane dihydrochloride (II)
[0048] Raney nickel (W-2 grade, 13.18 g) and then concentrated NH 4 OH (50 mL) were added to a solution of I (19.21 g, 0.171 mol) in methanol (207 mL) in a 500 mL Parr bottle. The suspension was cooled to 0° C., and ammonia was gently bubbled in for 40 min. Hydrogenation was carried out on a Parr shaker for 10 hours at 50-55 psi. The catalyst was filtered off (Celite) and the filtrate was concentrated. Bulb to bulb distillation of the crude product, up to 66° C./0.005 mm, followed by addition of EtOH and concentrated HCl (35 mL), and evaporation and drying gave 29.11 g (90%) of II as a white solid. NMR (D 2 O) δ1.28-1.55 (m, 6 H), 1.8-2.5 (m, 2 H), 3.12-3.75 (m, 5 H).
N,N′-Bis(p-toluenesulfonyl)-N-ethyl-1-methyl-1,3-diaminopropane (III)
[0049] A solution of p-toluenesulfonyl chloride (17.01 g, 89.2 mmol) in CH 2 Cl 2 (300 mL) was added to a solution of II (8.89 g, 47.0 mmol) in 1 N NaOH (300 mL) which had been cooled to 0° C. After addition was complete, the biphasic mixture was stirred for 14 hours (0° C. to room temperature). The layers were separated and the aqueous portion was extracted with CH 2 Cl 2 (2×50 mL). The combined organic phase was washed with 1 N HCl (2×100 mL) and H 2 O (100 mL) and evaporated in vacuo. Column chromatography on silica gel eluting with 3% EtOH/CHCl 3 produced 7.46 g (39%) of III. NMR δ0.77 (d, 3 H, J=7), 1.15 (t, 3 H, J=7), 1.45-1.76 (m, 2 H), 2.40 (s, 6 H), 2.79-3.25 (m, 4 H), 3.70-4.08 (m, 1 H), 5.47 (t, 1 H, J=7), 7.13-7.81 (m, 8 H). Anal. calcd. for C 20 H 28 N 2 O 4 S 2 : C, 56.58; H, 6.65; N, 6.60. Found: C, 56.60; H, 6.64; N, 6.65.
N 1 ,N 12 -Diethyl-1,12-dimethyl-N 1 ,N 4 ,N 9 ,N 12 -tetra (p-toluenesulfonyl)spermine (IV)
[0050] Sodium hydride (80% in oil, 0.45 g, 15.0 mmol) was added to a solution of III (4.98 g, 11.7 mmol) in DMF (95 mL). The suspension was stirred for 6 min. at room temperature. 1,4-Dibromobutane (0.65 mL, 5.44 mmol) was introduced and the reaction mixture was heated at 80° C. for 4.5 hours. After cooling to 0° C., excess EtOH was cautiously added to quench residual NaH, and solvents were removed under high vacuum. 1 N NaOH (100 mL) was added to the residue, followed by extraction with CH 2 Cl 2 (3×100 mL). The combined organic phase was washed with H 2 O (100 mL) and evaporated in vacuo. Column chromatography on silica gel eluting with 1.5% CH 3 OH/CHCl 3 led to 2.55 g (52%) of IV as a white amorphous solid. NMR δ0.91 (d, 6 H, J=7), 1.24 (t, 6 H, J=7), 1.45-1.95 (m, 8 H), 2.37 and 2.39 (2 s, 12 H), 2.9-3.3 (m, 12 H), 3.63-4.05 (m, 2 H), 7.1-7.8 (m, 8 H).
N 1 ,N 12 -diethyl-1,12-dimethylspermine (V)
[0051] A solution of IV (2.54 g, 2.81 mmol) in dry THF (150 mL) was cooled to −78° C. under N 2 . Ammonia (450 mL) was condensed using a dry ice condenser and then sodium (2.93 g, 0.127 mol) was added in portions. After the reaction was stirred for 1 day (−78° C. to room temperature), EtOH (100 mL) was added at 0° C., and solvents were removed, followed by extraction with CH 2 Cl 2 (3×200 mL). The organic portion was evaporated and the residue was distilled (bulb to bulb, up to 123° C./0.005 mm), followed by the addition of EtOH and concentrated HCl (2 mL) and evaporation, giving crude tetrahydrochloride salt (V). The product was converted to its tetra(tert-butoxycarbonyl) derivative (BOC-ON, NEt 3 , aq THF), which was purified by column chromatography on silica gel eluting with 4% EtOH/CHCl 3 . BOC group removal (TFA), extraction as above and treatment with ethanolic HCl furnished 0.38 g (31%) of V as a white solid. NMR (D 2 O), δ1.2-1.5 (m, 12 H), 1.68-2.37 (m, 8 H), 2.98-3.67 (m, 14 H). Anal. calcd. for C 16 H 42 Cl 4 N 4 ; C, 44.45; H, 9.79; N, 12.96. Found: C, 44.37, H, 9.73, N, 12.94. | wherein R 1 and R 2 are alkyl, aralkyl or aryl having up to 10 carbon atoms; and
a and b may be the same or different and are integers from 1 to 8; or
a salt thereof with a pharmaceutically acceptable acid. Anti-neoplastic, anti-diarrheal, anti-peristaltic, gastro-intestinal anti-spasmodic, anti-viral, anti-retroviral, anti-psoriasis and insecticidal compositions comprising biologically effective amounts of the above-described amines and biologically acceptable carriers therefor are also disclosed, as well as methods of treatment, administration or application of biologically effective amounts of the polyamines of the invention. Also disclosed are methods for preparing the polyamines of the invention. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a support for a computer peripheral device, and in particular, to a support for a computer peripheral device that can be positioned to stand by itself on a working surface or to clamp an object.
2. Description of the Prior Art
Computer peripheral devices are commonly used in many applications, such as for web cams, microphones, speakers, and security monitoring, among others. However, because a user's desk space is usually crowded and limited, it is important to provide supports for these peripherals that will help to conserve precious desk space.
SUMMARY OF THE DISCLOSURE
It is an object of the present invention to provide a steady clamping force for a computer peripheral device support.
It is another object of the present invention to provide a support for a computer peripheral device that is capable of either standing on a working surface or clamping on an object.
In order to accomplish the objects of the present invention, the present invention provides a support for a computer peripheral device. The support has a base, a post having a first end extending through the base and a second end that couples a computer peripheral device, and a pair of base supports. Each base support has an extension which is received within the base and which engages the first end of the post. When the post is rotated, the base supports are separated from each other to define a clamping space therebetween.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of a support according to the present invention.
FIG. 2 is a perspective view of the support of FIG. 1 .
FIG. 3 is a bottom perspective view of a bottom plate of the support of FIG. 1 .
FIG. 4A is a cross-sectional view of the support of FIG. 1 .
FIG. 4B is another cross-sectional view of the support of FIG. 1 .
FIG. 5A is a perspective view of the support of FIG. 1 shown in use with a web cam in a standing position.
FIG. 5B is a simplified top plan view of the support when in the position shown in FIG. 5A .
FIG. 6A is a perspective view of the support of FIG. 1 shown in use with a web cam in a clamping position.
FIG. 6B is a simplified top plan view of the support when in the position shown in FIG. 6A .
FIG. 7 is a perspective view of the support of FIG. 1 shown coupled to a web cam and clamped to a computer display.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following detailed description is of the best presently contemplated modes of carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating general principles of embodiments of the invention. The scope of the invention is best defined by the appended claims.
FIGS. 1 to 4B illustrate a support according to present invention, which includes a guiding base 11 , a supporting post 12 , and a pair of base supports 13 and 14 . The base supports 13 and 14 can be moved towards, or away from, each other using the guide mechanisms described below.
The base 11 has an opening 111 . One end of the post 12 extends through the opening 111 and is coupled to a threaded ball joint 122 , while the other end of the post 12 carries a gear wheel 121 that is retained inside the base 11 . The base 11 has a bottom plate 15 which has wings 151 , 152 , 153 , 154 positioned in spaced-apart manner on the upper surface of the bottom plate 15 . In particular, the wings 151 , 152 , 153 , 154 can be spaced apart from each other by about 45 degrees from each other, with each wing 151 , 152 , 153 , 154 extending above and parallel to the plane of the bottom plate 15 . Referring also to FIG. 3 , guide elements in the form of ribs 157 a , 157 b can be provided on the bottom surface of the bottom plate 15 .
Recesses 156 a and 156 b are provided on the bottom plate 15 adjacent the wings 151 and 152 , respectively. A passage 155 a is defined between the wings 151 and 154 , and another passage 155 b is defined between the wings 152 and 153 . Now referring to FIGS. 1 , 4 A, 5 B and 6 B, each base support 13 and 14 has an extension 135 and 136 , respectively, that extends through a corresponding passage 155 a and 155 b , respectively, to engage the gear wheel 121 via a plurality of teeth 1351 and 1361 provided on the extensions 135 and 136 , respectively. Thus, the extensions 135 and 136 are adapted to always move in directions opposite to each other. For example, if the base supports 13 and 14 are moved towards each other (e.g., see FIGS. 5A and 5B ), the extensions 135 and 136 will be moved towards the gearwheel 121 , while if the base supports 13 and 14 are moved away from each other (e.g., see FIGS. 6A and 6B ), the extensions 135 and 136 will be moved away from the gear wheel 121 . The base supports 13 and 14 can be moved together or apart by rotating the post 12 , which will in turn rotate the gear wheel 121 .
Each base support 13 and 14 further has a groove 1322 and 1323 , respectively, that function as guide elements for receiving a corresponding rib 157 a and 157 b from the base plate 15 , with the ribs 157 a and 157 b adapted for reciprocal movement along the respective groove 1322 and 1323 as the extensions 135 and 136 move about the gear wheel 121 . In addition, each extension 135 and 136 has a hook 1352 and 1362 , respectively (see FIGS. 5B and 6B ), that is received inside the corresponding recess 156 a and 156 b , respectively, for movement inside a moving space 134 which is defined by the space between the top surface 139 of the base supports 13 , 14 and the recessed surfaces 132 and 133 of the base supports 13 and 14 , respectively, as the extensions 135 and 136 move about the gear wheel 121 .
Pads 1321 can be provided on the recessed surfaces 132 , 133 for increasing the friction between the bottom plate 15 and the recessed surfaces 132 , 133 . In addition, pads 1311 can be oriented vertically on the inner face 131 of the base supports 13 and 14 to protect an object that is to be clamped between the base supports 13 and 14 . These pads 1321 and 1311 can be provided in the form of a rubber-like material, or any similar material that can function to increase friction to grip an object while also being able to protect the surface of this object.
FIGS. 5A-7 illustrate the various ways in which the support of the present invention can be used. Referring first to FIGS. 5A and 5B , the post 12 can be coupled to a web cam 20 via the ball joint 122 such that the web cam 20 can be positioned at an angled position. The base supports 13 and 14 can be moved together to form a closed standing position, in which the wings 151 , 152 , 153 and 154 are positioned on the top of the base supports 13 and 14 . The extensions 135 and 136 are engaged with the gear wheel 121 at each side of the gear wheel 121 .
Referring now to FIGS. 6A and 6B , the base supports 13 and 14 can be separated to form a clamping position, where a clamping space is defined between the two base supports 13 and 14 . In this clamping position, the wings 151 and 152 are still positioned on the top of the base supports 13 and 14 , while the wings 153 and 154 are separated from the top of the base supports 13 and 14 . The extensions 135 and 136 still engage the gear wheel 121 at each side of the gear wheel 121 .
The rotation of the post 12 can force the gear wheel 121 to separate the base supports 13 and 14 from each other to obtain a desired width therebetween, in which the increased friction between the pads 1321 and the bottom plate 15 will reinforce the clamping effect and the friction caused by legs 13 and 14 . As the post 12 rotates and the extensions 135 and 136 travel along the gear wheel 121 , the hooks 1352 and 1362 will move along the respective recesses 156 a and 156 b , and the ribs 157 a and 157 b will move along the respective grooves 1322 and 1323 . As a result of the guided movements of the extensions 135 , 136 , the hooks 1352 , 1362 and the ribs is 157 a , 157 b , the base supports 13 and 14 will remain fully attached to the bottom plate 15 yet be capable of experiencing relative movement along the bottom plate 15 . In other words, the bottom plate 15 forms a platform upon which the base supports 13 and 14 can be moved with respect to each other.
As shown in FIG. 7 , the post 12 can be rotated to force the gear wheel 121 to separate the base supports 13 and 14 to a desired width that is somewhat larger than the thickness of an LED display 30 . Then, the user can rotate the post 12 in the opposite direction to reduce the desired width so as to tightly clamp the web cam 20 (from FIG. 6A ) on to the LED display 30 through the protection of the pads 1311 . The user can further adjust the ball joint 122 to set the web cam 20 to a desired angle position.
While the description above refers to particular embodiments of the present invention, it will be understood that many modifications may be made without departing from the spirit thereof. The accompanying claims are intended to cover such modifications as would fall within the true scope and spirit of the present invention. | A support for a computer peripheral device has a base, a post having a first end extending through the base and a second end that couples a computer peripheral device, and a pair of base supports. Each base support has an extension which is received within the base and which engages the first end of the post. When the post is rotated, the base supports are separated from each other to define a clamping space therebetween. | 0 |
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 12/027,218, filed Feb. 6, 2008, which is a continuation of U.S. application Ser. No. 11/688,124, filed Mar. 19, 2007, which is a continuation of U.S. application Ser. No. 11/006,448, filed Dec. 6, 2004, now U.S. Pat. No. 7,192,381, which is a continuation of U.S. application Ser. No. 10/770,966 filed on Feb. 3, 2004, now U.S. Pat. No. 6,949,049, which is a continuation of U.S. application Ser. No. 10/134097 filed on Apr. 25, 2002, now U.S. Pat. No. 6,689,012, which in turn claims the benefit of U.S. Provisional Application No. 60/286803, filed Apr. 26, 2001. The entire disclosure of each of those applications is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The field of the invention relates generally to transmissions, and more particularly the invention relates to continuously variable transmissions.
[0004] 2. Description of the Related Art
[0005] The present invention relates to the field of continuously variable transmissions and includes several novel features and inventive aspects that have been developed and are improvements upon the prior art. In order to provide an infinitely variable transmission, various traction roller transmissions in which power is transmitted through traction rollers supported in a housing between torque input and output disks have been developed. In such transmissions, the traction rollers are mounted on support structures which, when pivoted, cause the engagement of traction rollers with the torque disks in circles of varying diameters depending on the desired transmission ratio.
[0006] However, the success of these traditional solutions has been limited. For example, in one solution, a driving hub for a vehicle with a variable adjustable transmission ratio is disclosed. This method teaches the use of two iris plates, one on each side of the traction rollers, to tilt the axis of rotation of each of the rollers. However, the use of iris plates can be very complicated due to the large number of parts that are required to adjust the iris plates during transmission shifting. Another difficulty with this transmission is that it has a guide ring that is configured to be predominantly stationary in relation to each of the rollers. Since the guide ring is stationary, shifting the axis of rotation of each of the traction rollers is difficult.
[0007] One improvement over this earlier design includes a shaft about which a driving member and a driven member rotate. The driving member and driven member are both mounted on the shaft and contact a plurality of power adjusters disposed equidistantly and radially about the shaft. The power adjusters are in frictional contact with both members and transmit power from the driving member to the driven member. A support member located concentrically over the shaft and between the power adjusters applies a force to keep the power adjusters separate so as to make frictional contact against the driving member and the driven member. A limitation of this design is the absence of means for generating an adequate axial force to keep the driving and driven members in sufficient frictional contact against the power adjusters as the torque load on the transmission changes. A further limitation of this design is the difficulty in shifting that results at high torque and very low speed situations as well as insufficient means for disengaging the transmission and coasting.
[0008] Therefore, there is a need for a continuously variable transmission with an improved power adjuster support and shifting mechanism, means of applying proper axial thrust to the driving and driven members for various torque and power loads, and means of disengaging and reengaging the clutch for coasting.
SUMMARY OF THE INVENTION
[0009] The systems and methods have several features, no single one of which is solely responsible for its desirable attributes. Without limiting the scope as expressed by the claims that follow, its more prominent features will now be discussed briefly. After considering this discussion, and particularly after reading the section entitled “Detailed Description of the Preferred Embodiments” one will understand how the features of the system and methods provide several advantages over traditional systems and methods.
[0010] In one aspect, a continuously variable transmission is disclosed having a longitudinal axis, and a plurality of speed adjusters. Each speed adjuster has a tiltable axis of rotation is located radially outward from the longitudinal axis. Also provided are a drive disk that is annularly rotatable about the longitudinal axis and also contacts a first point on each of the speed adjusters and a support member that is also annularly rotatable about the longitudinal axis. A bearing disk is provided that is annularly rotatable about the longitudinal axis as well, and at least two axial force generators. The axial force generators are located between the drive disk and the bearing disk and each axial force generator is configured to apply an axial force to the drive disk.
[0011] In another aspect, a bearing disk annularly rotatable about the longitudinal axis is disclosed along with a disengagement mechanism. The disengagement mechanism can be positioned between the bearing disk and the drive disk and is adapted to cause the drive disk to disengage the drive disk from the speed adjusters.
[0012] In yet another aspect, an output disk or rotatable hub shell is disclosed along with a bearing disk that is annularly rotatable about the longitudinal axis of the transmission. A support member is included that is annularly rotatable about the longitudinal axis as well, and is adapted to move toward whichever of the drive disk or the output disk is rotating more slowly.
[0013] In still another aspect, a linkage subassembly having a hook is disclosed, wherein the hook is attached to either the drive disk or the bearing disk. Included is a latch attached to either the drive disk or and the bearing disk.
[0014] In another aspect, a plurality of spindles having two ends is disclosed, wherein one spindle is positioned in the bore of each speed adjuster and a plurality of spindle supports having a platform end and spindle end is provided. Each spindle support is operably engaged with one of the two ends of one of the spindles. Also provided is a plurality of spindle support wheels, wherein at least one spindle support wheel is provided for each spindle support. Included are annular first and second stationary supports each having a first side facing the speed adjusters and a second side facing away from the speed adjusters. Each of the first and second stationary supports have a concave surface on the first side and the first stationary support is located adjacent to the drive disk and the second stationary support is located adjacent to the driven disk.
[0015] Also disclosed is a continuously variable transmission having a coiled spring that is positioned between the bearing disk and the drive disk.
[0016] In another aspect, a transmission shifting mechanism is disclosed comprising a rod, a worm screw having a set of external threads, a shifting tube having a set of internal threads, wherein a rotation of the shifting tube causes a change in the transmission ratio, a sleeve having a set of internal threads, and a split shaft having a threaded end.
[0017] In yet another aspect, a remote transmission shifter is disclosed comprising a rotatable handlegrip, a tether having a first end and a second end, wherein the first end is engaged with the handlegrip and the second end is engaged with the shifting tube. The handlegrip is adapted to apply tension to the tether, and the tether is adapted to actuate the shifting tube upon application of tension.
[0018] These and other improvements will become apparent to those skilled in the art as they read the following detailed description and view the enclosed figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a cutaway side view of an embodiment of the transmission.
[0020] FIG. 2 is a partial end cross-sectional view taken on line II-II of FIG. 1 .
[0021] FIG. 3 is a perspective view of a split shaft and two stationary supports of the transmission of FIG. 1 .
[0022] FIG. 4 is a schematic cutaway side view of the transmission of FIG. 1 shifted into low.
[0023] FIG. 5 is a schematic cutaway side view of the transmission of FIG. 1 shifted into high.
[0024] FIG. 6 is a schematic side view of a ramp bearing positioned between two curved ramps of the transmission of FIG. 1 .
[0025] FIG. 7 is a schematic side view of a ramp bearing positioned between two curved ramps of the transmission of FIG. 1 .
[0026] FIG. 8 is a schematic side view of a ramp bearing positioned between two curved ramps of the transmission of FIG. 1 .
[0027] FIG. 9 is a perspective view of the power adjuster sub-assembly of the transmission of FIG. 1 .
[0028] FIG. 10 is a cutaway perspective view of the shifting sub-assembly of the transmission of FIG. 1 .
[0029] FIG. 11 is a perspective view of a stationary support of the transmission of FIG. 1 .
[0030] FIG. 12 is a perspective view of the screw and nut of the transmission of FIG. 1 .
[0031] FIG. 13 is a schematic perspective view of the frame support of the transmission of FIG. 1 .
[0032] FIG. 14 is a partial cutaway perspective view of the central ramps of the transmission of FIG. 1 .
[0033] FIG. 15 is a perspective view of the perimeter ramps of the transmission of FIG. 1 .
[0034] FIG. 16 is a perspective view of the linkage sub-assembly of the transmission of FIG. 1 .
[0035] FIG. 17 is a perspective view of the disengagement mechanism sub-assembly of the transmission of FIG. 1 .
[0036] FIG. 18 is a perspective view of the handlegrip shifter of the transmission of FIG. 1 .
[0037] FIG. 19 is a cutaway side view of an alternative embodiment of the transmission of FIG. 1 .
[0038] FIG. 20 is a cutaway side view of yet another alternative embodiment of the transmission of FIG. 1 .
[0039] FIG. 21 is a perspective view of the transmission of FIG. 20 depicting a torsional brace.
[0040] FIG. 22 is a perspective view of an alternative disengagement mechanism of the transmission of FIG. 1 .
[0041] FIG. 23 is another perspective view of the alternative disengagement mechanism of FIG. 22 .
[0042] FIG. 24 is a view of a sub-assembly of an alternative embodiment of the axial force generators of the transmission of FIG. 20 .
[0043] FIG. 25 is a schematic cross sectional view of the splines and grooves of the axial force generators of FIG. 24 .
[0044] FIG. 26 is a perspective view of an alternative disengagement mechanism of the transmission of FIG. 1 .
[0045] FIG. 27 is a perspective view of the alternative disengagement mechanism of FIG. 26 .
[0046] FIG. 28 is a schematic illustration of a power generator having a continuously variable transmission with certain inventive features.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0047] Embodiments of the invention will now be described with reference to the accompanying figures, wherein like numerals refer to like elements throughout. The terminology used in the description presented herein is not intended to be interpreted in any limited or restrictive manner simply because it is being utilized in conjunction with a detailed description of certain specific embodiments of the invention. Furthermore, embodiments of the invention may include several novel features, no single one of which is solely responsible for its desirable attributes or which is essential to practicing the inventions herein described.
[0048] The transmissions described herein are of the type that utilize speed adjuster balls with axes that tilt as described in U.S. patent application Ser. No. 09/695,757, filed on Oct. 24, 2000 and the information disclosed in that application is hereby incorporated by reference for all that it discloses. A drive (input) disk and a driven (output) disk are in contact with the speed adjuster balls. As the balls tilt on their axes, the point of rolling contact on one disk moves toward the pole or axis of the ball, where it contacts the ball at a circle of decreasing diameter, and the point of rolling contact on the other disk moves toward the equator of the ball, thus contacting the disk at a circle of increasing diameter. If the axis of the ball is tilted in the opposite direction, the disks respectively experience the converse situation. In this manner, the ratio of rotational speed of the drive disk to that of the driven disk, or the transmission ratio, can be changed over a wide range by simply tilting the axes of the speed adjuster balls.
[0049] With reference to the longitudinal axis of embodiments of the transmission, the drive disk and the driven disk can be located radially outward from the speed adjuster balls, with an idler-type generally cylindrical support member located radially inward from the speed adjuster balls, so that each ball makes three-point contact with the inner support member and the outer disks. The drive disk, the driven disk, and the support member can all rotate about the same longitudinal axis. The drive disk and the driven disk can be shaped as simple disks or can be concave, convex, cylindrical or any other shape, depending on the configuration of the input and output desired. The rolling contact surfaces of the disks where they engage the speed adjuster balls can have a flat, concave, convex or other profile, depending on the torque and efficiency requirements of the application.
[0050] Referring to FIGS. 1 and 2 , an embodiment of a continuously variable transmission 100 is disclosed. The transmission 100 is shrouded in a hub shell 40 , which functions as an output disk and is desirable in various applications, including those in which a vehicle (such as a bicycle or motorcycle) has the transmission contained within a driven wheel. The hub shell 40 can, in certain embodiments, be covered by a hub cap 67 . At the heart of the transmission 100 are a plurality of speed adjusters 1 that can be spherical in shape and are circumferentially spaced more or less equally or symmetrically around the centerline, or axis of rotation, of the transmission 100 . In the illustrated embodiment, eight speed adjusters 1 are used. However, it should be noted that more or fewer speed adjusters 1 can be used depending on the use of the transmission 100 . For example, the transmission may include 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or more speed adjusters. The provision for more than 3, 4, or 5 speed adjusters can provide certain advantages including, for example, widely distributing the forces exerted on the individual speed adjusters 1 and their points of contact with other components of the transmission 100 . Certain embodiments in applications with low torque but a high transmission ratio can use few speed adjusters 1 but large speed adjusters 1 , while certain embodiments in applications where high torque and a transmission high transmission ratio can use many speed adjusters 1 and large speed adjusters 1 . Other embodiments in applications with high torque and a low transmission ratio can use many speed adjusters 1 and small speed adjusters 1 . Finally, certain embodiments in applications with low torque and a low transmission ratio may use few speed adjusters 1 and small speed adjusters 1 .
[0051] Spindles 3 are inserted through holes that run through the center of each of the speed adjusters 1 to define an axis of rotation for each of the speed adjusters 1 . The spindles 3 are generally elongated shafts about which the speed adjusters 1 rotate, and have two ends that extend out of either end of the hole through the speed adjusters 1 . Certain embodiments will have cylindrical shaped spindles 3 , though any shape can be used. The speed adjusters 1 are mounted to freely rotate about the spindles 3 . In FIG. 1 , the axes of rotation of the speed adjusters 1 are shown in an approximately horizontal direction (i.e., parallel to the main axis of the transmission 100 ).
[0052] FIGS. 1 , 4 and 5 , can be utilized to describe how the axes of the speed adjusters 1 can be tilted in operation to shift the transmission 100 . FIG. 4 depicts the transmission 100 shifted into a low transmission ratio, or low, while FIG. 5 depicts the transmission 100 shifted into a high transmission ratio, or high. Now also referring to FIGS. 9 and 10 , a plurality of spindle supports 2 are attached to the spindles 3 near each of the ends of the spindles 3 that extend out of the holes bored through the speed adjusters 1 , and extend radially inward from those points of attachment toward the axis of the transmission 100 . In one embodiment, each of the spindle supports 2 has a through bore that receives one end of one of the spindles 3 . The spindles 3 preferably extend through and beyond the spindle supports 2 such that they have an exposed end. In the embodiments illustrated, the spindles 3 advantageously have spindle rollers 4 coaxially and slidingly positioned over the exposed ends of the spindles 3 . The spindle rollers 4 are generally cylindrical wheels fixed axially on the spindles 3 outside of and beyond the spindle supports 2 and rotate freely about the spindles 3 . Referring also to FIG. 11 , the spindle rollers 4 and the ends of the spindles 3 fit inside grooves 6 that are cut into a pair of stationary supports 5 a, 5 b.
[0053] Referring to FIGS. 4 , 5 and 11 , the stationary supports 5 a, 5 b are generally in the form of parallel disks annularly located about the axis of the transmission on either side of the power adjusters 1 . As the rotational axes of the speed adjusters 1 are changed by moving the spindle supports 2 radially out from the axis of the transmission 100 to tilt the spindles 3 , each spindle roller 4 fits into and follows a groove 6 cut into one of the stationary supports 5 a, 5 b. Any radial force, not rotational but a transaxial force, the speed adjusters 1 may apply to the spindles 3 is absorbed by the spindles 3 , the spindle rollers 4 and the sides 81 of the grooves 6 in the stationary supports 5 a, 5 b. The stationary supports 5 a, 5 b are mounted on a pair of split shafts 98 , 99 positioned along the axis of the transmission 100 . The split shafts 98 , 99 are generally elongated cylinders that define a substantial portion of the axial length of the transmission 100 and can be used to connect the transmission 100 to the object that uses it. Each of the split shafts 98 , 99 has an inside end near the middle of the transmission 100 and an outside end that extends out of the internal housing of the transmission 100 . The split shafts 98 , 99 are preferably hollow so as to house other optional components that may be implemented. The stationary supports 5 a, 5 b, each have a bore 82 , through which the split shafts 98 , 99 are inserted and rigidly attached to prevent any relative motion between the split shafts 98 , 99 and the stationary supports 5 a, 5 b. The stationary supports 5 a, 5 b are preferably rigidly attached to the ends of the split shafts 98 , 99 closest to the center of the transmission 100 . A stationary support nut 90 may be threaded over the split shaft 99 and tightened against the stationary support 5 b on corresponding threads of the stationary support 5 a, 5 b. The grooves 6 in the stationary supports 5 a, 5 b referred to above, extend from the outer circumference of the stationary supports 5 a, 5 b radially inwardly towards the split shafts 98 , 99 . In most embodiments, the groove sides 81 of the grooves 6 are substantially parallel to allow the spindle rollers 4 to roll up and down the groove sides 81 as the transmission 100 is shifted. Also, in certain embodiments, the depth of the grooves 6 is substantially constant at the circumference 9 of the stationary supports 5 a, 5 b, but the depth of the grooves 6 becomes shallower at points 7 closer to the split shaft 98 , 99 , to correspond to the arc described by the ends of the spindles 3 as they are tilted, and to increase the strength of the stationary supports 5 a, 5 b. As the transmission 100 is shifted to a lower or higher transmission ratio by changing the rotational axes of the speed adjusters 1 , each one of the pairs of spindle rollers 4 , located on the opposite ends of a single spindle 3 , move in opposite directions along their corresponding grooves 6 .
[0054] Referring to FIGS. 9 and 11 , stationary support wheels 30 can be attached to the spindle supports 2 with stationary support wheel pins 31 or by any other attachment method. The stationary support wheels 30 are coaxially and slidingly mounted over the stationary support wheel pins 31 and secured with standard fasteners, such as ring clips for example. In certain embodiments, one stationary support wheel 30 is positioned on each side of a spindle 2 with enough clearance to allow the stationary support wheels 30 to roll radially on concave surfaces 84 of the stationary supports 5 a, 5 b when the transmission 100 is shifted. In certain embodiments, the concave surfaces 84 are concentric with the center of the speed, adjusters 1 .
[0055] Referring to FIGS. 2 , 3 , and 11 , a plurality of elongated spacers 8 are distributed radially about, and extend generally coaxially with, the axis of the transmission. The elongated spacers 8 connect the stationary supports 5 a to one another to increase the strength and rigidity of the internal structure of the transmission 100 . The spacers 8 are oriented generally parallel to one another, and in some embodiments, each one extends from a point at one stationary support 5 a near the outer circumference to a corresponding point on the other stationary support 5 b. The spacers 8 can also precisely fix the distance between the stationary supports 5 a, 5 b, align the grooves 6 of the stationary supports 5 a, 5 b, ensure that the stationary supports 5 a, 5 b are parallel, and form a connection between the split shafts 98 , 99 . In one embodiment, the spacers 8 are pressed through spacer holes 46 in the stationary supports 5 a, 5 b. Although eight spacers 8 are illustrated, more or less spacers 8 can be used. In certain embodiments, the spacers 8 are located between two speed adjusters 1 .
[0056] Referring to FIGS. 1 , 3 , and 13 , the stationary support 5 a, in certain embodiments, is rigidly attached to a stationary support sleeve 42 located coaxially around the split shaft 98 , or alternately, is otherwise rigidly attached to or made an integral part of the split shaft 98 . The stationary sleeve 42 extends through the wall of the hub shell 40 and attaches to a frame support 15 . In some embodiments, the frame support 15 fits coaxially over the stationary sleeve 42 and is rigidly attached to the stationary sleeve 42 . The frame support 15 uses a torque lever 43 , in some embodiments, to maintain the stationary position of the stationary sleeve 42 . The torque lever 43 provides rotational stability to the transmission 100 by physically connecting the stationary sleeve 42 , via the frame support 15 , and therefore the rest of the stationary parts to a fixed support member of the item to which the transmission 100 is to be mounted. A torque nut 44 threads onto the outside of the stationary sleeve 42 to hold the torque lever 43 in a position that engages the frame support 15 . In certain embodiments, the frame support 15 is not cylindrical so as to engage the torque lever 43 in a positive manner thereby preventing rotation of the stationary sleeve 42 .
[0057] For example, the frame support 15 could be a square of thickness equal to the torque lever 43 with sides larger than the stationary sleeve and with a hole cut out of its center so that the square may fit over the stationary sleeve 42 , to which it may then be rigidly attached. Additionally, the torque lever 43 could be a lever arm of thickness equal to that of the frame support 15 with a first end near the frame support 15 and a second end opposite the first. The torque lever 43 , in some embodiments, also has a bore through one of its ends, but this bore is a square and is a slightly larger square than the frame support 15 so the torque lever 43 could slide over the frame support 15 resulting in a rotational engagement of the frame support 15 and the torque lever 43 . Furthermore, the lever arm of the torque lever 43 is oriented so that the second end extends to attach to the frame of the bike, automobile, tractor or other application that the transmission 100 is used upon, thereby countering any torque applied by the transmission 100 through the frame support 15 and the stationary sleeve 42 . A stationary support bearing 48 fits coaxially around the stationary sleeve 42 and axially between the outside edge of the hub shell 40 and the torque lever 43 . The stationary support bearing 48 supports the hub shell 40 , permitting the hub shell 40 to rotate relative to the stationary support sleeve 42 .
[0058] Referring to FIGS. 1 and 10 , in some embodiments, shifting is manually activated by rotating a rod 10 , positioned in the hollow split shaft 98 . A worm screw 11 , a set of male threads in some embodiments, is attached to the end of the rod 10 that is in the center of the transmission 100 , while the other end of the rod 10 extends axially to the outside of the transmission 100 and has male threads affixed to its outer surface. In one embodiment, the worm screw 11 is threaded into a coaxial sleeve 19 with mating threads, so that upon rotation of the rod 10 and worm screw 11 , the sleeve 19 moves axially. The sleeve 19 is generally in the shape of a hollow cylinder that fits coaxially around the worm screw 11 and rod 10 and has two ends, one near stationary support 5 a and one near stationary support 5 b. The sleeve 19 is affixed at each end to a platform 13 , 14 . The two platforms 13 , 14 are each generally of the form of an annular ring with an inside diameter, which is large enough to fit over and attach to the sleeve 19 , and is shaped so as to have two sides. The first side is a generally straight surface that dynamically contacts and axially supports the support member 18 via two sets of contact bearings 17 a, 17 b. The second side of each platform 13 , 14 is in the form of a convex surface. The platforms 13 , 14 are each attached to one end of the outside of the sleeve 19 so as to form an annular trough around the circumference of the sleeve 19 . One platform 13 is attached to the side nearest stationary support 5 a and the other platform 14 is attached to the end nearest stationary support 5 b. The convex surface of the platforms 13 , 14 act as cams, each contacting and pushing multiple shifting wheels 21 . To perform this camming function, the platforms 13 , 14 preferably transition into convex curved surfaces 97 near their perimeters (farthest from the split shafts 98 , 99 ), that may or may not be radii. This curve 97 contacts with the shifting wheels 21 so that as the platforms 13 , 14 move axially, a shifting wheel 21 rides along the platform 13 , 14 surface in a generally radial direction forcing the spindle support 2 radially out from, or in toward, the split shaft 98 , 99 , thereby changing the angle of the spindle 3 and the rotation axis of the associated speed adjuster 1 . In certain embodiments, the shifting wheels 21 fit into slots in the spindle supports 2 at the end nearest the centerline of the transmission 100 and are held in place by wheel axles 22 .
[0059] Still referring to FIGS. 1 and 10 , a support member 18 is located in the trough formed between the platforms 13 , 14 and sleeve 19 , and thus moves in unison with the platforms 13 , 14 and sleeve 19 . In certain embodiments, the support member 18 is generally of one outside diameter and is generally cylindrical along the center of its inside diameter with a bearing race on each edge of its inside diameter. In other embodiments, the outer diameter of the support member 18 can be non-uniform and can be any shape, such as ramped or curved. The support member 18 has two sides, one near one of the stationary supports 5 a and one near the other stationary support 5 b. The support member 18 rides on two contact bearings 17 a, 17 b to provide rolling contact between the support member 18 and the sleeve 19 . The contact bearings 17 a, 17 b are located coaxially around the sleeve 19 where the sleeve 19 intersects the platforms 13 , 14 allowing the support member 18 to freely rotate about the axis of the transmission 100 . The sleeve 19 is supported axially by the worm screw 11 and the rod 10 and therefore, through this configuration, the sleeve 19 is able to slide axially as the worm screw 11 positions it. When the transmission 100 is shifted, the sleeve 19 moves axially, and the bearings 17 a, 17 b, support member 18 , and platforms 13 , 14 , which are all attached either dynamically or statically to the sleeve, move axially in a corresponding manner.
[0060] In certain embodiments, the rod 10 is attached at its end opposite the worm screw 11 to a shifting tube 50 by a rod nut 51 , and a rod flange 52 . The shifting tube 50 is generally in the shape of a tube with one end open and one end substantially closed. The open end of shifting tube 50 is of a diameter appropriate to fit over the end of the split shaft 98 that extends axially out of the center of the transmission 100 . The substantially closed end of the shifting tube 50 has a small bore through it so that the end of the rod 10 that is opposite of the worm screw 11 can pass through it as the shifting tube 50 is placed over the outside of the split shaft 98 . The substantially closed end of the shifting tube 50 can then be fixed in axial place by the rod nut 51 , which is fastened outside of the shifting tube 50 , and the rod flange 52 , which in turn is fastened inside of the shifting tube's 50 substantially closed end, respectively. The shifting tube 50 can, in some embodiments, be rotated by a cable 53 attached to the outside of the shifting tube 50 . The cable 53 , in these embodiments, is attached to the shifting tube 50 with a cable clamp 54 and cable screw 56 , and then wrapped around the shifting tube 50 so that when tension is applied to the cable 53 a moment is developed about the center of the axis of the shifting tube 50 causing it to rotate. The rotation of shifting tube 50 may alternately be caused by any other mechanism such as a rod, by hand rotation, a servo-motor or other method contemplated to rotate the rod 10 . In certain embodiments, when the cable 53 is pulled so that the shifting tube 50 rotates clockwise on the split shaft 98 , the worm screw 11 rotates clockwise, pulling the sleeve 19 , support member 18 and platforms 13 , 14 , axially toward the shifting tube 50 and shifting the transmission 100 towards a low transmission ratio. A worm spring 55 , as illustrated in FIG. 3 , that can be a conical coiled spring capable of producing compressive and torsional force, attached at the end of the worm screw 11 , is positioned between the stationary support 5 b and the platform 14 and resists the shifting of the transmission 100 . The worm spring 55 is designed to bias the shifting tube 50 to rotate so as to shift the transmission 100 towards a low transmission ratio in some embodiments and towards a high transmission ratio in other embodiments.
[0061] Referring to FIGS. 1 , 10 , and 11 , axial movement of the platforms 13 , 14 , define the shifting range of the transmission 100 . Axial movement is limited by inside faces 85 on the stationary supports 5 a, 5 b, which the platforms 13 , 14 contact. At an extreme high transmission ratio, platform 14 contacts the inside face 85 on one of the stationary supports 5 a, 5 b, and at an extreme low transmission ratio, the platform 13 contacts the inside face 85 on the other one of the stationary supports 5 a, 5 b. In many embodiments, the curvature of the convex radii of the platforms 13 , 14 , are functionally dependant on the distance from the center of a speed adjuster 1 to the center of the wheel 21 , the radius of the wheel 21 , the distance between the two wheels 21 that are operably attached to each speed adjuster 1 , and the angle of tilt of the speed adjuster 1 axis.
[0062] Although a left hand threaded worm screw 11 is disclosed, a right hand threaded worm screw 11 , the corresponding right hand wrapped shifting tube 50 , and any other combination of components just described that is can be used to support lateral movement of the support member 18 and platforms 13 , 14 , can be used. Additionally, the shifting tube 50 can have internal threads that engage with external threads on the outside of the split shaft 98 . By adding this threaded engagement, the shifting tube 50 will move axially as it rotates about the split shaft 98 causing the rod 10 to move axially as well. This can be employed to enhance the axial movement of the sleeve 19 by the worm screw 11 so as to magnify the effects of rotating the worm screw 11 to more rapidly shift the gear ratio or alternatively, to diminish the effects of rotating the worm screw 11 so as to slow the shifting process and produce more accurate adjustments of the transmission 100 .
[0063] Referring to FIGS. 10 and 18 , manual shifting may be accomplished by use of a rotating handlegrip 132 , which can be coaxially positioned over a stationary tube, a handlebar 130 , or some other structural member. In certain embodiments, an end of the cable 53 is attached to a cable stop 133 , which is affixed to the rotating handlegrip 132 . In some embodiments, internal forces of the transmission 100 and the conical spring 55 tend to bias the shifting of the transmission towards a lower transmission ratio. As the rotating handlegrip 132 is rotated by the user, the cable 53 , which can be wrapped along a groove around the rotating handlegrip 132 , winds or unwinds depending upon the direction of rotation of the cable 53 , simultaneously rotating the shifting tube 50 and shifting the transmission 100 towards a higher transmission ratio. A set of ratchet teeth 134 can be circumferentially positioned on one of the two sides of the rotating handlegrip 132 to engage a mating set of ratchet teeth on a first side of a ratcheted tube 135 , thereby preventing the rotating handlegrip 132 from rotating in the opposite direction. A tube clamp 136 , which can bean adjustable screw allowing for variable clamping force, secures the ratcheted tube 135 to the handlebar 130 . When shifting in the opposite direction, the rotating handlegrip 132 , is forcibly rotated in the opposite direction toward a lower transmission ratio, causing the tube clamp 136 to rotate in unison with the rotating handlegrip 132 . A handlebar tube 137 , positioned proximate to the ratcheted tube 135 , on a side opposite the ratchet teeth 134 , is rigidly clamped to the handlebar 130 with a tube clamp 138 , thereby preventing disengagement of the ratcheted tube 135 from the ratchet teeth 134 . A non-rotating handlegrip 131 is secured to the handlebar 130 and positioned proximate to the rotating handlegrip 132 , preventing axial movement of the rotating handlegrip 132 and preventing the ratchet teeth 134 from becoming disengaged from the ratcheted tube 135 .
[0064] Now referring to embodiments illustrated by FIGS. 1 , 9 , and 11 , a one or more stationary support rollers 30 can be attached to each spindle support 2 with a roller pin 31 that is inserted through a hole in each spindle support 2 . The roller pins 31 are of the proper size and design to allow the stationary support rollers 30 to rotate freely over each roller pin 31 . The stationary support rollers 30 roll along concave curved surfaces 84 on the sides of the stationary supports 5 a, 5 b that face the speed adjusters 1 . The stationary support rollers 30 provide axial support to prevent the spindle supports 2 from moving axially and also to ensure that the spindles 2 tilt easily when the transmission 100 is shifted.
[0065] Referring to FIGS. 1 , 12 , 14 , and 17 , a three spoked drive disk 34 , located adjacent to the stationary support 5 b, partially encapsulates but generally does not contact the stationary support 5 b. The drive disk 34 may have two or more spokes or may be a solid disk. The spokes reduce weight and aid in assembly of the transmission 100 ine embodiments using them, however a solid disk can be used. The drive disk 34 has two sides, a first side that contacts with the speed adjusters 1 , and a second side that faces opposite of the first side. The drive disk 34 is generally an annular disk that fits coaxially over, and extends radially from, a set of female threads or nut 37 at its inner diameter. The outside diameter of the drive disk 34 is designed to fit within the hub shell 40 , if the hub shell 40 employed is the type that encapsulates the speed adjusters 1 and the drive disk 34 , and engages with the hub cap 67 . The drive disk 34 is rotatably coupled to the speed adjusters 1 along a circumferential bearing surface on the lip of the first side of the drive disk 34 . As mentioned above, some embodiments of the drive disk 34 have a set of female threads 37 , or a nut 37 , at its center, and the nut 37 is threaded over a screw 35 , thereby engaging the drive disk 34 with the screw 35 . The screw 35 is rigidly attached to a set of central screw ramps 90 that are generally a set of raised surfaces on an annular disk that is positioned coaxially over the split shaft 99 . The central screw ramps 90 are driven by a set of central drive shaft ramps 91 , which are similarly formed on a generally annular disk. The ramp surfaces of the central drive ramps 91 and the central screw ramps 90 can be linear, but can be any other shape, and are in operable contact with each other. The central drive shaft ramps 91 , coaxially and rigidly attached to the drive shaft 69 , impart torque and an axial force to the central screw ramps 90 that can then be transferred to the drive disk 34 . A central drive tension member 92 , positioned between the central drive shaft ramps 91 and the central screw ramps 90 , produces torsional and/or compressive force, ensuring that the central ramps 90 , 91 are in contact with one another.
[0066] Still referring to FIGS. 1 , 12 , 14 , and 17 , the screw 35 , which is capable of axial movement, can be biased to move axially away from the speed adjusters 1 with an annular thrust bearing 73 that contacts a race on the side of the screw 35 that faces the speed adjusters 1 . An annular thrust washer 72 , coaxially positioned over the split shaft 99 , contacts the thrust bearing 73 and can be pushed by a pin 12 that extends through a slot in the split shaft 99 . A compression member 95 capable of producing a compressive force is positioned in the bore of the hollow split shaft 99 at a first end. The compression member 95 , which may be a spring, contacts the pin 12 on one end, and at a second end contacts the rod 10 . As the rod 10 is shifted towards a higher transmission ratio and moves axially, it contacts the compression member 95 , pushing it against the pin 12 . Internal forces in the transmission 100 will bias the support member 18 to move towards a high transmission ratio position once the transmission ratio goes beyond a 1:1 transmission ratio towards high and the drive disk 34 rotates more slowly than the hub shell 40 . This bias pushes the screw 35 axially so that it either disconnects from the nut 37 and no longer applies an axial force or a torque to the drive disk 34 , or reduces the force that the screw 35 applies to the nut 37 . In this situation, the percentage of axial force applied to the drive disk 34 by the perimeter ramps 61 increases. It should be noted that the internal forces of the transmission 100 will also bias the support member 18 towards low once the support member 18 passes beyond a position for a 1:1 transmission ratio towards low and the hub shell 40 rotates more slowly than the drive disk 34 . This beneficial bias assists shifting as rpm's drop and torque increases when shifting into low.
[0067] Still referring to FIGS. 1 , 12 , 14 , and 17 , the drive shaft 69 , which is a generally tubular sleeve having two ends and positioned coaxial to the outside of the split shaft 99 , has at one end the aforementioned central drive shaft ramps 91 attached to it, while the opposite end faces away from the drive disk 34 . In certain embodiments, a bearing disk 60 is attached to and driven by the drive shaft 69 . The bearing disk 60 can be splined to the drive shaft 69 , providing for limited axial movement of the bearing disk 60 , or the bearing disk 60 can be rigidly attached to the drive shaft 69 . The bearing disk 60 is generally a radial disk coaxially mounted over the drive shaft 69 extending radially outward to a radius generally equal to that of the drive disk 34 . The bearing disk 60 is mounted on the drive shaft 69 in a position near the drive disk 34 , but far enough away to allow space for a set of perimeter ramps 61 , associated ramp bearings 62 , and a bearing race 64 , all of which are located between the drive disk 34 and the bearing disk 67 . In certain embodiments, the plurality of perimeter ramps 61 can be concave and are rigidly attached to the bearing disk 60 on the side facing the drive disk 34 . Alternatively, the perimeter ramps 61 can be convex or linear, depending on the use of the transmission 100 . Alternatively, the bearing race 64 , can be replaced by a second set of perimeter ramps 97 , which may also be linear, convex, or concave, and which are rigidly attached to the drive disk 34 on the side facing the bearing disk 60 . The ramp bearings 62 are generally a plurality of bearings matching in number the perimeter ramps 61 . Each one of the plurality of ramp bearings 62 is located between one perimeter ramp 61 and the bearing race 64 , and is held in its place by a compressive force exerted by the ramps 61 and also by a bearing cage 63 . The bearing cage 63 is an annular ring coaxial to the split shaft 99 and located axially between the concave ramps 61 and convex ramps 64 . The bearing cage 63 has a relatively large inner diameter so that the radial thickness of the bearing cage 63 is only slightly larger than the diameter of the ramp bearings 62 to house the ramp bearings 62 . Each of the ramp bearings 62 fits into a hole that is formed in the radial thickness of the bearing cage 63 and these holes, together with the previously mentioned compressive force, hold the ramp bearings 62 in place. The bearing cage 63 , can be guided into position by a flange on the drive disk 34 or the bearing disk 60 , which is slightly smaller than the inside diameter of the bearing cage 63 .
[0068] Referring to FIGS. 1 , 6 , 7 , 8 , and 15 , the bearing disk 60 , the perimeter ramps 61 , and a ramp bearing 62 of one embodiment are depicted. Referring specifically to FIG. 6 , a schematic view shows a ramp bearing 62 contacting a concave perimeter ramp 61 , and a second convex perimeter ramp 97 . Referring specifically to FIG. 7 , a schematic view shows the ramp bearing 62 , the concave perimeter ramp 61 , and the second convex perimeter ramp 97 of FIG. 6 at a different torque or transmission ratio. The position of the ramp bearings 62 on the perimeter ramps 61 depicted in FIG. 7 produces less axial force than the position of the ramp bearings 62 on the perimeter ramps 61 depicted in FIG. 6 . Referring specifically to FIG. 8 , a ramp bearing 62 is shown contacting a convex perimeter ramp 61 , and a concave second perimeter ramp 97 in substantially central positions on those respective ramps. It should be noted that changes in the curves of the perimeter ramps 61 , 97 change the magnitude of the axial force applied to the power adjusters 1 at various transmission ratios, thereby maximizing efficiency in different gear ratios and changes in torque. Depending on the use for the transmission 100 , many combinations of curved or linear perimeter ramps 61 , 97 can be used. To simplify operation and reduce cost, in some applications one set of perimeter ramps may be eliminated, such as the second set of perimeter tramps 97 , which are then replaced by a bearing race 64 . To further reduce cost, the set of perimeter ramps 61 may have a linear inclination.
[0069] Referring to FIG. 1 , a coiled spring 65 having two ends wraps coaxially around the drive shaft 69 and is attached at one end to the bearing disk 60 and at its other end to the drive disk 34 . The coiled spring 65 provides force to keep the drive disk 34 in contact with the speed adjusters 1 and biases the ramp bearings 62 up the perimeter ramps 61 . The coiled spring 65 is designed to minimize the axial space within which it needs to operate and, in certain embodiments, the cross section of the coiled spring 65 is a rectangle with the radial length greater than the axial length.
[0070] Referring to FIG. 1 , the bearing disk 60 preferably contacts an outer hub cap bearing 66 on the bearing disk 60 side that faces opposite the concave ramps 61 . The outer hub cap bearing 66 can be an annular set of roller bearings located radially outside of, but coaxial with, the centerline of the transmission 100 . The outer hub cap bearing 66 is located radially at a position where it may contact both the hub cap 67 and the bearing disk 60 to allow their relative motion with respect to one another. The hub cap 67 is generally in the shape of a disk with a hole in the center to fit over the drive shaft 69 and with an outer diameter such that it will fit within the hub shell 40 . The inner diameter of the hub cap engages with an inner hub cap bearing 96 that is positioned between the hub cap 67 and the drive shaft 69 and maintains the radial and axial alignment of the hub cap 67 and the drive shaft 69 with respect to one another. The edge of the hub cap 67 at its outer diameter can be threaded so that the hub cap 67 can be threaded into the hub shell 40 to encapsulate much of the transmission 100 . A sprocket or pulley 38 or other drive train adapter, such as gearing for example, can be rigidly attached to the rotating drive shaft 69 to provide the input rotation. The drive shaft 69 is maintained in its coaxial position about the split shaft 99 by a cone bearing 70 . The cone bearing 70 is an annular bearing mounted coaxially around the split shaft 99 and allows rolling contact between the drive shaft 69 and the split shaft 99 . The cone bearing 70 may be secured in its axial place by a cone nut 71 which threads onto the split shaft 99 or by any other fastening method.
[0071] In operation of certain embodiments, an input rotation from the sprocket or pulley 38 is transmitted to the drive shaft 69 , which in turn rotates the bearing disk 60 and the plurality of perimeter ramps 61 causing the ramp bearings 62 to roll up the perimeter ramps 61 and press the drive disk 34 against the speed adjusters 1 . The ramp bearings 62 also transmit rotational energy to the drive disk 34 as they are wedged in between, and therefore transmit rotational energy between, the perimeter ramps 61 and the convex ramps 64 . The rotational energy is transferred from the drive disk 34 to the speed adjusters 1 , which in turn rotate the hub shell 40 providing the transmission 100 output rotation and torque.
[0072] Referring to FIG. 16 , a latch 115 rigidly attaches to the side of the drive disk 34 that faces the bearing disk 60 and engages a hook 114 that is rigidly attached to a first of two ends of a hook lever 113 . The engaging area under the latch 115 opening is larger than the width of the hook 114 and provides extra room for the hook 114 to move radially, with respect to the axis, within the confines of the latch 114 when the drive disk 34 and the bearing disk 60 move relative to each other. The hook lever 113 is generally a longitudinal support member for the hook 114 and at its second end, the hook lever 113 has an integral hook hinge 116 that engages with a middle hinge 119 via a first hinge pin 111 . The middle hinge 119 is integral with a first end of a drive disk lever 112 , a generally elongated support member having two ends. On its second end, the drive disk lever 112 has an integral drive disk hinge 117 , which engages a hinge brace 110 via the use of a second hinge pin 118 . The hinge brace 110 is generally a base to support the hook 114 , the hook lever 113 , the hook hinge 116 , the first hinge pin 111 , the middle hinge 119 , the drive disk lever 112 the second hinge pin 118 , and the drive disk hinge 117 , and it is rigidly attached to the bearing disk 60 on the side facing the drive disk 34 . When the latch 73 and hook 72 are engaged the ramp bearings 62 are prevented from rolling to an area on the perimeter ramps 61 that does not provide the correct amount of axial force to the drive disk 34 . This ensures that all rotational force applied to the ramp bearings 62 by perimeter ramps 61 is transmitted to the drive disk 34 .
[0073] Referring to FIGS. 1 and 17 , a disengagement mechanism for one embodiment of the transmission 100 is described to disengage the drive disk 34 from the speed adjusters 1 in order to coast. On occasions that input rotation to the transmission 100 ceases, the sprocket or pulley 38 stops rotating but the hub shell 40 and the speed adjusters 1 can continue to rotate. This causes the drive disk 34 to rotate so that the set of female threads 37 in the bore of the drive disk 34 wind onto the male threaded screw 35 , thereby moving the drive disk 34 axially away from the speed adjusters 1 until the drive disk 34 no longer contacts the speed adjusters 1 . A toothed rack 126 , rigidly attached to the drive disk 34 on the side facing the bearing disk 60 , has teeth that engage and rotate a toothed wheel 124 as the drive disk 34 winds onto the screw 35 and disengages from the power adjusters 1 . The toothed wheel 124 , has a bore in its center, through which a toothed wheel bushing 121 is located, providing for rotation of the toothed wheel 124 . Clips 125 that are coaxially attached over the toothed wheel bushing 121 secure the toothed wheel 124 in position, although any means of fastening may be used. A preloader 120 , coaxially positioned over and clamped to the central drive shaft ramps 91 , extends in a direction that is radially outward from the center of the transmission 100 . The preloader 120 , of a resilient material capable of returning to its original shape when flexed, has a first end 128 and a second end 127 . The first end of the preloader 128 extends through the toothed wheel bushing 121 and terminates in the bearing cage 63 . The first end of the preloader 128 biases the bearing cage 63 and ramp bearings 62 up the ramps 61 , ensuring contact between the ramp bearings 62 and the ramps 61 , and also biases the toothed wheel 124 against the toothed rack 126 . A pawl 123 , engages the toothed wheel 124 , and in one embodiment engages the toothed wheel 124 on a side substantially opposite the toothed rack 126 . The pawl 123 has a bore through which a pawl bushing 122 passes, allowing for rotation of the pawl 123 . Clips 125 , or other fastening means secure the pawl 123 to the pawl bushing 121 . A pawl spring 122 biases rotation of the pawl 123 to engage the toothed wheel 124 , thereby preventing the toothed wheel 124 from reversing its direction of rotation when the drive disk 34 winds onto the screw 35 . The pawl bushing 121 is positioned over a second end of the preloader 127 , which rotates in unison with the drive shaft 69 .
[0074] Referring again to FIG. 1 , a coiled spring 65 , coaxial with and located around the drive shaft 69 , is located axially between and attached by pins or other fasteners (not shown) to both the bearing disk 60 at one end and drive disk 34 at the other end. In certain embodiments, the coiled spring 65 replaces the coiled spring of the prior art so as to provide more force and take less axial space in order to decrease the overall size of the transmission 100 . In some embodiments, the coiled spring 65 is produced from spring steel wire with a rectangular profile that has a radial length or height greater than its axial length or width. During operation of the transmission 100 , the coiled spring 65 ensures contact between the speed adjusters 1 and the drive disk 34 . However, once the drive disk 34 has disengaged from the speed adjusters 1 , the coiled spring 65 is prevented from winding the drive disk 34 so that it again contacts the speed adjusters 1 by the engagement of the toothed wheel 124 and the pawl 123 . When the input sprocket, gear, or pulley 38 , resumes its rotation, the pawl 123 also rotates, allowing the toothed wheel 124 to rotate, thus allowing the drive disk 34 to rotate and unwind from the screw 35 due to the torsional force created by the coiled spring 65 . Relative movement between the pawl 123 and the toothed wheel 124 is provided by the fact that the first end of the preloader 128 rotates at approximately half the speed as the second end of the preloader 127 because the first end of the preloader 128 is attached to the bearing cage 63 . Also, because the ramp bearings 62 are rolling on the perimeter ramps 61 of the bearing disk 60 , the bearing cage 63 will rotate at half the speed as the bearing disk 60 .
[0075] Referring now to FIG. 19 , an alternative embodiment of the transmission 100 of FIG. 1 is disclosed. In this embodiment, an output disk 201 replaces the hub shell 40 of the transmission 100 illustrated in FIG. 1 . Similar to the drive disk 34 , the output disk 201 contacts, and is rotated by, the speed adjusters 1 . The output disk 201 is supported by an output disk bearing 202 that contacts both the output disk 201 and a stationary case cap 204 . The case cap 204 is rigidly attached to a stationary case 203 with case bolts 205 or any other fasteners. The stationary case 203 can be attached to a non-moving object such as a frame or to the machine for which its use is employed. A gear, sprocket, or pulley 206 is attached coaxially over and rigidly to the output disk 201 outside of the case cap 204 and stationary case 203 . Any other type of output means can be used however, such as gears for example. A torsional brace 207 can be added that rigidly connects the split shaft 98 to the case cap 204 for additional support.
[0076] Referring now to FIGS. 20 and 21 , an alternative embodiment of the transmission 100 of FIG. 1 is disclosed. A stationary support race 302 is added on a side of stationary support 5 a facing away from the speed adjusters 1 and engages with a stationary support bearing 301 and a rotating hub shell race 303 to maintain correct alignment of the stationary support 5 a with respect to the rotating hub shell 40 . A torsional brace 304 is rigidly attached to the stationary support 5 a and can then be rigidly attached to a stationary external component to prevent the stationary supports 5 a, 5 b from rotating during operation of the transmission 300 . A drive shaft bearing 306 is positioned at an end of the drive shaft 69 facing the speed adjusters 1 and engages a drive shaft race 307 formed in the same end of the drive shaft 69 and a split shaft race 305 formed on a radially raised portion of the split shaft 99 to provide additional support to the drive shaft 69 and to properly position the drive shaft 69 relative to the stationary supports 5 a, 5 b.
[0077] Referring now to FIGS. 22 and 23 , an alternative disengagement mechanism 400 of the transmission 100 of FIG. 1 is disclosed. A toothed wheel 402 is coaxially positioned over a wheel bushing 408 and secured in position with a clip 413 or other fastener such that it is capable of rotation. The wheel bushing 408 is coaxially positioned over the first end of a preloader 405 having first and second ends (both not separately identified in FIGS. 22 , and 23 ). The preloader 405 clamps resiliently around the central drive shaft ramps 91 . The first end of the preloader 405 extends into the bearing cage 63 , biasing the bearing cage 63 up the perimeter ramps 61 . Also positioned over the wheel bushing 408 is a lever 401 that rotates around the wheel bushing 408 and that supports a toothed wheel pawl 411 and a pinion pawl 409 . The toothed wheel pawl 411 engages the toothed wheel 402 to control its rotation, and is positioned over a toothed wheel bushing 414 that is pressed into a bore in the lever 401 . A toothed wheel pawl spring 412 biases the toothed wheel pawl 411 against the toothed wheel 402 . The pinion pawl 409 , positioned substantially opposite the toothed wheel pawl 411 on the lever 401 , is coaxially positioned over a pinion pawl bushing 415 that fits into another bore in the lever 401 and provides for rotational movement of the pinion pawl 409 . A pinion pawl spring 410 biases the pinion pawl 409 against a pinion 403 .
[0078] Referring now to FIGS. 1 , 22 and 23 , the pinion 403 has a bore at its center and is coaxially positioned over a first of two ends of a rod lever 404 . The rod lever is an elongated lever that engages the pinion pawl 409 during coasting until input rotation of the sprocket, pulley, or gear 38 resumes. A bearing disk pin 406 that is affixed to the bearing disk 60 contacts a second end of the rod lever 404 , upon rotation of the bearing disk 60 , thereby pushing the rod lever 404 against a drive disk pin 407 , which is rigidly attached to the drive disk 34 . This action forces the first end of the rod lever 404 to swing away from the toothed wheel 402 , temporarily disconnecting the pinion 403 from the toothed wheel 402 , allowing the toothed wheel 402 to rotate. A lever hook 401 is attached to the the lever 401 and contacts a latch (not shown) on the drive disk 34 and is thereby pushed back as the coiled spring 65 biases the drive disk 34 to unwind and contact the speed adjusters 1 . During occasions that the input rotation of the sprocket, pulley, or gear 38 ceases, and the speed adjusters 1 continue to rotate, the drive disk 34 winds onto the screw 35 and disengages from the speed adjusters 1 . As the drive disk 34 rotates, the drive disk pin 407 disengages from the rod lever 404 , which then swings the pinion 403 into contact with the toothed wheel 402 , preventing the drive disk 34 from re-engaging the speed adjusters 1 .
[0079] Referring to FIGS. 24 and 25 , a sub-assembly of an alternative set of axial force generators 500 of the transmission 300 of FIG. 20 is disclosed. When rotated by the input sprocket, gear, or pulley 38 , a splined drive shaft 501 rotates the bearing disk 60 , which may have grooves 505 in its bore to accept and engage the splines 506 of the splined drive shaft 501 . The central drive shaft ramps 508 are rigidly attached to the bearing disk 60 or the splined drive shaft 501 and rotate the central screw ramps 507 , both of which have bores that clear the splines 506 of the splined drive shaft 501 . The central tension member 92 (illustrated in FIG. 1 ) is positioned between the central drive shaft ramps 508 and the central screw ramps 507 . A grooved screw 502 having a grooved end and a bearing end is rotated by the central screw ramps 90 and has grooves 505 on its bearing end that are wider than the splines 506 on the splined drive shaft 501 to provide a gap between the splines 506 and the grooves 505 . This gap between the splines 506 and the grooves 505 allows for relative movement between the grooved screw 502 and/or bearing disk 60 and the splined drive shaft 501 . On occasions when the grooved screw 502 is not rotated by the central drive shaft ramps 508 and the central screw ramps 507 , the splines 506 of the splined drive shaft 501 contact and rotate the grooves 505 on the grooved screw 502 , thus rotating the grooved screw 502 . An annular screw bearing 503 contacts a race on the bearing end of the grooved screw 502 and is positioned to support the grooved screw 502 and the splined drive shaft 501 relative to the axis of the split shaft 99 . The bore of the grooved screw 502 is slightly larger than the outside diameter of the splined drive shaft 501 to allow axial and rotational relative movement of the grooved screw 502 . A screw cone race 504 contacts and engages the annular screw bearing 503 and has a hole perpendicular to its axis to allow insertion of a pin 12 . The pin 12 engages the rod 10 , which can push on the pin 12 and move the grooved screw 502 axially, causing it to disengage from, or reduce the axial force that it applies to, the nut 37 .
[0080] Referring to FIG. 26 , an alternative disengagement means 600 of the disengagement means 400 of FIGS. 22 and 23 is disclosed. The lever 401 is modified to eliminate the T-shape used to mount both the pinion pawl 409 and the toothed wheel pawl 411 so that the new lever 601 has only the toothed wheel pawl 411 attached to it. A second lever 602 , having a first end and a second end. The pinion pawl 409 is operably attached to the first end of the second lever 602 . The second lever 602 has a first bore through which the first end of the preloader 405 is inserted. The second lever 602 is rotatably mounted over the first end of the preloader 405 . The second lever 602 has a second bore in its second end through which the second end of the preloader 603 is inserted. When rotation of the sprocket, gear, or pulley 38 ceases, the drive disk 34 continues to rotate forward and wind onto the screw 36 until it disengages from the speed adjusters 1 . The first end of the preloader 405 rotates forward causing the pinion pawl 409 to contact and rotate the pinion 403 clockwise. This causes the toothed wheel 402 to rotate counter-clockwise so that the toothed wheel pawl 411 passes over one or more teeth of the toothed wheel 402 , securing the drive disk 34 and preventing it from unwinding off of the screw 36 and contacting the speed adjusters 1 . When rotation of the sprocket, gear, or pulley 38 resumes, the second end of the preloader 603 rotates, contacting the second end of the second lever 602 causing the pinion pawl 409 to swing out and disengage from the pinion 403 , thereby allowing the drive disk 34 to unwind and reengage with the speed adjusters 1 .
[0081] With this description in place, some of the particular improvements and advantages of the present invention will now be described. Note that not all of these improvements are necessarily found in all embodiments of the invention.
[0082] Referring to FIG. 1 , a current improvement in some embodiments includes providing variable axial force to the drive disk 34 to respond to differing loads or uses. This can be accomplished by the use of multiple axial force generators. Axial force production can switch between a screw 35 and a nut 37 , with associated central drive shaft ramps 91 and screw ramps 90 , to perimeter ramps 61 , 64 . Or the screw 35 , central ramps 90 , 91 , and perimeter ramps 61 , 64 can share axial force production. Furthermore, axial force at the perimeter ramps 61 , 64 can be variable. This can be accomplished by the use of ramps of variable inclination and declination, including concave and convex ramps. Referring to FIG. 1 and FIGS. 6-8 and the previous detailed description, an embodiment is disclosed where affixed to the bearing disk 60 is a first set of perimeter ramps 61 , which may be concave, with which the ramp bearings 62 contact. Opposite the first set of perimeter ramps 61 are a second set of perimeter ramps 97 that are attached to the drive disk 34 , which may be convex, and which are in contact with the ramp bearings 62 . The use of concave and convex ramps to contact the ramp bearings 62 allows for non-linear increase or decrease in the axial load upon the drive disk 34 in response to adjustments in the position of the speed adjusters 1 and the support member 18 .
[0083] Another improvement of certain embodiments includes positively engaging the bearing disk 60 and the drive disk 34 to provide greater rotational transmission and constant axial thrust at certain levels of torque transmission. Referring to an embodiment illustrated in FIG. 1 as described above, this may be accomplished, for example, by the use of the hook 114 and latch 115 combination where the hook 114 is attached to the bearing cage 63 that houses the ramp bearings 62 between the drive disk 34 and the bearing disk 60 , and the latch 115 is attached to the drive disk 34 that engages with the hook 114 when the ramp bearings 62 reach their respective limit positions on the ramp faces. Although such configuration is provided for example, it should be understood that the hook 114 and the latch 115 may be attached to the opposite component described above or that many other mechanisms may be employed to achieve such positive engagement of the bearing disk 60 and the drive disk 34 at limiting positions of the ramp bearings 62 .
[0084] A further improvement of certain embodiments over previous designs is a drive disk 34 having radial spokes (not separately identified), reducing weight and aiding in assembly of the transmission 100 . In a certain embodiment, the drive disk 34 has three spokes equidistant from each other that allow access to, among other components, the hook 114 and the latch 115 .
[0085] Another improvement of certain embodiments includes the use of threads 35 , such as acme threads, to move the drive disk 34 axially when there is relative rotational movement between the drive disk 34 and the bearing disk 60 . Referring to the embodiment illustrated in FIG. 1 , a threaded male screw 35 may be threaded into a set of female threads 37 , or a nut 37 , in the bore of the drive disk 34 . This allows the drive disk 34 to disengage from the speed adjusters 1 when the drive disk 34 ceases to provide input torque, such as when coasting or rolling in neutral, and also facilitates providing more or less axial force against the speed adjusters 1 . Furthermore, the threaded male screw 35 is also designed to transmit an axial force to the drive disk 34 via the set of female threads 37 .
[0086] Yet another improvement of certain embodiments over past inventions consists of an improved method of shifting the transmission to higher or lower transmission ratios. Again, referring to the embodiment illustrated in FIG. 1 , this method can be accomplished by using a threaded rod 10 , including, for example, a left hand threaded worm screw 11 and a corresponding right hand threaded shifting tube 50 , or sleeve, that operates remotely by a cable 53 or remote motor or other remote means. Alternatively, left-handed threads can be used for both the worm screw 11 and the shifting tube, or a non-threaded shifting tube 50 could be used, and any combinations thereof can also be used as appropriate to affect the rate of shifting the transmission 100 with respect to the rate of rotation of the shifting tube 50 . Additionally, a conical spring 55 can be employed to assist the operator in maintaining the appropriate shifting tube 50 position. The worm screw 11 is preferably mated with a threaded sleeve 19 so as to axially align the support member 18 so that when the worm screw 11 is rotated the support member 18 will move axially.
[0087] Another improvement of some embodiments over past inventions is the disengagement mechanism for the transmission 100 . The disengagement mechanism allows the input sprocket, pulley, or gear 38 to rotate in reverse, and also allows the transmission 100 to coast in neutral by disengaging the drive disk 34 from the speed adjusters 1 .
[0088] Referring to FIG. 28 , a power generator 800 can include a wind turbine rotor 802 and a continuously variable transmission (CVT) 804 . In one embodiment, the CVT 804 is substantially similar to the CVT 100 of FIG. 1 . The power generator 800 can include a motor/generator 806 coupled to the CVT 804 . In one embodiment, the power generator 800 includes a planetary gear set 808 coupled to the CVT 804 . In some embodiments, the power generator 800 includes a shaft 810 coupled to the wind turbine rotor 802 and the planetary gear set 808 .
[0089] The foregoing description details certain embodiments of the invention. It will be appreciated, however, that no matter how detailed the foregoing appears in text, the invention can be practiced in many ways. As is also stated above, it should be noted that the use of particular terminology when describing certain features or aspects of the invention should not be taken to imply that the terminology is being re-defined herein to be restricted to including any specific characteristics of the features or aspects of the invention with which that terminology is associated. The scope of the invention should therefore be construed in accordance with the appended claims and any equivalents thereof. | A continuously variable transmission is disclosed for use in rotationally or linearly powered machines and vehicles. The transmission provides a simple manual shifting method for the user. Further, the practical commercialization of traction roller transmissions requires improvements in the reliability, ease of shifting, function and simplicity of the transmission. The present invention includes a continuously variable transmission that may be employed in connection with any type of machine that is in need of a transmission. For example, the transmission may be used in (i) a motorized vehicle such as an automobile, motorcycle, or watercraft, (ii) a non-motorized vehicle such as a bicycle, tricycle, scooter, exercise equipment or (iii) industrial equipment, such as a drill press, power generating equipment, or textile mill. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e) from U.S. Provisional Patent Application No. 60/876,581 filed on Dec. 22, 2006, the subject matter of which is herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to an improved Municipal Waste Combustion system and method. Particularly, the embodiments of the present invention improve upon known municipal waste combustors (MWCs) by incorporating means for accurately calculating the moisture content of the input waste to be combusted in the MWC.
BACKGROUND OF THE INVENTION
[0003] In the Waste-to-Energy (WTE) industry, the heating value of municipal solid waste (MSW) is generally considered to be an unmeasurable and uncontrollable variable. Local weather, particularly rainfall, dramatically impacts MSW heating value, and in turn, the processing capacity and operating characteristics of waste-to-energy boilers. This variable is the largest distinction between mass burn waste-to-energy and other forms of combustion-based steam generation. The ability to measure effectively changes in MSW heating value would enhance boiler operation by providing a critical input to boiler combustion controls that has been previously unavailable. In addition, the ability to control the moisture content of the MSW to a relatively constant value, by regulating the addition of water or liquid waste, would further enhance the boiler operation, as well as improve the predictability of waste processing rates, by making constant a previously uncontrolled variable.
[0004] It is known to measure moisture content in liquid waste, such as sludge. For example, U.S. Pat. No. 6,553,924 issued to Beaumont, et al. relates to a system and method for injecting and co-combusting sludge in a municipal waste combustor, where the moisture content of the sludge is monitored and controlled prior to combustion, but these techniques are generally not applicable to solid waste management and combustion because it is technically challenging to accurately and efficiently measure the moisture content in large volumes of solid waste in hostile conditions near the MWC furnace.
SUMMARY OF THE INVENTION
[0005] In response to these and other needs, embodiments of the present invention enable direct measuring of the density of the MSW fuel as an indicator of moisture content using nuclear radiation density meters positioned to monitor input waste prior to combustion. In one embodiment, a typical nuclear moisture-density meter contains sealed radioactive materials, typically cesium and a combination of americium mixed with beryllium powder. The radioactive materials emit nuclear radiation that a detector can count when the radiation passes through the MSW. This count can be translated to a density value. The density value can then be used to infer a moisture content measurement for the MSW.
[0006] In one aspect of the invention a method for combustion control in solid waste incineration systems is provided. The method includes the steps of feeding solid waste into an input system; determining the moisture content of the solid waste prior to the solid waste entering a combustion chamber; adjusting the combustion process in response to the determined moisture content; and passing the solid waste into the combustion chamber.
[0007] In another aspect of the invention a solid waste combustion system is provided. The system includes a municipal waste combustor, the municipal waste combustor including a combustion chamber. The system also includes a waste input system configured to feed solid waste into the combustion chamber. Also included in the system is a moisture sensor adapted to determine moisture content of the solid waste prior to the waste entering the combustion chamber. Finally, the system includes a controller in communication with the moisture sensor, wherein said controller receives information from the moisture sensor and regulates the operation of the municipal waste combustor and/or the waste input system in response to said information.
[0008] In embodiments of the present invention, the moisture content measurement for the MSW can be used as a feed forward to the MWC to adjust the combustion process accordingly.
[0009] Because radiation-based measurement is a statistically random process, multiple density sensors can be configured in series to measure the waste density several times. Then a final density measure can be determined, for example, from an average reading from the multiple density sensors, with the moisture content estimate produced using the average measured density.
[0010] In one embodiment, the density sensor instrument(s) would be situated to read fuel density in a plane passing through the MSW feed hopper just above a ram table where the MSW is forced into a combustion chamber. In this way, the MSW could be measured just prior to introduction into the combustion chamber in the MWC.
[0011] Alternatively, multiple measuring points in this plane would ensure a fair representation of the MSW condition.
[0012] A smoothed density reading would then be used to characterize the boiler control parameters (such as air distribution and control system gains) to improve combustion control and enhance boiler stability. The MSW density reading would also be used to control liquid injection rates to maintain a relatively constant MSW heating value. The controlled heating value would be at the lower end of the normal range, enabling the boilers to operate close to their grate limit on a continuous basis, and thereby maximize the MSW tons processed, regardless of the variations in MSW composition and heating value.
[0013] In one embodiment, the output of this density measurement may be correlated to changes in MSW heating value and used as a feedforward input to the combustion controls.
[0014] In another embodiment, the moisture/density measurements may be used to control a water injection process to control the MSW heating value.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] A more complete understanding of the present invention and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings in which like reference numbers indicate like features, and wherein:
[0016] FIG. 1 depicts an improved Municipal Waste Combustion (MWC) system in accordance with embodiments of the present invention is presented;
[0017] FIG. 2 provides a schematic representation in the form of a longitudinal section through a combustion system of an MWC; and
[0018] FIG. 3 provides a flow chart of a method for controlling the heating value of municipal solid waste (MSW) in an MWC.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] As depicted in the figures and as described herein, the embodiments of the present invention provide an improved Municipal Waste Combustion system and method. Specifically, the embodiments of the present invention adapt known municipal waste combustors (MWCs) by incorporating means for accurately calculating the moisture content of the input waste to be combusted in the MWC. Through better measurement of the waste moisture contents, combustion in the MWC can be better controlled to achieve desired results, including reduced emissions and greater combustion efficiency.
[0020] Changes in moisture content can alter MSW tons processed as much as 10%, however, waste-to-energy boilers rarely operate at their grate capacity limit. The effect of this idea would be to maintain the boiler close to its grate limit at all times, which should result in an increased MSW throughput of about 5%.
[0021] Reduction in fuel variance would also improve consistency of operation resulting in more net power output by minimizing low swings caused by MSW composition and heating value changes.
[0022] Turning now to FIG. 1 , an improved MWC system 100 in accordance with embodiments of the present invention is presented. The MWC system 100 includes a MWC 100 for combusting Municipal Solid Waste (MSW) 110 and a waste input system 120 for supplying the MSW 110 to the MWC 100 . Various types of the MWC 100 are known and include, for example, moving grate combustors, rotary-kilns in which waste is transported through the furnace by moving teeth mounted on a central rotating shaft, and fluidized bed in which a strong airflow is forced through a sand bed. Likewise, depending on the type of MWC 110 a variety of kinds of waste input system 120 may be used.
[0023] Generally, MSW 110 is burned in the MSC 100 and the energy from the combustion is used to heat water to create high pressure steam. Combustion air from duct 150 and other variables may be adjusted to optimize the combustion process.
[0024] One or more moisture sensor 130 is located at a point generally prior to the furnace of the MWC 100 to measure the moisture content of the MSW 110 . The moisture sensor 130 may be in the form of a density sensor, such as a nuclear radiation density meter, which indirectly estimates moisture content of the MSW 110 . Other types of moisture sensor 130 may include an air humidity sensor located in the vicinity of the MSW 110 combustion. As another alternative, moisture sensor 130 may include a height measurement of the MSW 100 to estimate density and thereby estimate moisture content. Moisture sensor 130 may include a single sensor or multiple sensors of the same type that take measurements at different points in the MSW input stream. Moisture sensor 130 may also include a combination of different types of sensors, such as a nuclear radiation density meter and an air humidity sensor.
[0025] Continuing with the improved MWC system 100 in FIG. 1 , a controller 140 receives status information from and regulates the operation of the MWC 100 and the waste input system 120 . In known systems, the type of information received by the controller 140 typically includes feedback status information from the MWC 100 about combustion process, such as the furnace temperature(s), the measured levels of various output pollutants such as carbon monoxide, and other measured levels such as the amount of elemental oxygen within the furnace. In addition to this conventional information, information from moisture sensor 130 is provided to the controller 140 and used to adjust input flow from the waste input system 120 and the air flow from duct 150 . Furthermore, the controller 140 further receives feed-forward information about the status of the waste input system 120 . This information typically relates to the amount and timing of municipal waste introduced into the MWC 100 .
[0026] These systems are explained in more detail below by an example of the arrangement in FIG. 2 , which is a schematic representation in the form of a longitudinal section through a combustion system 200 of an MWC. While a particular combustion system 200 is depicted in FIG. 2 and described below, it should be appreciated that the principles of the present invention may be adapted to a variety of incineration system to achieve desired optimal MSW processing rates.
[0027] As can be seen in FIG. 2 , the combustion system 200 in this exemplary embodiment has a feed hopper 210 followed by a feed chute 220 for supplying the fuel to a feed table 235 , on which feed rams 240 that can be moved to and fro are provided to convey the fuel arriving from the feed chute 220 onto a combustion grate 250 on which combustion of the fuel takes place. Whether the grate is sloping or is horizontally arranged and which principle is applied is immaterial.
[0028] A density meter 230 is located to read fuel density in a plane passing through the feed chute 220 just above the ram table 235 . Preferably, multiple measuring points in the same plane may be used to ensure a fair representation of the MSW condition.
[0029] Still referring to FIG. 2 , a controller (such as controller 140 from FIG. 1 ) receives status information from a variety of monitored functions and regulates the operation of the MWC 200 and the MSW 290 input. The reading from density meter 230 would also be used by the controller to control liquid (e.g., water or liquid waste) injection rates, such that liquid would be added to comparatively dry waste to maintain a relatively constant MSW heating value. The controlled heating value would be at the lower end of the normal range, enabling the boilers to operate close to their grate limit on a continuous basis, and thereby maximize the MSW tons processed, regardless of the variations in MSW composition and heating value. As a compliment to liquid injection, automatic regulation of other process parameters including excess air ratio, feed water temperature and combustion air preheat temperature may be incorporated in the control strategy to permit process operation at a relatively constant firing rate. The target firing rate would be optimized for the specific financial goal of the facility in which the invention is deployed.
[0030] In the representative embodiment shown in FIG. 2 , below the combustion grate 250 is arranged a device, denoted in its totality by 260 , that supplies primary combustion air and that can consist of several chambers 261 to 265 into which primary combustion air is introduced via a duct 270 by means of a fan 275 . Through the arrangement of the chambers 261 to 265 , the combustion grate is divided into several underrate air zones so that the primary combustion air can be adjusted to different settings according to the requirements on the combustion grate.
[0031] Above the combustion grate 250 is a furnace 280 which leads into a flue gas pass 285 which is followed by components that are not shown, such as a heat recovery boiler and a flue gas cleaning system. The rear area of the furnace 280 is delimited by a roof 288 , a rear wall 283 and side walls 284 . Combustion of the fuel denoted by 290 takes place on the front part of the combustion grate 250 above which the flue gas pass 285 is located. Most of the primary combustion air is introduced into this area via the chambers 261 , 262 and 263 . On the rear area of the combustion grate 250 there is only predominantly burnt-out fuel, or bottom ash, and primary combustion air is introduced into this area via the chambers 264 and 265 primarily for cooling purposes and to facilitate residual burnout of the bottom ash.
[0032] The burnt-out fuel then falls into a discharger 295 at the end of the combustion grate 250 . Optionally, nozzles 271 and 272 are provided in the area of the flue gas pass 285 to supply secondary combustion gas to the rising flue gas, thereby mixing the flue gas flow and facilitating post combustion of the combustible portion remaining in the flue gas.
[0033] In certain embodiments of the invention, the improved MWC system described herein may be combined with other known combustion techniques for reducing unwanted emissions such as those described in co-pending and commonly assigned U.S. patent application Ser. Nos. 11/529,292, filed Sep. 29, 2006, and 11/905,809, filed Oct. 4, 2007 which are incorporated herein by reference in their entirety.
[0034] FIG. 3 provides a flow chart of a method 300 for controlling the heating value of MSW in an MWC. In step S 310 , the MSW is fed into the input system of an MWC. External factors such as weather, waste-types, and transport conditions can effect the heating value of the MSW, and in turn, the processing capacity and operating characteristics of waste-to-energy boilers. Thus, in step S 320 the moisture content of the input waste is monitored prior to the waste entering the combustion chamber of the MWC.
[0035] In one embodiment, monitoring step S 320 is accomplished using one or more nuclear radiation density meters to directly monitoring waste density to estimate moisture content. A typical nuclear moisture-density meter contains sealed radioactive materials, typically cesium and a combination of americium mixed with beryllium powder. The radioactive materials emit nuclear radiation that a detector can count when the radiation passes through the MSW. This count can be translated to a density value. The density value can then be used to infer a moisture content measurement for the MSW.
[0036] In step S 330 , the combustion process is adjusted in response to the monitored reading step S 320 . As discussed with respect to the previous figures, process variables may be adjusted to maintain a relatively constant MSW heating value. In certain embodiments, the controlled heating value would be at the lower end of the normal range. In step S 340 the MSW is forced into the combustion chamber and incinerated, creating heat used for high pressure steam or other energy sources.
[0037] While the invention has been described with reference to an exemplary embodiments various additions, deletions, substitutions, or other modifications may be made without departing from the spirit or scope of the invention. Accordingly, the invention is not to be considered as limited by the foregoing description, but is only limited by the scope of the appended claims. | Having an indication of changes to the heating value of municipal solid waste (MSW) and having a means to control it before the MSW is fed to the boiler enables improved combustion control and increased capacity of waste-to-energy boilers. The moisture content of MSW has a significant impact on its heating value and on boiler efficiency when combusted. Changes in moisture content also change the density of the MSW. Directly measuring the density of the MSW prior to feeding it to the boiler permits controlled addition of additional water or liquid waste to reduce the variance of the MSW heating value. | 5 |
The present invention concerns an anchoring harpoon intended in particular for an aircraft able to cooperate with an anchoring grate of a platform, and an anchoring system including one such harpoon.
Such harpoons and such anchoring systems are already generally known in the state of the art.
Thus for example, document FR-A-2 701 689 describes a harpoon intended to equip a rotocraft such as a helicopter, for example, and that can be pulled towards a landing platform of a vessel so that the head of the harpoon attaches on the grate and thus forms an anchoring point of the aircraft, in particular facilitating the landing operation thereof.
The anchoring harpoon described in the aforementioned document includes cylinder means wherein piston means move provided with a shaft extending beyond the cylinder means and the free end of which includes a harpoon head for hooking in the grate. This harpoon head is in fact provided with retaining fingers for retention in the grate, radially movable between a retracted position and an active position using control means.
Such harpoons have already been successfully implemented on a number of vessels to ensure anchoring in particular of helicopter-type aircrafts.
For some time, a number of attempts have also been made to land drone-type rotocrafts on platforms, in particular military ones.
The applicant has also successfully developed and tested an automatic landing and take-off system for a rotary-wing drone on and from such a vessel.
The implementation of these drones also requires the use of harpoons and anchoring grates.
Studies have shown that adapting already known anchoring harpoons for helicopters directly on rotary-wing drones could not be done successfully.
Indeed, these studies have shown problems related to size, power, maintenance, etc.
The aim of the invention is therefore to resolve these problems.
SUMMARY OF THE INVENTION
To that end, the invention concerns an anchoring harpoon, intended in particular for an aircraft, able to cooperate with an anchoring grate of a platform, including jack means comprising cylinder means containing mobile piston means provided with a rod that extends beyond the cylinder means and the free end of which includes a harpoon head that is hooked in the grate, provided with retaining fingers for retention therein, that can be moved between a retracted position and an active position by control means, characterized in that the means for controlling the movements of the fingers comprise a control piston that can slide inside the rod of the jack and that is associated with a bistable actuator of the fingers, capable of moving between a retracted position and an active position in which the fingers are deployed with the application of successive pressure pulses in the jack means.
According to other features of the invention, considered separately or in combination:
the bistable actuator is a rotary mechanical jack,
the bistable actuator includes a wheel with beveled teeth inserted between the control piston and a rod for actuating the fingers, positioned in a sleeve connected to the jack rod, the end of the piston opposite the wheel with beveled teeth itself including teeth, so as, when pressure pulses are applied in the jack means and therefore the control piston moves, to cause the beveled toothed wheel to rotate in the sleeve, the teeth of the wheel also being adapted to cooperate with successive notches having different heights of the sleeve, in order to define stable positions, active and retracted, of the rod for actuating the fingers,
it includes a spring for stressing the rod for actuating the fingers in the retracted position,
the cylinder means of the jack include at least two cylinder portions telescoping one in the other and capable of being moved between a retracted position one in the other and an active position with one protruding relative to the other,
the jack means are connected to a pressurized fluid source through control means and said pressurized fluid source includes a consumable gas cartridge,
the gas is CO 2 ,
the control means comprise solenoid valve means steered upon opening and closing to feed the jack means,
the corresponding end of the jack means is associated with the aircraft and a helical return and pressing spring is inserted between said end of the jack and the harpoon head,
the helical spring is arranged around the jack means,
it includes trigger means for prohibiting the movement of the fingers towards their active position when the harpoon head is not positioned abutting in the anchoring grate.
The invention also concerns an anchoring system, in particular for a drone-type rotocraft comprising an anchoring harpoon as previously described.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood using the following description, provided solely as an example, and done in reference to the appended drawings, in which:
FIGS. 1 and 2 show cross-sectional views of an anchoring harpoon according to the invention in the retracted and active anchoring positions, respectively, in an anchoring grate of a platform,
FIG. 3 illustrates an exploded perspective view of a hooking harpoon head included in a harpoon according to the invention,
FIG. 4 shows a summary diagram illustrating the pressurized fluid supply of a harpoon according to the invention, and
FIG. 5 illustrates the operation of such a harpoon.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
These figures, and in particular FIGS. 1 and 2 , illustrate an anchoring harpoon, intended in particular for an aircraft on a platform of the military vessel type or another type.
The aircraft can for example be a rotary-wing drone.
This harpoon is designated by general reference 1 in these figures and is adapted to cooperate with an anchoring grate of the platform, this grate being designated by general reference 2 in these figures.
Indeed, the harpoon includes jack means designated by general reference 3 , including cylinder means designated by general reference 4 , wherein piston means designated by general reference 5 move.
These piston means are provided with a rod 6 extending beyond the cylinder means and whereof the free end includes a harpoon head that hooks in the grate, said harpoon head being designated by general reference 7 .
In fact and as described in the aforementioned prior art document, this harpoon head is provided with retaining fingers for retention in the grate, capable of being radially moved between a retracted position and an active position by control means, as will be described in more detail hereinafter.
In these figures, one of the fingers is designated by general reference 8 and the control means thereof by general reference 9 .
The structure of these control means will also be described in more detail relative to FIG. 3 .
Returning to FIGS. 1 and 2 , the fingers and the control means are shown in the retracted position in FIG. 1 and the active position in FIG. 2 , when the harpoon is deployed, the control means being movable in the rod to cause a radial movement of the retaining fingers between the retracted position, in FIG. 1 , in the head of the harpoon, and the active retaining position in FIG. 2 , radially protruding relative to said head to lock it in the grate.
To resolve the various problems of integration in a drone, in particular as previously described, in the anchoring harpoon according to the invention, the cylinder means of the jack comprise at least two cylinder portions telescoping one in the other and capable of being moved between a position with one retracted in the other and an active anchoring position with one protruding relative to the other, as illustrated in FIGS. 1 and 2 , respectively.
In these figures, the two cylinder portions telescoping one in the other are designated by references 10 and 11 , respectively.
The upper cylinder portion 10 is then associated with hooking means for hooking on the drone, said means having any suitable traditional structure, while the other end of this upper cylinder portion 10 is adapted to receive the lower cylinder portion 11 , which itself supports the rod 6 whereof the free end supports the harpoon head 7 .
The jack means are then connected to a pressurized fluid source through control means to control their operation, i.e. the deployment of the anchoring harpoon and its hooking or unhooking relative to the anchoring grate.
To that end, a helical return and pressing spring 12 is inserted between the end of the upper cylinder portion associated with the aircraft and the harpoon head to ensure, as illustrated in FIG. 2 , when the harpoon head is anchored in the grate, correct pressing of the drone on the platform.
The harpoon head 7 can be similar to that already described in the document previously mentioned and for example include three retaining fingers arranged 120° from each other and for example designated by general references 8 , 13 and 14 in FIG. 3 . These fingers can then be moved between a retracted position and an active position radially protruding relative to the rest of the head in order to anchor the harpoon in the grate under the control of the control means designated by general reference 9 in FIGS. 1 , 2 and 3 .
Also traditionally, the harpoon head 7 can include an arming trigger for these control means 9 to prohibit the movement of the fingers towards their active position when the harpoon head is not positioned abutting in the anchoring grate, i.e. in the correct anchoring position in the grate.
This trigger was also previously described and is designated by general reference 15 in FIG. 3 .
This trigger 15 is then positioned transversely in the harpoon head 7 , protrudes radially from the head, and is associated with a spring 16 and a stop member 17 to be pushed back in the harpoon head when the latter is in its correct position in the anchoring grate as illustrated in FIG. 2 , and to allow the control means 9 and the retaining fingers to move.
The control means 9 comprise a piston designated by general reference 18 capable of sliding in the rod of the jack and associated with a bistable actuator of the fingers, capable of being moved between retracted and active, deployed positions of the fingers with the application of successive pressure pulses in the jack means.
This bistable actuator of the fingers is designated by general reference 19 and includes several pieces forming what is commonly called a rotary lock.
This bistable actuator in fact includes a wheel with beveled teeth that is designated by general reference 20 in FIG. 3 , inserted between the control piston 18 and an actuating rod of the fingers designated by general reference 21 in FIG. 3 .
The piston 18 and the beveled toothed wheel 20 are arranged in a sleeve designated by general reference 22 connected to the rod 6 of the jack for example through a pin designated by general reference 23 .
A spring for stressing the actuating rod 21 of the fingers in the retracted position is also provided, said spring being designated by general reference 24 in FIG. 3 .
The end of the piston 18 opposite the beveled toothed wheel itself includes teeth like the tooth designated by general reference 25 in that figure, so as, when pressure pulses are applied in the jack means and therefore corresponding movements of the piston 18 occur, to make the beveled toothed wheel 20 rotate in the sleeve 22 . The beveled teeth 20 of the wheel are also adapted to cooperate with successive notches having different heights of the sleeve 22 in order to define stable positions, active and retracted, in the actuating rod 21 of the fingers and therefore of said fingers.
Two successive notches with different heights of the sleeve are for example designated by general references 26 and 27 in that figure.
In the retracted position of the control means 9 , the teeth of the wheel 20 for example bear against the notches such as the notch 26 . When pressure is applied in the jack means, the piston 18 causes the toothed wheel 20 and the actuating rod 21 to move against the elastic stress of the spring 24 if the trigger 15 is armed, i.e. pushed back, the head being in the correct position in the grate.
During this pushing, the teeth 25 of the piston 18 also tend to cause the toothed wheel to rotate. However, this rotational movement of the wheel is prevented by the cooperation of the teeth of the wheel with the edges of the sleeve 22 of each side of the notch 26 until the beveled teeth of the wheel 20 can cross the corresponding end of the sleeve 22 to cooperate with the notch 27 for maintaining the teeth and therefore of the actuating rod 21 in the active deployed position of the fingers of the hooking head.
Locking in position is thus ensured by stressing the spring 24 , which pushes the actuating rod 21 and the toothed wheel 20 to remain in position against the notch 27 .
The fluid pressure can then be released in the jack means while keeping the aircraft anchored in the grate.
A new application of a fluid pressure pulse in the jack means causes a new angular movement of the beveled toothed wheel opposite the following notch corresponding to the retracted position of the rod of the actuating means under the action of the spring 24 in order to unlock the head.
It of course goes without saying that other embodiments of this bistable actuator controlled by applying successive pressure pulses in the jack means can be considered.
It can thus be conceived that the use of such a bistable mechanical lock can make it possible to use only pressure pulses in the jack means and no longer requires that pressure be maintained therein as was the case with the jack means of the prior art.
A single pressure pulse indeed makes it possible to deploy the fingers, and a single additional pressure pulse makes it possible to retract them back in.
Moreover, it also makes it possible to modify the pressurized fluid supply means of the jack means.
A summary diagram of these supply means is provided in FIG. 4 .
Indeed, the supply means can include a pressurized fluid source for example assuming the form of a consumable gas cartridge, for example such as a consumable CO 2 cartridge, designated by general reference 30 in that figure.
This gas cartridge 30 is then removed at the inlet of the solenoid valve means 3 / 2 that are normally closed, designated by general reference 31 , itself connected to adjustable restricting means making it possible to limit the gas flow rate during harpooning and bleeding, designated by general reference 32 .
A pressure relief valve adjusted to a pressure slightly higher than the desired harpooning pressure is also provided, said valve being designated by general reference 33 , the harpoon still being designated by general reference 1 .
The control upon opening and closing of the solenoid valve means thus makes it possible to steer the supply of the jack means in the form of pressure pulses.
This pulse-based operation is illustrated in FIG. 5 , which shows that the harpooning and release of harpooning are done through successive applications of pressure pulses in the jack means, which makes it possible on one hand to deploy the telescoping harpoon, which remains in the deployed position as long as the anchoring head is locked in the grate, and which also makes it possible to obtain a force pressing the aircraft on the platform.
Applying a pressure pulse by controlling the opening of the solenoid valve means 31 previously described can allow cylinder portions of the jack means to deploy in order to make the hooking head of the harpoon penetrate the grate.
The harpoon head is then housed in a cell of the grate, which makes it possible to push back the arming trigger 15 and therefore the piston 18 , under the action of the pressure of the fluid in the jack means, to push the actuating rod 21 of the fingers 8 towards the deployed position of said fingers in order to lock the head in the grate.
The rotary bistable mechanical lock makes it possible to lock the rod and the fingers in said active position anchoring the head in the grate and the fluid pressure can then be released in the jack means, the helical return and pressing spring 12 making it possible to keep the drone pressed in position on the grate.
When a new pressure pulse is applied in the jack means, the piston 18 causes the beveled toothed wheel 20 to rotate to unlock the rotary mechanical lock, which allows, when the fluid pressure is released in the jack means, the spring 24 to push the actuating rod 21 of the fingers back, towards a retracted position, and allows said fingers to return to a position retracted in the anchoring head, which releases said anchoring head from the grate and makes it possible, via the helical spring 12 , to return the jack means towards a retracted position ( FIG. 1 ).
It is then seen that such a structure has a certain number of advantages relative to the harpoons of the state of the art.
The use of a telescoping jack in fact makes it possible to double the deployment travel of the harpoon for a same folded length and therefore considerably decrease the length of the harpoon in the folded position, which makes it possible to adapt to the bulk constraints related to placing it on board a drone.
The use of a pressing and return spring placed outside the jack means also makes it possible to obtain a correct pressing force against the grate.
The use of a bistable actuator with a rotary mechanical lock makes it possible to maintain the harpoon in its position between two pulse orders to change state, i.e. folded or locked in the grate.
The transition from one state to the other is done by applying a pulse of the pressurized fluid in the jack means. This then makes it possible to use a consumable cartridge, for example a gas cartridge, associated with solenoid valve control means to ensure the supply.
Of course, different embodiments of the described parts can be considered and other applications can also be considered, for example for anchoring aircrafts on oil or other platforms. | An anchoring harpoon intended in particular for an aircraft, capable of cooperating with an anchoring grate of a platform, includes jack elements including a cylinder element containing mobile piston elements provided with a rod that extends beyond the cylinder element, the free end of which includes a harpoon head ( 7 ) that is hooked in the grate and includes retaining fingers ( 8, 13, 14 ) that can be moved between a retracted position and an active position by control elements ( 9 ). The control element ( 9 ) for controlling the movements of the fingers include a control piston ( 18 ) which can slide inside the rod of the jack and which is associated with a bistable actuator ( 19 ) of the fingers, capable of moving between a retracted position and an active position in which the fingers are deployed with the application of successive pressure pulses in the jack elements. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The contents of this application are related to United States design patent applications titled “ELECTRONIC ARTICLE SURVEILLANCE TAG” and “ELECTRONIC ARTICLE SURVEILLANCE UNIT” having serial numbers 29/240,195 and 29/240,196, respectively, filed on Oct. 11, 2005, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
The invention relates to theft deterrent security tags in general, and in particular to a security tag that is attachable to items to be monitored which items cannot be penetrated by a pin.
BACKGROUND OF THE INVENTION
Various types of electronic article surveillance (EAS) systems are known having the common feature of employing a marker or tag which is affixed to an article to be protected against theft from a controlled area, such as merchandise in a store. When a legitimate purchase of the article is made, the marker can either be removed from the article, or converted from an activated state to a deactivated state. Such systems employ a detection arrangement, commonly placed at all exits of a store, and if an activated marker passes through the detection system, it is detected by the detection system and an alarm is triggered.
Such electronic detection arrangements, as used in the present invention, are well known in the art and are more clearly discussed in co-pending U.S. patent application Ser. No. 10/410,486, titled “Article Surveillance Tag Having a Metal Clip,” filed on Apr. 8, 2003, which is incorporated herein by reference. A discussion of the inventions in the field, known to the inventor, and their differences from the present invention is provided below.
U.S. Pat. Nos. 3,911,534 and 3,974,581 to Henry J. Martens et al. disclose a security tag having the pin contained on a first strip that is hingedly attached to a second strip that has the locking component thereon. The pin of the first strip penetrates the article that is to be secured and is received in the locking component of the second strip such that the article is maintained therebetween. The hinged attachment may lead to the bending of the pin when contacting the locking component because of the predetermined arc that it must travel as a result of the hinged arrangement. Some items of merchandise are solid and cannot be pierced with the attachment pin used by some EAS tags. Lanyards have been developed for these products.
The '534 and '581 patents also disclose a pin soldered to a chain at one end and the other end of the chain riveted to the tag cover. A drawback with existing lanyards is that they may be severed to remove the tag holder from the item of merchandise. Once severed, the tag holder is destroyed and must be replaced. Some existing lanyards are difficult to assemble and require both ends of the lanyard to be held in alignment while the sharp tack of the holder is threaded through the ends of the lanyard.
In addition, the prior art, such as U.S. Pat. No. 5,069,047 to Lynch, discloses pin clutch mechanisms that function by forcing a plurality of balls around the pin member by a resilient means, which balls are disengaged from said pin by the use of a magnet. However, such pin clutch mechanisms are defeated by sharply striking the tag with a tool, such as a hammer, which release the balls from engagement with the pin. The prior art, such as U.S. Pat. No. 5,140,836 to Hogan, discloses a tag that can be attached to articles without piercing the same with a pin. However, such devices may be defeated by simply cutting through the engaging member. Furthermore, because the engaging member is detachable from the tag, it can be misplaced or lost by the user.
The prior art does not address the need for an EAS tag that is difficult to defeat and easy to use. In addition, the prior art fails to provide a theft deterrent tag assembly that can be securely engaged to articles that cannot be penetrated by a pin. Therefore, there remains a long standing and continuing need for an advance in the art of EAS and theft deterrent tags that makes the tags more difficult to defeat, simpler in both design and use, more economical and efficient in their construction and use, and provide a more secure and reliable engagement of the article to be monitored.
SUMMARY OF THE INVENTION
Accordingly, it is a general object of the present invention to overcome the disadvantages of the prior art.
It is another objective of the invention to provide a cost-efficient EAS tag.
It is another objective of the invention to provide an EAS tag that is durable.
It is a further objective of the invention to provide an EAS tag that is detachable when used with an authorized detaching unit.
It is a further objective of the invention to provide an EAS tag that provides a tag that can be attached to an item to be monitored without penetrating the item.
It is still a further objective of the invention to provide a theft deterrent device that can be quickly and easily secured to an article made of varying materials to prevent the unauthorized removal of the article.
It is yet a further object of the invention to provide a rugged theft deterrent unit to permit the repeated use thereof.
It is still a further object of the invention to provide a theft deterrent unit with a locking mechanism that can withstand a strike thereto by a hammer.
In keeping with the principles of the present invention, a unique EAS theft deterrent tag is disclosed wherein the tag is capable of engaging articles that are to be monitored without necessitating the puncture of the articles with a pin. In addition, by providing a first and second half that are hingedly attached, labor time and costs are reduced when removing the tag from an article being protected thereby because separate bins are not required for the two halves. In addition, replacement costs are further reduced because the mates to the tags cannot be separated and lost.
In addition, the magnetic force necessary to disengaged the attaching mechanism of the tag is greater than required in the prior art ball and clutch mechanisms. Furthermore, the attaching mechanism of the instant invention provides a shock absorbing mechanism to prevent defeat of the attaching mechanism by the application of a strike force thereto by a blunt object.
Such stated objects and advantages of the invention are only examples and should not be construed as limiting the present invention. These and other objects, features, aspects, and advantages of the invention herein will become more apparent from the following detailed description of the embodiments of the invention when taken in conjunction with the accompanying drawings and the claims that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
It is to be understood that the drawings are to be used for the purposes of illustration only and not as a definition of the limits of the invention. In the drawings, wherein similar reference characters denote similar elements throughout the several views:
FIG. 1 is a front perspective view of the tag of the instant invention in an unengaged state.
FIG. 2 is a front outer perspective view of the tag.
FIG. 3 is a front perspective view of the tag in an engaged state.
FIG. 4 is a left side perspective view of the tag in an engaged state.
FIG. 5 is a left side elevational view of the tag with the first left wall removed.
FIG. 6 is a partial cut-away view of a first half of the tag in an unassembled and unengaged state.
FIG. 7 is a perspective view of first and second members as removed from the tag.
FIG. 8 is a cross-sectional view of the tag taken along line 8 - 8 of FIG. 3 .
FIG. 9 is a right side perspective view of an alternate preferred embodiment of the tag in an unengaged state.
FIG. 10 is a front outer perspective view of the alternate preferred embodiment of the tag in an unengaged state.
FIG. 11 is a right side elevational view of the alternate preferred embodiment of the tag in an engaged state.
FIG. 12 is a front perspective view of the alternate preferred embodiment of the tag in an engaged state.
FIG. 13 is a rear plan view of the alternate preferred embodiment of the tag in an engaged state.
FIG. 14 is a partial cut away side view of first member of the tag.
FIG. 15 is a partial cut away front view of first member of the tag.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIGS. 1 through 4 , a tag 20 is illustrated having a first half 22 and a second half 24 . First and second halves 22 and 24 are preferably made of a hard or rigid material and are adapted to attach to one another and form a front end 26 and a rear end 28 . A usable rigid or hard material might be a hard plastic such as, for purposes of illustration but not limitation, an injection molded ABS plastic. First and second halves 22 and 24 are hingedly attached at rear end 28 and are detachably attached at the front end 26 by an attaching means.
Now also referring to FIGS. 5 and 6 , first half 22 has first left wall 30 and a first right wall 32 interconnected at the periphery thereof by a first outer wall 34 and a first inner wall 36 , thereby a space is formed therebetween. In a preferred embodiment, ABS plastic material is used to make tag 20 whereby first left wall 30 and, first outer wall 34 , and first inner wall 36 may be injection molded and then first right wall 32 is then joined with first outer wall 34 and first inner wall 36 via an ultrasonic weld, or adhesive, or other joining means known in the art.
First half 22 has a first compartment 38 defined therein which receives an electronic surveillance means 40 . Electronic surveillance means may be a resonant tag circuit which is not the subject of the instant invention and a detailed description thereof is disclosed in U.S. patent application Ser. No. 10/410,486, titled “Article Surveillance Tag Having a Metal Clip,” filed on Apr. 8, 2003, which is incorporated herein by reference. It is to be understood that alternate resonant tag circuitry that is known in the art may also be used with the instant invention. Electronic surveillance means 40 functions with electronic article surveillance systems that are well known in the art to prevent theft and similar unauthorized removal of articles from a controlled area.
A second compartment 42 is formed within first half 22 and an opening 44 to second compartment 42 is formed through first inner wall 36 . A first partition 46 and end partition 48 extend between first left wall 30 and first right wall 32 , wherein first partition 46 is substantially perpendicular to end partition 48 . A second partition 50 extends substantially perpendicularly from end partition 48 and from first right wall 32 and is substantially parallel to first partition 46 . Second partition 50 has a second semi-circular cut out region 52 defined therein and second partition 50 does not extend to first left wall 30 . A third partition 54 extends substantially perpendicularly from first right wall 32 and is substantially parallel to second partition 50 . Third partition 54 also defines a third semi-circular cut-out region 56 that is axially aligned with second semi-circular cut out region 52 of second partition 50 . A fourth partition 58 extends perpendicularly from first right wall 32 and is substantially perpendicular to third partition 54 . Fourth partition 58 also defines a fourth semicircular cut-out region 60 . Similar partitions as partitions 50 , 54 and 58 extend from first left wall 30 in mirror fashion (not shown).
Now also referring to FIGS. 7 and 8 , an attaching mechanism 62 has a first member 64 and a second member 66 . First member 64 is substantially tubular having a first aperture 68 at a top end 70 and a second aperture 72 at a bottom end 74 , wherein said top end 70 curves inwardly such that first aperture 68 has a smaller circumference than second aperture 72 . First member 74 has a circumferentially extending first lip 76 that is of sufficient thickness to be received between second partition 50 and third partition 54 when the tag is in an assembled state. In addition, third partition 58 also engages top end 70 of first member 64 when the tag 20 is in an assembled state. When the tag 20 is in an assembled state, first aperture 68 is axially aligned with an orifice 77 defined through first outer wall 34 of first half 22 .
Second member 66 has a domed end 78 and a third aperture 80 defined at an opposing end 82 . A circumferential second lip 84 extends outwardly from second member 66 at a region closer to opposing end 82 . The domed end 78 extends through first aperture 68 of first member 64 such that second lip 84 engages top end 70 thereof and is securely maintained therein. The domed end 78 further extends through orifice 77 when tag 20 is in an assembled state. A first resilient means 86 is received and maintained within the domed end 78 , and in a preferred embodiment, first resilient means 86 is a spring. An attaching member 88 has a base region 90 and an elongated attaching region 92 and attaching member 88 is slideably received within second member 66 and engages first resilient means 86 at the base region 90 such that attaching region 92 extends away from domed end 78 . Resilient means 86 is positioned for forcing attaching member 88 toward third aperture 80 . Attaching member 88 is made of a material that responds to magnetic forces and in a preferred embodiment is made of stainless steel. A second resilient means 94 , which in a preferred embodiment is a spring, engages second lip 84 and extends towards third aperture 80 .
A cover 96 , that is substantially circular, is secured to first member 64 and covers second aperture 72 and encloses second member 66 , first resilient means 86 , attaching member 88 , and second resilient means 94 . A bore 98 is defined through cover 96 and is axially aligned with third aperture 80 . Bore 98 is of sufficient size to allow attaching region 92 to pass through yet engages base region 90 by cover 96 .
Second half 24 has a second left wall 100 and a second right wall 102 interconnected at the periphery thereof by a second outer wall 104 and a second inner wall 106 , thereby a space is formed therebetween. Second half 24 has a leading end 108 that is distal to rear end 28 . An attaching component 110 extends from leading end 108 and attaching component 110 is adapted to engage attaching member 88 in a secure yet releasable manner. Attaching component 110 defines a cavity 112 which is adapted to receive attaching region 92 of attaching member 88 therein in a secure manner. In a preferred embodiment, attaching component 110 has a front edge 114 that is beveled and when attaching component 110 is inserted into second compartment 42 , front edge 114 forces attaching region 92 towards domed end 78 . As attaching component 110 travels further into second compartment 42 , cavity 112 becomes axially aligned with attaching region 92 and first resilient means 86 forces attaching region 92 into cavity 112 and securely maintains attaching component 110 within second compartment 42 .
In such attached position, as illustrated in FIG. 8 , first inner wall 36 and second inner wall 106 oppose one another and can maintain an article to be monitored securely therebetween. In a preferred embodiment, first inner wall 36 and second inner wall 106 define a opening 116 , which is preferably circular in nature, that can receive an article to be monitored securely therein. Opening 116 can be made to predetermined dimensions to receive various sporting articles such as, but not limited to, baseball bats, golf clubs, tennis racquets, and baseball mitts. In a preferred embodiment, strips of material 118 (e.g. rubber or elastic material) may be attached to first and second inner walls 36 and 10 to provide additional friction in engaging the article retained therebetween. Additionally, a plurality of ribs 120 may extend inwardly from material 118 to add further friction in engaging the article retained therein.
In order to allow the removal of tag 20 from an article maintained therein, a magnet having a predetermined amount of magnetic force for overcoming the force applied by first resilient means 86 on attaching member 88 is applied to domed end 78 . When the predetermined amount of magnetic force is applied to domed end 78 , attaching member 88 is forced to move towards domed end 78 by compressing first resilient means 86 which thereby withdraws attaching region 98 from engagement with attaching component 110 and attaching component 110 can now be withdrawn from second compartment 42 . Upon removal of the magnetic force, resilient means 86 recoils and forces attaching region 92 to its attaching state to receive attaching component 110 .
The amount of magnetic force necessary to overcome the force applied by the first resilient means 86 , is greater than the force necessary to overcome the force applied by springs of the ball and clutch mechanisms in the prior art. Such stronger magnets are not as readily available to miscreants that would attempt to defeat the article surveillance provided by tag 20 .
Second resilient mans 94 acts as a shock absorber if tag 20 is struck with a hammer in an attempt to defeat tag 20 . When tag 20 is struck, second resilient means 94 absorbs the oscillations that may be caused by movement of second member 66 toward cover 96 . Furthermore, as a result of such movement, second resilient means 86 is compressed and applies greater force on base region 90 of attaching member 88 thereby maintaining secure engagement of attaching region 92 with attaching component 110 .
In a preferred embodiment, a biasing element 122 is installed in rear end 28 and functions with the hinged attachment thereof to maintain tag 20 in a normally unattached state as illustrated in FIGS. 1 and 2 . Accordingly, when a magnetic force is applied to domed end 78 causing withdrawal of attaching region 92 from attaching component 110 , tag 20 assumes the unattached state as a result of biasing element 122 . In a preferred embodiment, biasing element 122 is a coiled member.
Now referring to FIGS. 9 through 15 , an alternate preferred embodiment of tag 20 is disclosed having another preferred attaching means. Second member 66 now has an opposing end 82 that is of a greater diameter than domed end 78 whereby a substantially conical form is achieved. A retaining wall 124 extends from first half 22 is adapted to retain second member 66 therein in a secure yet moveable manner. Retaining wall 124 has a top half 126 and a bottom half 128 , wherein bottom half 128 is injection molded with first half 22 and top half 126 is attached to bottom half 22 to enclose second member 66 therebetween. Top half 126 and bottom half 128 define a leading end 130 which defines a hole 132 through which domed end 78 extends. A trailing end 134 is formed at an end of retaining wall 124 that is distal to the leading and 130 . Trailing end 134 has cover 96 attached thereto with bore 98 that allows passage of attaching region 92 . By allowing second member 66 to move within retaining wall 124 , it allows shock absorption if tag 20 is struck by a hammer. Authorized disengagement of tag 20 is achieved in the manner as previously detailed by the application of a magnetic force sufficient to overcome the force applied by first resilient means 86 .
While the above description contains many specificities, these should not be construed as limitations on the scope of the invention, but rather as an exemplification of one preferred embodiment thereof. Many other variations are possible without departing from the essential spirit of this invention. Accordingly, the scope of the invention should be determined not by the embodiment illustrated, but by the appended claims and their legal equivalents. | An article surveillance tag that has a shock absorbing mechanism that prevents unauthorized removal of the tag by the application of a strike force to the tag by a blunt object. In one embodiment, the article surveillance tag is adapted to engage articles that cannot be penetrated by pins. | 4 |
BACKGROUND
The present disclosure relates to a memory device to/from which data is written/erased by a change in a conduction type of an amorphous semiconductor layer and, more particularly, to a memory device having an MISFET (Metal Insulator Semiconductor Field Effect Transistor) structure.
With the dramatic spread of small devices for individuals such as information communication devices and, particularly, portable terminals, elements such as memories and logics constructing the devices are demanded to achieve higher performances such as higher integration, higher speed, and lower power. A nonvolatile memory such as a semiconductor flash memory or an FeRAM (Ferroelectric Random Access Memory) is being actively studied and developed for further higher performances.
In recent years, one of nonvolatile memories which are regarded as promising ones is a phase-change memory (refer to, for example, S. Hudgens, et al., “Overview of Phase-Change Chalcogenide Nonvolatile Memory Technology”, MRS BULLETIN NOVEMBER 2004, p. 829). A phase-change memory has a chalcogenide semiconductor layer between two electrodes one of which is connected to a selection diode or a selection transistor, and a part of the chalcogenide semiconductor layer is in contact with one of the electrodes. In the interface with the electrode, the chalcogenide semiconductor layer changes from a crystal state of low electric resistance to an amorphous state of high electric resistance or from the amorphous state to the crystal state by generation of Joule heat. When the crystal state is set as “1” and the amorphous state is set as “0”, by reading the change in the resistance state, “1” and “0” can be discriminated from each other. A resistance value histogram corresponding to the state of “1” and that corresponding to the state of “0” are a resistance separation characteristic which is an important characteristic to increase memory performance.
An amorphous chalcogenide used for a phase-change memory is glass containing a chalcogen element (S, Se, Te) and its representative one is Ge 2 Sb 2 Te 5 or the like. Glass and an amorphous material are almost equivalent terms. Both of them are solids but do not have the long-range order of a crystal structure unlike liquids. A material having no clear glass-transition point is defined here as an amorphous material.
A phase transition between the amorphous state and the crystal state in the chalcogenide semiconductor layer always accompanies latent heat and is therefore classified as a so-called phase transition of the first kind. The phase transition of the first kind defined here relates to the case where the first order differential (the following expression (1)) of the Gibbs free energy G is discontinuous. In this case, discontinuity occurs in volume or enthalpy. In the expression (1), p denotes pressure of a system, and T denotes absolute temperature of the system. Latent heat necessary for the phase transition of the first kind is equal to discontinuity in enthalpy and, in a state where the pressure or temperature of the system is constant, endothermic reaction or exothermic reaction occurs.
(
∂
G
∂
P
)
T
OR
(
∂
G
∂
T
)
P
(
1
)
A chalconide semiconductor is used as a channel layer of a TFT (Thin Film Transistor) in the past. Particularly, a thin film transistor using Te (tellurium) has a relatively good characteristic including hall mobility of about 250 cm 2 /Vs. However, there are issues such as toxicity of Te, limitation only to a p-type thin film transistor, and magnitude of leak current. With the advent of an amorphous hydrogenated silicon semiconductor, the chalcogenide semiconductor is not used for the channel layer.
SUMMARY
In a phase-change memory based on such phase transition of the first kind, when the chalcogenide semiconductor layer changes from the crystal state to the amorphous state, almost half of input Joule heat is absorbed as latent heat. In other words, in a phase-change memory as a related art, the Joule heat higher than the latent heat has to be generated, and it is difficult to largely reduce power consumption in principle.
In the phase transition of the first kind, temperature rise exceeding the melting point of the chalcogenide semiconductor is necessary. Due to the temperature rise, the material in the periphery of the chalcogenide semiconductor layer is thermally damaged very severely.
Further, the phase transition of the first kind accompanies a large volume change of about a few % corresponding to reconstruction of the crystal state—the amorphous state before and after the phase transition, so that a film peeling phenomenon due to the difference between the thermal expansion coefficient of the chalcogenide semiconductor layer and the thermal expansion coefficient of the electrode occurs. Such temperature rise and volume change restrict the number of rewriting times and reliability.
In the case of using the chalcogenide semiconductor for the phase change memory, most often, it is used as a single-layer film. There is also a case such that, as described above, the chalcogenide semiconductor is used for the channel layer of a thin film transistor. However, for example, even in a complicated MISFET structure, as long as the resistance change caused by the phase transition of the first kind is used as a principle, occurrence of issues such as power consumption and reliability is not avoided, and a realistic advantage is not obtained.
It is therefore desirable to provide a nonvolatile memory device achieving low power consumption and high reliability.
A memory device according to an embodiment of the disclosure includes: an amorphous semiconductor layer of a first conduction type; a solid electrolyte layer containing movable ions and provided in contact with a part of one of faces of the amorphous semiconductor layer; a first electrode electrically connected to the amorphous semiconductor layer via the solid electrolyte layer; a second electrode electrically connected to one of the faces of the amorphous semiconductor layer; and a third electrode provided over the other face of the amorphous semiconductor layer with an insulating layer therebetween. At the time of application of voltage to the third electrode, at least a part of the amorphous semiconductor layer reversibly changes to a second conduction type.
In the memory device, by application of predetermined voltage to the third electrode, an accumulation layer is formed on the surface of the amorphous semiconductor layer, and movable ions move from the solid electrolyte layer to the amorphous semiconductor layer. It changes the conduction type of a part of the amorphous semiconductor layer, a pn junction is formed, and a resistance value between the first and second electrodes changes. By the change in the resistance value, data is written/erased. By adjusting the magnitude and time of the voltage applied to the first and second electrodes, the position of the pn junction formed in the amorphous semiconductor layer is adjusted, and the magnitude of the resistance value between the first and second electrodes is selected. In other words, multivalue recording is achieved.
In the memory device as an embodiment of the disclosure, the conduction type of the amorphous semiconductor layer is changed by making movable ions move between the solid electrolyte layer and the amorphous semiconductor layer, so that data is written/erased and those states are retained. The change in the conduction type in the amorphous state does not accompany release/absorption of latent heat and a volume change and is carried out by the phase transition of the second kind which does not need a temperature rise exceeding the melting point of the amorphous semiconductor layer. Therefore, power consumption is reduced, and the reliability improves.
It is to be understood that both the foregoing general description and the following detailed description are exemplary, and are intended to provide further explanation of the technology as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and, together with the specification, serve to explain the principles of the technology.
FIG. 1 is a cross section illustrating the configuration of a memory device according to an embodiment of the present disclosure.
FIG. 2 is an energy band conceptual diagram of a channel part when voltage is applied to an electrode.
FIG. 3 is a schematic diagram illustrating states of an amorphous semiconductor layer before and after a phase transition of the second kind.
FIG. 4 is a conceptual diagram of a memory device in a set state.
FIG. 5 is a conceptual diagram of a memory device in a reset state.
FIG. 6 is a cross section illustrating the configuration of a memory device as a modification.
FIG. 7 is a characteristic diagram illustrating characteristics of memory switching.
FIG. 8 is a characteristic diagram illustrating characteristics of threshold switching.
FIG. 9 is a characteristic diagram illustrating negative resistance in an S-shape type.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present disclosure will be described in detail below with reference to the drawings. The description will be given in the following order.
1. Embodiment
Memory device having MISFET structure
2. Modification
Memory device having heat barrier layer
Embodiment
FIG. 1 illustrates a sectional configuration of a memory device 1 according to an embodiment of the present disclosure. The memory device 1 has an electrode 11 (third electrode) on a substrate 10 , and an amorphous semiconductor layer 13 is provided over the electrode 11 via an insulating layer 12 . An electrode 14 (second electrode) and an electrode 15 (first electrode) are provided on/over the surface of the amorphous semiconductor layer 13 . A solid electrolyte layer 16 is provided between the electrode 15 and the amorphous semiconductor layer 13 . An insulating layer 17 is provided between the electrode 14 on the amorphous semiconductor layer 13 and the electrode 15 . In other words, the memory device 1 has an MISFET structure using the electrode 11 as a gate electrode, the electrode 14 as a source electrode, and the electrode 15 as a drain electrode.
The substrate 10 is made of, for example, semiconductor such as silicon. The insulating layers 12 and 17 are made of, for example, silicon dioxide (SiO 2 ).
The amorphous semiconductor layer 13 functions as a channel part in which carriers flow between the electrodes 14 and 15 . The amorphous semiconductor layer 13 has a conduction type (first conduction type) which is the n type or the p type in the initial state. At the time of application of voltage to the electrode 11 , movable ions move from the solid electrolyte layer 16 , so that the conduction type of at least a part of the amorphous semiconductor layer 13 changes reversibly to the second conduction type. Specifically, while forming an accumulation layer, the movable ions move from the solid electrolyte layer 16 to the amorphous semiconductor layer 13 or from the amorphous semiconductor layer 13 to the solid electrolyte layer 16 , the conduction type of at least a part of the amorphous semiconductor layer 13 changes from the n type to the p type or from the p type to the n type. It changes the resistance state (resistance value) between the electrodes 14 and 15 , data is written/erased, and the state is retained.
In the embodiment, by adjusting time and magnitude of the voltage applied across the electrodes 14 and 15 as will be described later to change the position of a pn junction formed in the amorphous semiconductor layer 13 , the value of resistance between the electrodes 14 and 15 is controlled.
As such an amorphous semiconductor layer 13 , it is preferable to use chalcogenide semiconductor containing a chalcogen element such as S, Se, or Te or an alloy of the chalcogen element.
The conduction type of the amorphous semiconductor layer 13 changes according to the polarity of the voltage applied to the electrode 11 . (A) to (C) of FIG. 2 are conceptual diagrams of the energy band of a channel part in the case of applying voltage to an electrode of a thin film transistor. Electrons or holes are accumulated on the surface of the channel part in accordance with the polarity of voltage V gs applied to the electrode, and the energy band in the surface of the channel part is bent by the voltage. The phenomenon is so-called band bending. The state where the conduction type of the channel part is inverted is called an inversion state, and a state where the band bending reaches the limit and a depletion layer does not expand further is called a strong inversion state. In the strong inversion state, an enormous number of carriers are generated. In the memory device 1 , by using the concept of the band bending, the phase shift of the second kind which will be described later occurs in the amorphous semiconductor layer 13 .
The solid electrolyte layer 16 provided between the amorphous semiconductor layer 13 and the electrode 15 has the function of supplying positive or negative movable ions to the amorphous semiconductor layer 13 or receiving movable ions from the amorphous semiconductor layer 13 . Preferably, the solid electrolyte layer 16 has proper electric conduction property and uses a high-strength high-corrosion-resistance material. For example, a metal glass or metal amorphous material as an alloy whose metal element is a main component is desirable. Particularly, Zr-based metal glass and ZrCuAl-based metal glass have relatively high viscosity and are suitable to finely control a supply amount of movable ions to the amorphous semiconductor layer 13 . To facilitate movement of the movable ions to the amorphous semiconductor layer 13 , preferably, the property of the solid electrolyte layer 16 and that of the amorphous semiconductor layer 13 as viscous fluids are close to each other. Concretely, in mathematical expression (2) showing a temperature characteristic which determines viscosity η, preferably, activation energy Ea of both of the solid electrolyte layer 16 and the amorphous semiconductor layer 13 is equal to or larger than 2 eV. In the expression (2), η 0 denotes proportional constant, k B denotes Boltzmann constant, and T denotes absolute temperature.
η
=
η
0
exp
(
E
a
k
B
T
)
(
2
)
The movable ion is, preferably, a monoatomic ion whose radius is small enough to pass through the lattice of the amorphous semiconductor layer 13 . For example, in the case of using the amorphous semiconductor layer 13 of the p-type, preferably, the solid electrolyte layer 16 contains any of a monovalent positive ion H + , Li + (hydron containing D + and T + ), Na + , K + , Ag + , Cu + , Hg + , Ti + , Rb + , or Cs + , a bivalent positive ion Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cd 2+ , Ni 2+ , Zn 2+ , Cu 2+ , Hg 2+ , Fe 2+ , Co 2+ , Sn 2+ , Pb 2+ , or Mn 2+ , a trivalent positive ion Al 3+ , Fe 3+ , or Cr 3+ , a tetravalent positive ion Sn 4+ , and the like. For example, in the case of using the amorphous semiconductor layer 13 of the n-type, it is preferable to contain any of a monovalent negative ion H − (hydride), F − , Cl − , Br − , or I − , a bivalent negative ion O 2− or S 2− , and the like. Preferably, the operation temperature at which ions become movable is equal to or higher than 300K, and the concentration of movable ions in the solid electrolyte layer 16 at room temperature is equal to or less than the trap concentration of the amorphous semiconductor layer 13 . Consequently, in the manufacturing process, after stacking the solid electrolyte layer 16 on the amorphous semiconductor layer 13 , the movable ions are prevented from being excessively diffused to the amorphous semiconductor layer 13 by annealing process or the like to disturb a change in the conduction type of the amorphous semiconductor layer 13 .
The electrodes 11 and 15 are made of a low-resistance metal such as aluminum (Al) or copper (Cu), and the electrode 14 is made of, for example, tungsten (W) or titanium nitride (TiN) to facilitate temperature rise in the amorphous semiconductor layer 13 .
In the memory device 1 of the embodiment, when pulse voltage Vg (gate voltage) is applied to the electrode 11 , movable ions move between the solid electrolyte layer 16 and the amorphous semiconductor layer 13 . While forming an accumulation layer on the surface of the amorphous semiconductor layer 13 , the conduction type of a partial region in the amorphous semiconductor layer 13 changes. By the change in the conduction type of the amorphous semiconductor layer 13 , data is written/erased. In the following, the change in the conduction type in the amorphous semiconductor layer 13 will be described in detail.
The change in the conduction type of the amorphous semiconductor layer 13 is caused by the phase transition of the second kind which occurs between two distinguishable states of the amorphous state. First, the two states existing in the amorphous state will be described.
It is known that the chalcogenide semiconductor containing a chalcogen element (S, Se, Te) or an alloy of the chalcogen element exhibits two kinds of electric switching characteristics (P. G. Le Comber and J. Mort, “Electronic and Structural Properties of Amorphous Semiconductors”, Academic press, 1973).
One of the characteristics is a voltage-current characteristic called “memory switching” illustrated in FIG. 7 . Ge 2 Sb 2 Te 5 , Te 81 Ge 51 X 4 , or the like has a soft glass structure and, when application voltage exceeds a threshold voltage V th , changes from the amorphous state to the crystal state in very short time. The voltage-current characteristic obtained at this time is “memory switching”. On the other hand, Te 30 As 30 Si 10 Ge 10 or the like has a hard tetrahedral structure, is not easily crystallized, and exhibits a switching phenomenon as illustrated in FIG. 8 in the amorphous state. This is another voltage-current characteristic called “threshold switching”.
However, Ge 2 Sb 2 Te 5 which normally displays the memory switching also exhibits the threshold switching by sweeping an application voltage in time shorter than the crystallization time. Two amorphous states appearing in the threshold switching, that is, an amorphous state in high resistance and an amorphous state in low resistance relate to the present disclosure. Next, the mechanism that the amorphous state in high resistance and the amorphous state in low resistance appear will be described.
A sufficient Joule heat is necessary for crystallization of Ge 2 Sb 2 Te 5 , and high current to generate the Joule heat is passed only in the amorphous state in low resistance. Since a voltage-current characteristic which is seen when the amorphous state in low resistance appears exhibits an S-shaped negative resistance as illustrated in FIG. 9 , the current is called an “S-shaped negative current (SNDC)”. The SNDC appearing mechanism relates to formation of a coarse/dense distribution of current density called filament and is caused by collisional ionization (E. Scholl, “Non-equilibrium Phase Transition in Semiconductors”, Springer-Verlag, 1987). The collisional ionization refers to a phenomenon that carriers accelerated by electric field collide with a lattice and new carriers are created. A phenomenon such that repetition of the collisional ionization starts autocatalytic multiplication of the number of carriers and, finally, electric insulation is lost is called avalanche breakdown in semiconductor (Y. Okuto, “Threshold energy effect on avalanche breakdown voltage in semiconductor junction”, Solid-state Electronics, 18, 161 (1975)).
In a chalcogenide semiconductor, a trap level created by a not-coordinated (dangling bond) lone electron pair in a chalcogen element relates to the collisional ionization. The amorphous state in low resistance is stable only when the electric field is applied and is therefore also called an ionization equilibrium state. Since the chalcogenide semiconductor has two stable amorphous states and the stable states are determined by the electric field, E. Scholl classifies the state transition between the amorphous states as a so-called phase transition of the second kind using the electric field as an order parameter. In this case, the phase transition of the second kind refers to a phenomenon that the second order differential (the following expression (3)) of Gibbs free energy G becomes discontinuous. In the expression (3), p denotes pressure of a system and T denotes absolute temperature of the system. All of the structural phase transition, magnetic phase transition, transition from a normal conducting state to a superconducting state, a superfluid state of liquid helium, and the like are the phase transition of the second kind which appears when the order parameter changes from an order state to a disorder state. Since the first order differential of the Gibbs free energy is continuous in the second or higher-order phase transition, latent heat is not generated, and a discontinuous point in specific volume is not also generated. In the present disclosure, the phase transition of the second kind is used as the principle of the resistance change in the memory device, so that release/absorption of the latent heat and a volume change as drawbacks of the memory device which writes/erases data by the phase transition of the first kind are unaccompanied, and a temperature rise exceeding the melting point of the chalcogenide semiconductor is also unnecessary. Next, the reason why the conduction type is changed by the phase transition of the second kind between the two amorphous states will be described.
(
∂
2
G
∂
P
2
)
T
OR
(
∂
2
G
∂
T
2
)
P
(
3
)
When collisional ionization via the trap level occurs in the chalcogenide semiconductor, an original majority carrier (holes in most cases of the chalcogenide semiconductors) is trapped and cannot move in space. To satisfy an electroneutrality condition, only another carrier (electrons in most cases of chalcogenide semiconductors) generated by pair production by the collisional ionization can contribute to current. This is the mechanism of the change in the conduction type between the amorphous state in low resistance and the amorphous state in high resistance. In the case where the majority carrier is an electron, the semiconductor is classified as the n-type semiconductor. In the case where the majority carrier is a hole, the semiconductor is classified as the p-type semiconductor. It is known that, in most cases, the chalcogenide semiconductor is of the p type and, by stacking a silicon semiconductor of the n type, the threshold switching is provided with the diode characteristic (K. E. Petersen, “On state of amorphous threshold switches” J. Appl. Phys., 47, 256 (1976)). Since the amorphous state in high resistance changes to the p type and the amorphous state in low resistance changes to the n type, the diode characteristic appears in the threshold switching.
However, as described above, the amorphous state in low resistance exists stably only when the electric field is applied. When the electric field is set to be zero, the amorphous state returns to the amorphous state in high resistance. Consequently, the mechanism cannot be applied as it is to the memory device. The embodiment provides the following mechanism capable of maintaining the amorphous state in low resistance even when the electric field is set to zero.
Since the viscosity of the amorphous semiconductor changes according to the composition and temperature, when ions are introduced by electric field acceleration while increasing the temperature of the amorphous semiconductor, a part of a glass network can be substituted with ions (R. Fairman and B. Ushkov, “Semiconducting Chalcogenide Glass”, Elsevier Academic press, 2004). Such an ion implantation method is called substitutional doping. Even when avalanche breakdown does not occur, by the band bending of the inversion state or the strong inversion stage as described above, the amorphous state in low resistance is allowed to appear. In the memory device 1 of the embodiment, the amorphous semiconductor layer 13 is formed in contact with the solid electrolyte layer 16 containing movable ions, and the movable ions are introduced along the inversion region subjected to the band bending from the solid electrolyte layer 16 to the amorphous semiconductor layer 13 . In other words, the concept of substitutional doping and band bending is used. (A) and (B) of FIG. 3 are schematic diagrams illustrating states of the amorphous semiconductor layer 13 before and after a phase transition of the second kind in the case where the amorphous semiconductor layer 13 is made of GeTe and positive ions are Cu 2+ .
In the memory device 1 of the embodiment, when the pulse voltage Vg (gate voltage) is applied to the electrode 11 , movable ions move between the solid electrolyte layer 16 and the amorphous semiconductor layer 13 , while forming an accumulation layer on the surface of the amorphous semiconductor layer 13 , the conduction type of a part of the amorphous semiconductor layer 13 changes. In other words, a pn junction is formed in the amorphous semiconductor layer 13 , the state of resistance between the electrodes 14 and 15 changes, and data is written or erased. In the following, the amorphous state in high resistance (original conduction type) of the amorphous semiconductor layer 13 is defined as a reset state, the amorphous state in low resistance (opposite conduction type) of at least a part of the amorphous semiconductor layer 13 is defined as a set state, and the operation will be described concretely.
For example, the amorphous semiconductor layer 13 is made of a chalcogenide semiconductor of the p type. First, when the pulse voltage Vg is applied to the electrode 11 , Joule heat is generated in the amorphous semiconductor layer 13 , temperature rises, and movable ions are supplied by the electric field acceleration from the solid electrolyte layer 16 to the amorphous semiconductor layer 13 . When the positive ions are implanted from the solid electrolyte layer 16 to the amorphous semiconductor layer 13 of the p type by the electric field acceleration, a part of a not-coordinated lone electron pair in the chalcogen element is used to trap the implanted positive ions, and the conduction type of at least a part of the amorphous semiconductor layer 13 changes to the n type. The movable ions are guided into the amorphous semiconductor layer 13 along the band-bent inversion region in the surface of the amorphous semiconductor layer 13 , and a pn junction occurs in the amorphous semiconductor layer 13 .
FIG. 4 is a conceptual diagram of the memory device 1 in the set state. Since movement of the movable ions is accelerated by the voltage applied to the electrodes 14 and 15 , by adjusting the magnitude and time of the voltage applied to the electrodes 14 and 15 , the degree of drifting of the movable ions in the amorphous semiconductor layer 13 is controlled. In other words, the position of the pn junction formed in the amorphous semiconductor layer 13 is controlled, and the value of resistance between the electrodes 14 and 15 is arbitrarily adjusted, and multivalue information can be held. For example, by selecting four combinations of the magnitude and time of the voltage applied to the electrodes 14 and 15 so that the resistance state is expressed in four values, multivalue recording of two bits is performed. Sense current which flows when the voltage Vg is applied to the electrode 11 changes step by step only by the number of resistance states selected.
To make the phase transition of the second kind in which the conduction type changes as described above occur, first, when the amorphous semiconductor layer 13 is of the p type, the solid electrolyte layer 16 has to contain movable positive ions. When the amorphous semiconductor layer 13 is of the n type, the solid electrolyte layer 16 has to contain movable negative ions. Further, by the movement of the movable ions, the trap concentration in the amorphous semiconductor layer 13 has to become equal to or higher than donor concentration or acceptor concentration. An amorphous semiconductor containing a chalcogen element or an alloy of the chalcogen element has many not-coordinated lone electron pairs and has excellent property to trap atoms of a different kind, so that it is preferable for the amorphous semiconductor layer 13 . For example, germanium telluride (Ge X Te 100-X ) may be used for the amorphous semiconductor layer 13 . In this case, when atomic percent of Ge atoms in Ge X Te 100-X is X (at %), more preferably, X is in the range of 10 at % to 60 at % both inclusive.
For example, when Ge 2 Sb 2 Te 5 is used for the amorphous semiconductor layer 13 , it is estimated that the trap concentration is 10 21 cm −3 and the donor concentration and acceptor concentration is about 10 17 to 10 19 cm −3 (A. Pirovano, “Electronic Switching in PCM”, Trans. Electron. Devices, 51, 452 (2004)). The concentration of positive ions introduced from the solid electrolyte layer 16 has to be equal to or higher than 0.01 to 1% of the trap concentration.
On the other hand, in the reset state, the not-coordinated lone electron pairs of the chalcogen element form a glass network or are used to trap holes as the major carrier. The conduction type of the amorphous semiconductor layer 13 is the p type as the original conduction type as illustrated in FIG. 5 . In a state where movable ions are not introduced from the solid electrolyte layer 16 to the amorphous semiconductor layer 13 , the resistance between the electrodes 14 and 15 is very high. Consequently, the amount of sense current which flows when the voltage Vg is applied to the electrode 11 is slight.
The amorphous semiconductor layer 13 is preferably made of a material which is not easily crystallized in order to prevent occurrence of the phase transition of the first kind before the phase transition of the second kind occurs or simultaneous occurrence of the phase transitions of the second and first kinds in the amorphous semiconductor layer 13 . The phase transition of the second kind may be caused in time shorter than crystallization time necessary to cause the phase transition of the first kind in the amorphous semiconductor layer 13 , or the phase transition of the first kind may be prevented by generating heat so that temperature rise stops at a temperature sufficiently lower than the crystallization temperature or the melting point.
A method of manufacturing the memory device 1 of the embodiment will be described below.
First, on the substrate 10 made of silicon or the like, the electrode 11 is formed by, for example, sputtering. After that, the insulating layer 12 made of silicon dioxide is formed by, for example, plasma CVD (Chemical Vapor Deposition). Subsequently, a Ge 20 Te 80 film is formed as the amorphous semiconductor layer 13 by, for example, sputtering and is shaped in a predetermined shape by photolithography and etching. A silicon dioxide film is formed by sputtering and selectively etched to form the insulating layer 17 . A Zr 20 Cu 20 Al 40 (GeTe) 20 film is formed and selectively etched to form the solid electrolyte layer 16 . After that, by vacuum deposition, sputtering, or CVD, the electrodes 14 and 15 are selectively formed. In such a manner, the memory device 1 illustrated in FIG. 1 is completed.
In the memory device 1 of the embodiment, when the pulse voltage is applied to the electrode 11 (gate electrode), movable ions move between the solid electrolyte layer 16 and the amorphous semiconductor layer 13 , and the conduction type of at least a part of the amorphous semiconductor layer 13 changes. By the change, the resistance state between the electrodes 14 and 15 changes, and data is written or erased.
In the memory device 1 of the embodiment, by controlling the magnitude and application time of the voltage applied to the electrodes 14 and 15 , the position of the pn junction formed in the amorphous semiconductor layer 13 is adjusted, and the resistance state (the value of resistance) between the electrodes 14 and 15 can be selected. In other words, multivalue recording is performed. Further, the change in the conduction type of the amorphous semiconductor layer 13 is caused by the phase transition of the second kind which does not accompany release/absorption of latent heat and volume change and does not need a temperature rise exceeding the melting point of the amorphous semiconductor. Therefore, power consumption is reduced, and reliability improves.
A modification of the embodiment will be described below.
(Modification)
As illustrated in FIG. 6 , a heat barrier layer 18 A each having a thickness of 2 nm or less may be provided between the solid electrolyte layer 16 and the electrode 15 , and a heat barrier layer 18 B having a thickness of 2 nm or less may be provided between the amorphous semiconductor layer 13 and the electrode 14 . As the material of the heat barrier layers 18 A and 18 B, for example, titanium oxide (Ti 2 O 3 ), alumina (Al 2 O 3 ), silica (SiO 2 ), or the like may be used. When the movable ions are accelerated by the electric field while the temperature of the amorphous semiconductor layer 13 is increased, the time of the movement of the movable ions between the solid electrolyte layer 16 and the amorphous semiconductor layer 13 can be shortened. The heat barrier layers 18 A and 18 B function as thermal barrier layers and contribute to temperature rise in the amorphous semiconductor layer 13 and the solid electrolyte layer 16 . On the other hand, since the thickness of the heat barrier layers 18 A and 18 B is 2 nm or less, there is no possibility that the electric influence is exerted on the memory device 1 by the tunnel effect.
Although the present disclosure has been described above by the embodiment and the modification, the disclosure is not limited to the embodiment and the like but may be variously modified. For example, the thin film transistor of the foregoing embodiment and the like is classified as an inverted staggered TFT but any of a staggered TFT, a coplanar TFT, an inverted coplanar TFT, and the like may be used.
Although the solid electrolyte layer 16 is provided on the side of the electrode 15 in the embodiment and the like, since the position of the solid electrolyte layer 16 is determined by the polarity of the voltage applied to the electrodes 14 and 15 , it may be provided on the side of any of the electrodes 14 and 15 .
Further, the materials of the layers, the film forming method, the film forming conditions, and the like described in the foregoing embodiment and modification are not limited. Other materials and other film forming methods may be also employed. For example, when the trap concentration is made exceed the donor concentration or the acceptor concentration by movement of movable ions, an oxide semiconductor or a nitride semiconductor may be used for the amorphous semiconductor layer 13 . For example, although the configuration of the memory device 1 has been concretely described in the embodiment and the modification, another layer may be also provided.
The present disclosure contains subject matter related to that disclosed in Japanese Priority Patent Application JP 2010-180490 filed in the Japanese Patent Office on Aug. 11, 2010, the entire content of which is hereby incorporated by reference.
It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alterations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims or the equivalents thereof. | A memory device includes: an amorphous semiconductor layer of a first conduction type; a solid electrolyte layer containing movable ions and provided in contact with a part of one of faces of the amorphous semiconductor layer; a first electrode electrically connected to the amorphous semiconductor layer via the solid electrolyte layer; a second electrode electrically connected to one of the faces of the amorphous semiconductor layer; and a third electrode provided over the other face of the amorphous semiconductor layer with an insulating layer therebetween. At the time of application of voltage to the third electrode, at least a part of the amorphous semiconductor layer reversibly changes to a second conduction type. | 7 |
BACKGROUND OF THE INVENTION
This invention relates generally to radio frequency antenna and more particularly to radio frequency antenna adapted to operate with radio frequency energy having any one of a variety of polarizations.
As is known in the art, it is frequently desirable to use an antenna element which may operate with any one of a variety of polarization (i.e. linear or circular). One type of antenna element capable of such operation is sometimes referred to as a "double ridged" horn. One antenna element of such type generally would include a vertical feed and an independent horizontal feed, the phase centers of such feeds being coincident. For circular polarization the two feeds are fed with radio frequency energy having a quadrature phase difference. In order to provide efficient matching to free space over a relatively wide frequency band, say in the order of 3.5 to 1, it is generally required that the width of the horn be larger than half the wavelength at the nominal operating frequency of the antenna and sometimes be as large as one wavelength. In an array antenna, a plurality of antenna elements are provided in order to attain a relatively wide scan angle, say in the order of 120 degrees. In such array, it is generally required that the phase centers of adjacent ones of the plurality of antenna elements be displaced by less than one half wavelength. It follows then that while a double ridged horn antenna may be adapted to operate with radio frequency energy having circular polarization, such an antenna element may not be readily used, because of its size, in an array antenna having relatively wide scan angles.
In another type of array antenna adapted to provide a variety of polarization each one of the antenna elements includes an orthogonally disposed pair of printed circuit notch shaped antenna elements. One such type of antenna is described in U.S. Pat. No. 3,836,976 entitled "Closely Spaced Orthogonal Dipole Array," inventors George J. Monser, George S. Hardie, John R. Ehrhardt and Terry M. Smith, issued Sept. 17, 1974, and assigned to the same assignee as the present invention. While such antenna is adapted to operate with circularly polarized radio frequency energy over relatively wide scan angles and over a relatively wide band of frequencies, such antenna is limited in its power handling capability and hence is not suitable for use in those applications where such antenna is fed by a transmitter adapted to transmit relatively large amounts of power.
SUMMARY OF THE INVENTION
In accordance with the present invention an antenna element is provided having an open ended waveguide section coupled to a first feed means for establishing radio frequency energy having linear polarization, the electric field vector of such energy being disposed normal to a pair of opposing wall portions of the waveguide. The antenna element includes a microwave circuit means for establishing radio frequency energy having a linear polarization orthogonal to the polarization of the first mentioned radio frequency energy. The microwave circuit includes a dielectric and a conductive sheet disposed over the dielectric; such sheet providing one of the wall portions of the waveguide section. The conductive sheet has an array of notches formed therein, such notches being disposed adjacent the open end of the waveguide section. A second feed means is coupled to the array of notches for establishing radio frequency energy having a linear polarization, the electric field thereof being in the plane of the dielectric and hence normal to the polarization established by the first feed means.
With such arrangement, the first and second feed means are fed in quadrature and the phase centers of the orthogonally disposed polarized radio frequency energy at the open end of the waveguide are substantially coincident to thereby enable the antenna to establish circularly polarized radio frequency energy in free space. Further, the radio frequency energy fed to the second feed means is distributed to an array of notch shaped elements thereby increasing the power handling capability of the antenna element. Still further, the antenna element is relatively compact and suitable to be arranged in an array for providing relatively wide scan angle coverage.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing features of this invention, as well as the invention itself, may be more fully understood from the description read together with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a radio frequency antenna system including an array of antenna elements according to the invention;
FIG. 2 is a perspective view of the array of antenna elements used in the antenna system of FIG. 1;
FIG. 3 is a top plan view of a member used to form a portion of one of the antenna elements of FIG. 2;
FIG. 4 is a bottom plan view of the member of FIG. 3;
FIG. 5 is a side elevation view of the member of FIG. 3;
FIG. 6 is an end elevation view of the member of FIG. 3;
FIG. 7 is an exploded, isometric view of a strip transmission line feed network used to form a portion of one of the antenna elements of FIG. 2;
FIG. 8 is a plan view of the member of FIG. 3 and the strip transmission line feed network of FIG. 7 disposed thereon;
FIG. 9 is an exploded isometric drawing, partly broken away, of one of the antenna elements in the array of FIG. 2;
FIG. 10 is a perspective view of the bottom portion of the member of FIG. 3;
FIG. 11 is an exploded cross-sectional side elevation view of a pair of members of FIG. 3 and a pair of strip transmission line networks of FIG. 7, such pair of feed networks, and pair of members forming the antenna element of FIG. 9, the cross-section of one of such members being taken along lines 11--11 of FIG. 3, one of such pair of members being the member shown in FIG. 3;
FIG. 12 is a cross-sectional side elevation view of the antenna element of FIG. 11; and
FIG. 13 is a cross-sectional view showing a portion of a feed probe used to feed the portion of the antenna element of FIG. 12 formed by the pair of members and also showing a portion of such pair of members, such FIG. 13 being of region 13--13 of FIG. 12.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 a multibeam radio frequency antenna system 10 adapted to operate over a relatively wide band of frequencies, here 4.8 GHZ to 18.0 GHZ is shown to include a radio frequency lens 12 having a plurality of feed ports 14a-14n disposed along a portion of the periphery of such lens 12 and a plurality of here eight array ports 16 1 -16 8 disposed along an opposing portion of the periphery of the lens 12, the plurality of array ports 16 1 -16 8 being coupled to an array 20 of a plurality of, here eight, identically constructed antenna elements 22 1 -22 8 through a power distribution network 24 the details of which will be described hereinafter. Sufficient to say here, however, that the shape of the lens 12, the construction of the power distribution network 24 and the arrangement of the antenna elements 22 1 -22 8 are selected such that n collimated beams of radio frequency energy are formed in free space by the antenna system 10, each one of such n beams having a different direction and each one of such n beams having circularly polarized radio frequency energy.
Referring to FIG. 2 array 20 is shown to include a plurality of identically constructed conductive members 26 1 -26 10 , an exemplary one thereof, here member 26 1 being shown in detail in FIGS. 3-6 and 10 and a plurality of, here nine, identically constructed microwave circuits, here strip transmission line circuits 27 1 -27 9 , an exemplary one thereof, here circuit 27 1 being shown in detail in FIG. 7. A pair of members 26 1 -26 10 and a pair of circuits 27 1 -27 9 form one of the identically constructed antenna elements 22 1 -22 8 . Thus, as shown FIGS. 9, 11 and 12 an exemplary one of the antenna elements 22 1 -22 8 , here antenna element 22 1 is shown to include conductive members 26 1 and 26 2 and strip transmission line circuits 27 1 and 27 2 . (It is noted that constituent parts of member 26 1 and circuit 27 1 are designated by a subscript 1 and constituent parts of member 26 2 and circuit 27 2 are designated by a subscript 2). More particularly, as shown in FIGS. 9, 11 and 12, the upper surface of the antenna 22 1 , is formed, in the frontal portion thereof, by the bottom surface 28 1 of strip transmission line circuit 27 1 and in the rearward portion thereof by the bottom surface 30 1 of conductive member 26 1 ; whereas the lower surface of antenna elements 22 1 is formed, in the frontal portion thereof, by the upper surface 32 2 of strip transmission line circuit 27 2 and, in the rearward portion thereof, by the upper surface 34 2 of conductive member 26 2 .
Referring now to FIG. 7 an exemplary one of the identically constructed strip transmission line circuit 27 1 -27 9 , here strip transmission line circuit 27 1 is shown in detail to include a pair of dielectric support structures 40 1 , 42 1 of any suitable material, here Teflon Fiberglas material having a dielectric constant of 2.56. Initially, each one of the dielectric support structures 40 1 , 42 1 has a sheet of conductive material, here copper clad on the upper and lower surfaces thereof. The sheet of conductive material on the lower surface of dielectric support structure 42 1 is removed entirely with a suitable chemical etchant whereas a plurality of, here four, flared notches 44 1 are etched into the conductive material 32 1 clad onto the upper surface of such dielectric support structure 40 1 using conventional photolithographic-chemical etching techniques. Each one of the notches 44 1 has a narrow portion 46 1 and a wider portion 48 1 . The notches 44 are separated from each other a distance less than a half wavelength at the smallest operating wavelength of the antenna. More particularly, here the center-to-center spacing of the notches 44 is 0.350 inches. The width of the wide portion 48 is here 0.260 inches and the widths of the narrow portion 46 is here 0.050 inches. The length of the wide portion 48 is here 0.130 inches and the length of the narrow portion 46 is here 0.842 inches. Considering now the second one of the pair of dielectric support structure 42 1 a similar pattern of four flared notches 50 1 is etched into the conductive sheet 28 1 clad to the bottom surface of such dielectric support structure 42 1 . Each one of the slots 50 1 is identical to the slots 44 1 formed on the conductive sheet 32 1 clad to the upper surface of dielectric support 40 1 . The conductive sheet clad to the upper surface of the dielectric support structure 42 1 is etched to form a feed network 52 1 . The feed network 52 1 is a strip transmission line circuit having strip conductor 54 1 disposed between a pair of ground plane conductors formed by the conductive sheets 28 1 , 32 1 , and separated from such sheets 28 1 , 32 1 by the dielectric support structures 40 1 , 42 1 . The feed network 52 1 includes a first two-to-one power divider section 56 1 the output of which into turn feeds a pair of two-to-one power divider sections 58 1 , 60 1 . Each one of the three power divider sections 56 1 , 58 1 , 60 1 includes a step-matching transformer section 62 1 . Thus, power fed to the strip transmission line feed network 52 1 is divided equally, and in phase, to each one of four feed lines 64 1 . Each feed line 64 1 is disposed underneath the narrow portions 46 1 of a pair of notches 48 1 , 50 1 as shown in FIG. 8, the notches 44 1 on conductive sheet 32 1 being in registration with the notches 50 1 formed in conductive sheet 28 1 . When strip transmission line feed network 54 1 is fed radio frequency energy from a coaxial connector 66 1 (FIG. 8) having a center conductor 68 1 electrically connected to a strip conductor 54 1 of the strip transmission line feed network 52 1 , 54 1 and outer conductors 70 1 electrically connected to conductive sheets 32 1 , 28 1 , the strip transmission line circuit 27 1 couples energy to the feed lines 64 1 and then to notches 44 1 and 50 1 whereupon such feed energy is then radiated into free space with an electric field vector disposed in the plane of the strip transmission line circuit 27 1 as shown by the vector E 1 in FIGS. 1 and 8. Thus, the energy radiated by the notches 44 1 , 50 1 is linearly polarized; more particularly, here horizontally polarized.
Referring now in more detail to members 26 1 -26 10 , each one of such members 26 1 -26 10 is constructed from a block of electrically conductive material, here aluminum, here having outer dimensions of 4.037 inches (length) and 2.250 inches (width). Such block has machined therein S-shaped side wall portions 74 1 , 76 1 (FIG. 3) and a rear wall portion 78 1 having a recess notch or 80 1 formed therein. The depth of the side wall and rear wall portions is here substantially 0.325 inches. Also machined into the upper surface 34 1 of the member 36 1 is a tapered ridge 82 1 , as shown, here having a width of 0.20 inches. The tapered ridge 82 1 has an aperture 84 1 formed in the upper, flat top portion 86 1 thereof, the flat top portion 86 1 terminating in a tapered portion 88 1 , (FIGS. 3, 9) as shown. The length from the end of the tapered ridge 82 1 to the end of the member 36 is here 2.2 inches. The length of the tapered portion 88 1 is here 0.9 inches. The depth of the notch 80 1 formed in the rear wall portion 78 1 is here 0.075 inches, such notch 80 1 having a length along the rear wall portion 78 1 of, here, 0.588 inches. It is noted that the separation between the side wall portions 74 1 , 76 1 disposed laterally to the tapered portion 88 1 is relatively constant, here 1.5 inches; however, such separation decreases, here along curved paths, 90 1 , 92 1 , as such rear wall portions 74 1 , 76 1 extend towards the rear wall portion 78 1 . As will be discussed in more detail hereinafter, the converging of the side wall portions 74 1 , 76 1 as they extend towards the rear wall portion 78 1 in the region behind the aperture 84 1 (such aperture being the area where the antenna element 22 1 formed by such member 26 1 together with member 26 2 is fed by the coaxial connector in a manner to be described) improves the impedance matching between the coaxial connector and the antenna element 22 1 . Member 26 1 also has holes 100 1 drilled through it, such being used for bolting the members together with bolts and screws 107 1 as shown in FIG. 2. A hole 108 1 is formed partly into the upper surface of the member 26 1 and is used to receive an alignment pin 109 2 (FIGS. 4-6) formed on the bottom surface of member 26 2 , as shown also in FIG. 10. Disposed along the curved regions 90 1 , 92 1 (FIG. 3) of the side wall portions 74 1 , 76 1 are open ended channels 110 1 , 112 1 . Channels 110 1 , 112 1 are here formed of curved conductive strips 114 1 , 116 1 here aluminum, having ends 118 1 , 120 1 spaced from, and affixed to, side walls 74 1 , 76 1 respectively. The spacing is provided by aluminum spacers 122 1 , 124 1 such ends 118 1 , 120 1 and spacers 122 1 , 124 1 being affixed to the side wall portions 74 1 , 76 1 through any convenient means as by bolts or a suitable electrically conductive epoxy, not shown. The spacers 122 1 , 124 1 here have a thickness of 0.1 inches and the length of the channels 110 1 , 112 1 is here 0.6 inches. The channels 110 1 , 112 1 , are effective in removing unwanted surface currents produced along the side wall portions 74 1 , 76 1 such currents being associated with radio frequency energy having a frequency of here 13.2 GHZ. That is, it was noted that there was a significant loss of gain the antenna at about 13.2 GHZ. It was also noticed that the channels 110 1 , 112 1 removed the loss of gain in the region of 13.2 GHZ. It is noted that the length of the channels 110 1 , 112 1 is here about three quarters of the wavelength of the frequency associated with the unwanted surface currents.
The side wall portion 74 1 , 76 1 (FIG. 3) disposed between the tapered ridge 82 1 and the frontal end of the member 26 1 are flared outwardly along a nonlinear path 131 1 to increase the surface length of the side wall portions 74 1 , 76 1 from the tapered ridge 82 1 to free space within the fixed longitudinal length of the antenna element 26 1 thereby providing a relatively compact antenna element with a side wall length sufficiently long to provide an adequate transition region between the tapered ridge and free space.
Referring now to the bottom surface 30 1 of member 26 1 (shown more clearly in FIGS. 4, 5, 6 and 10) such surface 30 1 also has a tapered ridge 126 1 formed thereon; here, however the flat portion 123 1 of the ridge 126 1 has a turret shaped conductive post 122 1 (here shown) press fit therein by a pin shaped end 127 1 as shown in FIG. 13. Post 122 1 has a hole 128 1 drilled therein as shown for receiving the center conductor 142 1 of a coaxial connector 140 1 (FIG. 11) in a manner to be described in detail in connection with FIG. 13. It is noted from FIG. 5 that the tapered ridges 82 1 , 126 1 formed on the upper and lower surfaces of member 26 1 are in alignment or registration with each other. Further, it is evident that the post 122 1 of member 26 1 fits into the aperture 84 2 of member 26 2 as shown in FIGS. 9, 11 and 12.
When members 26 1 , 26 2 and strip transmission line circuits 27 1 , 27 2 are affixed together (here by screws 107 (FIG. 2) and conductive epoxy, not shown, disposed on the portions of the copper conductive sheets 28, 32 of circuits 27 1 -27 9 (FIGS. 9 and 10) which contact portions of the conductive members 26 1 -26 10 ), the lower surface 30 1 of member 26 1 , and the upper surface 34 2 of member 26 2 form opposing upper and lower wide surfaces of the rear portions of a hollow rectangular, open ended waveguide structure; the bottom ground plane conductor 28 1 of circuit 27 1 and the upper ground plane conductor 32 2 of circuit 27 2 form opposing upper and lower wide wall portions of the forward portion of the rectangular waveguide structure and side wall portions 74 2 , 76 2 and rear wall portion 78 2 form narrow side and rear walls of such open ended, rectangular waveguide. More particularly, the affixed members 26 1 , 26 2 formed a tapered ridge rectangular waveguide antenna element 22 1 . Surfaces 145 1 of member 26 1 contact surfaces 149 2 of member 26 2 as shown in FIG. 11. The side and back edges of the circuits 27 1 -27 9 are covered with a conductive epoxy (not shown) to electrically connect the side and back edges of the conductive sheets 28, 32. Further, circuits 27 1 , 27 2 (FIG. 3) fit into a groove 146 1 , 148 1 , 152 1 formed in the conductive members 26 1 -26 8 so that the flat portions 86 2 , 123 1 of the ridges 126 2 , 82 1 are separated a distance "d" (FIG. 13), and the wide walls of the waveguide, i.e. conductive sheets 28 1 , 32 2 , are separated a distance "b" (FIG. 12). The distances "b" and "d" are designed so that the waveguide propagates even in the TE 10 mode. Here "d" is 0.045 inches and "b" is 0.325 inches. The tapered ridge waveguide antenna elements 22 1 -22 8 are fed by the coaxial transmission line through coaxial connectors 140 1 -140 8 (FIGS. 1, 9, 11 and 12) having a center conductor 142 1 (FIG. 13) passing through hole 144 1 (FIGS. 5, 11, 13) and the end of such center conductor 142 1 press fit to post 122 1 to provide electrical and mechanical contact to post 122 1 . The outer conductor 145 1 is electrically and mechanically connected to the member 26 2 through screws 141 1 as shown in FIGS. 9 and 11. The inner conductor 142 1 is separated from the walls of the hole 144 1 by a dielectric sleeve 143 1 as shown in FIG. 13. A ferrite ring 147 1 is disposed around the inner conductor 142 1 between the dielectric 143 1 and the post 126 1 , as shown in FIG. 13 to provide impedance matching between the coaxial connector 142 1 and the post 122 1 . Radio frequency energy fed to the antenna element 26 1 via connector 140 1 thus launches radio frequency energy into cavity 148 1 (FIG. 12), such energy travelling towards the open end 160 1 of the cavity in the TE 10 mode having an electric field vector extending between the wide surfaces of the waveguide as shown by arrow E 2 in FIGS. 1 and 12.
It is noted then that each one of the antenna elements 22 1 -22 8 is adapted to transmit radio frequency energy having vertical polarization, (as when feeding radio frequency energy to connector 140 1 -140 8 or horizontally polarized radio frequency energy (as when feeding radio frequency energy to connector 66 1 -66 9 ). Further, if radio frequency energy is fed equally to both connectors 140 1 -140 8 and 66 1 -66 9 and the phase of the energy fed to such connectors differs by ninety degrees, such antenna element will transmit circularly polarized radio frequency energy in free space.
Thus, referring again to FIG. 1 the details of the power distribution network 24 will now be described. As mentioned above in connection with FIG. 1 the array ports 16 1 -16 8 are coupled to the array 20 through a power distribution network 24. The power distribution network 24 includes a plurality of, here eight, hybrid couplers, 150 1 -150 8 having a pair of input terminals 152a 1 , 152b 1 -152a 8 , 152b 8 and a pair of output terminals 154a 1 , 154b 1 -154a 8 , 154b 8 . One of the input terminals 152a 1 -152a 8 is coupled to a corresponding one of the array ports 16 1 -16 8 , as shown and the other one of such input 152b 1 -152b 8 terminals is terminated in a matched load 156 1 -156 8 as shown. Hence the power fed to the couplers 150 1 -150 8 is divided equally between output ports 154a 1 , 154b 1 , through 154a 8 , 154b 8 respectively, but the signals at such output ports differ in phase from one another by ninety degrees. That is, considering coupler 150 1 for example, the signals at output ports 154a 1 , 154b 1 differ in phase by ninety degrees. The signals produced at ports 154a 1 -154a 8 are fed to two-to-one power dividers 160 1 -160 8 , respectively as shown. The power in the signals fed to dividers 160 1 -160 8 is divided equally and in phase. The pair of signals produced at the outputs of dividers 160 1 -160 8 are fed to two-to-one power combiners 162 1 -162a 1 as shown. It is noted that one of the inputs of combiners 162 1 , 162 9 are terminated in matched loads 164, 166. The outputs of power combiners 162 1 -162 9 are fed to coaxial connectors 66 1 -66 9 which feed strip transmission line circuits 27 1 -27 9 . Thus, if the radio frequency signal phases at output ports 154 a 1 -154a 8 are represented as: φ, 2φ, . . . 8φ respectively, the signal phases at connectors 66 1 -66 9 may be represented as: φ/2, 3φ/2, 5φ/2 . . . 15φ/2, 17φ/2, respectively and the signal phases at connectors 140 1 -140 8 may be represented as: φ+(π/2) . . . 8φ+(π/2) respectively.
Considering first an exemplary pair of the pair of inner connectors 66 2 , 66 3 through 66 7 , 66 8 , here for example the pair of connectors 66 6 , 66 7 it is noted that such connectors feed the strip transmission line circuits 27 6 , 27 8 which form a portion of the upper and lower wide walls of the antenna element 22 6 . Further, the signal phases fed to such terminals 27 6 , 27 8 may be represented as: 11φ/2 and 13φ/2 respectively. Therefore, in the region between the circuits 27 6 , 27 8 at the open end of the antenna element 26 6 , the signals combine so that the resulting signal phase may be represented as: 6φ in the region between the circuits 27 6 , 27 8 . Further, such signal has a horizontal polarization. Still further, the signal phase fed to connector 140 6 of such antenna element 22 6 may be represented as: 6φ+(π/2), has a vertical polarization, and has a phase center coincident with the phase center of the horizontally polarized energy of the signal produced by the pair of strip transmission line circuits 27 6 , 27 8 . Thus, the energy associated with antenna element 22 6 , in free space, is circularly polarized. It is noted that the above discussion applies to antenna elements 22 2 -22 7 , however there is some distortion with the antenna elements 22 1 , 22 8 which are at the end of the array 20. However, with a large array, i.e. an array having 16 elements or more the effect of the end elements is minimized.
Having described a preferred embodiment of the invention it will now be apparent to one of skill in the art that other embodiments incorporating its concept may be used. It is believed therefore that this invention should not be restricted to the disclosed embodiment but rather should be limited only by the spirit and scope of the appended claims. | A radio frequency antenna including an antenna element having an open-ended waveguide section coupled to a first feed means for establishing radio frequency energy having linear polarization, the electric field vector of such energy being disposed normal to a pair of opposing wall portions of the waveguide. The antenna element includes a microwave circuit means for establishing radio frequency energy having a linear polarization orthogonal to the polarization of the first mentioned radio frequency energy. The microwave circuit includes a dielectric and a conductive sheet disposed over the dielectric; such sheet providing one of the wall portions of the waveguide section. The conductive sheet has an array of notches formed therein, such notches being disposed adjacent the open end of the waveguide section. A second feed means is coupled to the array of notches for establishing radio frequency energy having a linear polarization, the electric field thereof being in the plane of the dielectric and hence normal to the polarization established by the first feed means. With such arrangement, the first and second feed means are fed in quadrature and the phase centers of the orthogonally disposed polarized radio frequency energy at the open end of the waveguide are substantially coincident to thereby enable the antenna to establish circularly polarized radio frequency energy in free space. Further, the radio frequency energy fed to the second feed means is distributed to an array of notch shaped elements thereby increasing the power handling capability of the antenna element. Still further, the antenna element is relatively compact and suitable to be arranged in relatively wide scan angle coverage. | 7 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application is a division of U.S. patent application Ser. No. 10/389,433, filed on Mar. 14, 2003, which is a division of U.S. patent application Ser. No. 10/068,159, filed on Feb. 5, 2002, presently pending.
FIELD OF THE INVENTION
[0002] This invention generally relates to assembling and packaging multiple semiconductor dies, and more particularly to a stacked multiple die device and methods for fabricating the device.
BACKGROUND OF THE INVENTION
[0003] Miniaturization of wireless products such as cellular phones and handheld computers such as personal digital assistants (PDA), has driven the increased demand for smaller component footprints, which in turn increases the popularity of multi-chip stack BGA packaging. Most multi-chip packages involve stacking dies on top of each other by means of adhesive elements. However, to achieve a low package height for multi-chip stacked die packages, a significantly reduced die thickness is needed together with the use of special wire bond techniques to reduce the height of the wire bond loop height.
[0004] Thin die handling and the required special bonding techniques poses many challenges to the assembly process. FIGS. 1-3 depict conventional ways of packaging a multi-chip stacked die package. As shown in FIG. 1 , one prior art package 10 includes two conventional stacked dies, the first (bottom) die 12 being surface mounted by means of an adhesive element 14 to a substrate 16 , and a smaller second (top) die 18 being mounted by a second adhesive element 20 onto the active surface 22 of the bottom die 12 , each of the dies being wire bonded 24 to the substrate 16 . FIG. 2 illustrates a prior art stack die package 10 a in which the first (bottom) die 12 a is mounted to a substrate 16 a in a flip chip attachment, and the second (top) die 18 a is surface mounted to the inactive surface 26 a of the first die 12 a by means of an adhesive element 20 a and wire bonded 24 a to the substrate 16 a . FIG. 3 shows a prior art three-die stack BGA package 10 b in which the first bottom die 12 b is mounted to a substrate 16 b by an adhesive element 14 b , a second (middle) die 18 b is mounted on the active surface 22 b of the bottom die 12 b by a second adhesive element 20 b , and a third (top) die 28 b is mounted on a spacer 30 b mounted on the active surface 32 b of the second (middle) die 18 b , with each of the dies being wire bonded 24 b to the substrate 16 b.
[0005] In stacked die assemblies in which the bottom die is a flip chip, there is a limit on the minimum overall thickness of the package that can be achieved. If a solder-bumped wafer having a 150 μm bump height were to be ground to a total thickness of 150 μm to 200 μm, there would be a high occurrence of broken wafers due to the stress induced on the wafers from the bumps. Furthermore, even if the wafer does not crack, the die strength will drop significantly due to the presence of “dimples” on the backside of the wafer. Such dimples are typical defects observed on bump wafers that are ground too thin or an inappropriate backgrinding tape is used in the process.
[0006] In addition, as depicted in FIG. 3 , with multiple stacked dies, a spacer 30 b is required to create the minimal clearance for the wire loop height between the second (middle) die 18 b and the third (top) die 28 b . This results in a higher package height, or requires ultrathin dies in order to meet the package height requirement. Thinner dies translate into a higher possibility of cracked dies during the assembly process.
[0007] In view of these and other deficiencies, improvements in stacked die modules are desirable.
SUMMARY OF THE INVENTION
[0008] The present invention provides semiconductor devices and stacked die assemblies, methods of fabricating the devices and assemblies for increasing semiconductor device density, and method of fabricating die packages of the assemblies.
[0009] In one aspect, the invention provides a stacked die assembly. In one embodiment, the stacked die assembly, comprises a first (bottom) die disposed on a substrate, a bonding element connecting bond pads on an active surface of the bottom die to terminal pads on the substrate, and a second die mounted on the bottom die. The second die has a bottom surface with a recessed edge along the perimeter of the die that provides an opening for the bonding element extending from the bond pads of the bottom die, thus eliminating the need for a spacer between the two dies to achieve sufficient clearance for the bonding element. A second bonding element connects the bond pads on the active surface of the second die to terminal pads on the substrate. Adhesive elements are typically disposed between the two dies and the bottom die and the substrate.
[0010] In another embodiment, the stacked die assembly, comprises a first (bottom) die disposed on a substrate, typically through a flip chip attachment, and having a recess formed in the upper (inactive) surface. A second die is at least partially disposed within the recess of the first die. A bonding element connects bond pads on the active surface of the second die to terminal pads on the substrate. An adhesive element can be disposed within the recess to attach the two dies. In a further embodiment of this assembly, a third die is mounted on the second die. The third die has a bottom surface with a recessed edge along the perimeter of the die that provides an opening for the bonding element extending from the bond pads of the second die, thus eliminating the need for a spacer between the two dies for clearance of the bonding element. A second bonding element connects the bond pads on the active surface of the third die to terminal pads on the substrate. An adhesive element can be used to attach the second and third dies.
[0011] In a further embodiment, the stacked die assembly, comprises a first (bottom) die disposed on a substrate, a bonding element connecting bond pads on the active surface of the first die to terminal pads on the substrate, and a second die mounted on the bottom die. A recess is formed on the bottom surface of the first die, and an adhesive element is disposed within the recess to attach to the first die to the substrate. The containment of the adhesive element in the recess rather than being disposed between the die and the substrate as a separate layer decreases the overall height of the die assembly. In an embodiment of this assembly, the second die has a recessed edge along the perimeter of the bottom surface for clearance of the bonding element extending from the bond pads of the second die, thus eliminating the need for a spacer between the two dies. Bond pads on the second die are connected to terminal pads on the substrate by a second bonding element, and an adhesive element can be used to attach the second and third dies.
[0012] In yet another embodiment, the stacked die assembly, comprises a first (bottom) die disposed on a substrate, typically through a flip chip attachment, and a second die having a recess formed in the bottom (inactive) surface. The first die is at least partially disposed in the recess of the second die, and a bonding element connects bonding pads on the second die. An adhesive element can be disposed within the recess to attach the two dies.
[0013] In another aspect, the invention provides a semiconductor package. In various embodiments, the package comprises a stacked die assembly according to the invention, at least partially encapsulated. The package can further include external contacts disposed on the second surface of the substrate for attaching the package as a component to an external electrical apparatus or device.
[0014] In another aspect, the invention provides methods of fabricating the foregoing stacked die assemblies and semiconductor packages.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Preferred embodiments of the invention are described below with reference to the following accompanying drawings, which are for illustrative purposes only. Throughout the following views, the reference numerals will be used in the drawings, and the same reference numerals will be used throughout the several views and in the description to indicate same or like parts.
[0016] FIGS. 1-3 depict cross-sectional, side elevational views of prior art embodiments of stacked die packages.
[0017] FIG. 4 is a cross-sectional, side elevational view of an embodiment of a stacked die package according to the invention.
[0018] FIG. 5 is an enlarged partial view of the package of FIG. 4 , showing the recessed edge and opening between the stacked dies.
[0019] FIGS. 6-11 illustrate sequential processing steps in the fabrication of the stacked die package of FIG. 4 , according to an embodiment of a method of invention. FIG. 6 is a bottom, perspective view of the second die of the package of FIG. 4 , showing the removed (etched) portion of the die forming the recessed edge along the perimeter of the die. FIGS. 7 and 9 - 11 are cross-sectional, side elevational views of sequential steps in the mounting of the dies. FIG. 8 is a top plan view of a panel with multiple die packages disposed thereon.
[0020] FIG. 12 is a cross-sectional, side elevational view of another embodiment of a stacked die package according to the invention.
[0021] FIGS. 13-16 illustrate sequential processing steps in the fabrication of the stacked die package of FIG. 12 , according to an embodiment of a method of invention. FIG. 14 is a top, perspective view of the first (bottom) die of the package of FIG. 12 , showing the recess formed in the die. FIGS. 13 and 15 - 16 are cross-sectional, side elevational views of sequential steps in the mounting of the dies.
[0022] FIG. 17 is a cross-sectional, side elevational view of another embodiment of a stacked die package according to the invention.
[0023] FIGS. 18-19 illustrate sequential processing steps in the fabrication of a portion of the stacked die package of FIG. 17 , according to an embodiment of a method of invention, showing the mounting of the third (top) die.
[0024] FIG. 20 is a cross-sectional, side elevational view of another embodiment of a stacked die package according to the invention.
[0025] FIGS. 21-24 illustrate sequential processing steps in the fabrication of the stacked die package of FIG. 20 , according to an embodiment of a method of invention. FIG. 22 is a bottom, perspective view of the first (bottom) die of the package of FIG. 20 , showing the recess formed in the bottom surface of the die. FIGS. 21 and 23 - 24 are cross-sectional, side elevational views of sequential steps in the mounting of the dies.
[0026] FIG. 25 is a cross-sectional, side elevational view of another embodiment of a stacked die package according to the invention.
[0027] FIGS. 26-29 illustrate sequential processing steps in the fabrication of the stacked die package of FIG. 25 , according to an embodiment of a method of invention. FIG. 26 is a bottom, perspective view of the second (top) die of the package of FIG. 25 , showing the recess formed in the bottom surface of the die. FIGS. 27-29 are cross-sectional, side elevational views of sequential steps in the mounting of the dies.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] The invention will be described generally with reference to the drawings for the purpose of illustrating embodiments only and not for purposes of limiting the same. The figures illustrate processing steps for use in fabricating semiconductor devices in accordance with the present invention. It should be readily apparent that the processing steps are only a portion of the entire fabrication process.
[0029] The terms “top” and “bottom”, and “upper” and “lower” are used herein for convenience and illustrative purposes only, and are not meant to limit the description of the invention inasmuch as the referenced item can be exchanged in position.
[0030] The invention advantageously reduces the overall height of stacked die packages, achieves a desirably low package profile, allows the use of thicker dies in the stack assembly to reduce the number of cracked dies, eliminate the need for a spacer between dies to provide clearance for bond wires extending from an underlying die, and reduces the number of passes required for manufacturing multiple stacked dies by eliminating the need for mounting a spacer. The invention further offers more reliable adhesion bleed out control, and the benefits increase as more dies are stacked. The method of the invention can be utilized to fabricate an assembly comprising additional stacked die layers to those of the illustrated embodiments using the described concepts herein.
[0031] In each of the described embodiments, prior to mounting the individual dies of a stacked assembly, the backside (inactive surface) of a die (wafer) can be backgrinded or otherwise processed to a desired thickness, flatness value and texture using conventional methods in the art.
[0032] Referring to FIG. 4 , a first embodiment of a multiple chip die assembly package 40 according to the invention is depicted in a cross-sectional, side elevational view. The package 40 comprises a first (bottom) die 42 mounted to a support substrate 44 , and a second (top) die 46 mounted on the bottom die 42 . Bond pads 48 a , 48 b on the first and second dies 42 , 44 are wire bonded 50 a , 50 b , respectively, to terminal pads 52 a , 52 b on the support substrate 44 . Substrate 44 further includes external contacts 54 , for example, in the form of conductive solder balls, to connect the die package 40 to an external electrical apparatus (not shown). As best seen in FIG. 5 , a portion or thickness 60 (shown in phantom) along the perimeter 56 of the second (inactive) surface 58 of the second (top) die 46 is removed (e.g, etched) to provide a recess (recessed edge) 62 . The recessed edge 62 has a height (h) and provides an opening 63 for sufficient clearance of the bond wires 50 a (or other connecting member such as TAB tape) extending from the bond pads 48 a on the bottom die 42 to the substrate 44 . This eliminates the need for a spacer (e.g., FIG. 3, 30 b ) between the two overlying dies to provide the necessary clearance for bond wires extending from the lower die 42 , and thus achieves a lower overall package height 67 . Adhesive elements 64 , 66 can be utilized, respectively, to secure the bottom die 42 onto the support substrate 44 , and the second (top) die 46 onto the bottom die 42 .
[0033] FIGS. 6-11 illustrate an embodiment of a process flow and method for forming the stacked die package 40 of FIG. 4 .
[0034] Prior to mounting, a portion or thickness of the second (inactive) surface 58 of the second (top) die 46 can be removed to form the recessed edge 62 . As shown in FIGS. 5-6 , a portion 60 (shown in phantom in FIG. 5 ) of the surface 58 has been removed along the perimeter 56 of the die. Known methods in the art can be used to selectively remove a portion 60 along the perimeter of the die 46 such that when the die 46 is subsequently mounted onto the first (bottom) die 42 , the recessed edge 62 provides an opening with sufficient clearance for the bond wires 50 a extending from the bottom die 42 to the support substrate 44 . The recessed edge 62 can be formed using known techniques in the art, for example, a chemical wet etch or dry etch, laser ablation, or other mechanical means of reducing the bottom surface 58 of the top die 46 to a predetermined depth.
[0035] Referring now to FIGS. 7-9 , the first (bottom) die 42 is mounted on a first surface 68 of the support substrate 44 . The bottom die 42 comprises a first (active) surface 70 with a plurality of bond pads 48 a along the periphery thereof, and a second (bottom) surface 72 . As shown in FIG. 7 , the bottom surface 72 of the bottom die 42 is aligned with and facing the first surface 68 of the support substrate 44 prior to assembly.
[0036] The support substrate 44 can comprise an electrically insulating polymer material such as a resin reinforced with glass fibers, for example, bismaleimide triazine (BT) resin, epoxy resins such as FR-4 or FR-5 laminates, ceramics, and polyimide resins; a metal leadframe (e.g., Alloy42 or copper); a flexible polyimide film (e.g., KAPTON from DuPont, Wilmington, Del., or UPILEX from Ube Industries, Ltd., Japan); among other substrates. A representative thickness of the substrate is about 50 μm to about 500 μm. As shown in FIG. 8 , the support substrate 44 can be in the form of a strip or panel 74 on which multiple die packages 40 are formed, whereby the panel 74 can be singulated, for example, by cutting or shearing along an expansion slot 76 , into individual packages.
[0037] Referring to FIG. 7 , the bottom die 42 can be attached to the support substrate 44 by use of an adhesive element 64 . The adhesive element 64 can be applied onto the bottom surface 72 of the bottom die 42 (as shown), and/or to the first surface 68 of the support substrate 44 . The adhesive element 64 can comprise any suitable adhesive material known in the art, including contact adhesives, thermoplastic adhesives and thermosetting adhesives, for example, a die-attach epoxy or equivalent, or a double-sided, multi-layered adhesive tape such as polyimide film coated on both sides with adhesive. The bottom die 42 and/or the support substrate 44 can be provided in a pre-taped form with an adhesive tape attached thereto, or an adhesive element 64 can be applied to either or both of the bottom die 42 and the support substrate 44 during fabrication of a stacked die package. Many suitable adhesive application methods for liquid or gel adhesive application are known in the art, such as screen printing, roller applicator, spray, and transfer. Similarly, an adhesive tape may be applied from a dispenser and severed from a roll of tape, or applied from a transfer (carrier) film.
[0038] Referring to FIG. 9 , with the first (bottom) die 42 mounted on the substrate 44 , the bond pads 48 a of the first (bottom) die 42 are then electrically connected to the terminal pads 52 a on the support substrate 44 , for example, by wire bonding (as shown) or by tape automated bonding (“TAB”). For example, ball bonds (not shown) can be thermosonically bonded to the bond pads 48 a , and the bond wires 50 a extended and bonded to the terminal pads 52 a on the support substrate 44 . In other embodiments, TAB bonding and ultrasonic bonding, as known in the art, can be used to connect the bond pads 48 a and the terminal pads 52 a.
[0039] Referring to FIGS. 10-11 , the second (top) die 46 is then mounted onto the first (active) surface 70 of the first (bottom) die 42 to form the stacked die assembly 78 . The second die 46 comprises a first (active) surface 80 with a plurality of bond pads 48 b along the periphery thereof, and a second (inactive) surface 58 . As shown in FIG. 10 , the second surface 58 of the second (top) die 46 is aligned with and facing the first surface 70 of the first (bottom) die 42 prior to assembly. The recessed edge 62 between the first (bottom) die 42 and the overlying second die 46 is sized with a height (h) to provide an opening 63 for sufficient clearance of the bond wires 50 a extending from the bottom die 42 to the support substrate 44 .
[0040] The second (top) die 46 can be attached to the bottom die 42 by means of an adhesive element 66 , for example, a tape or die-attach adhesive as described with reference to adhesive element 64 . The first (bottom) die 42 and/or the second (top) die 46 can be provided in a pre-taped form with an adhesive tape attached thereto, or an adhesive element 66 can be applied to either or both dies during mounting of the second (top) die onto the first (bottom) die.
[0041] As shown in FIG. 11 , the bond pads 48 b of the second (top) die 46 are then electrically connected to the terminal pads 52 b on the support substrate 44 , for example, by wire bonding, as shown in the illustrated example, or by TAB bonding, resulting in the wire-bonded stacked die assembly 78 .
[0042] The die assembly 78 can be partially or fully encapsulated with a dielectric encapsulation material 82 , typically a thermoset resin, the assembly 78 can be encapsulated using known techniques in the art, for example, screen printing, glob-top, pot molding, and transfer molding, resulting in the encapsulated stacked die package 40 depicted in FIG. 4 . In one embodiment, a number of die assemblies 78 can be placed in a lower mold plate or half of an open multi-cavity mold, one assembly within each cavity, and following encapsulation, the mold plates are separated and the individual packages 40 can be singulated.
[0043] In the embodiment illustrated in FIG. 4 , external contacts 54 , typically in the form of conductive solder balls (or other suitable conductive material such as conductive epoxies or conductor-filled epoxies), columns, pins, and the like, are mounted on the second (bottom) surface 84 of the support substrate 44 for electrical connection of the encased die package 40 as a component to an external electrical apparatus (not shown). Examples of such electric apparatus include a PCB or other external circuitry (not shown) such as a motherboard of a computer, program logic controller (PLC), a testing apparatus, among others. The support substrate 44 typically includes a variety of conductive through-holes or vias 86 that extend through the cross-section of the substrate and establish routing of the conductive elements through the substrate 44 , and further include electrically conductive metal lines or traces and pads formed on the second (bottom) surface 84 on which the external contacts 54 are mounted.
[0044] Where multiple die packages are fabricated on a panel substrate (e.g. panel 74 , FIG. 8 ), the panel can be singulated into individual die packages 40 , for example, by cutting or shearing.
[0045] Another embodiment of a multiple chip die assembly package according to the invention is depicted in a cross-sectional, side elevational view in FIG. 12 . The package 40 ′ comprises a first (bottom) die 42 ′ mounted to a support substrate 44 ′ in a flip chip attachment, and a second (top) die 46 ′ mounted in a recess 88 ′ formed in the first (upper) surface 72 ′ of the bottom die 42 ′. Bond pads 48 b ′ on the second (top) die 46 ′ are wire bonded 50 b ′ to terminal pads 52 b ′ on the support substrate 44 ′. The substrate further includes external contacts 54 ′ (e.g. solder balls) for connection of the die package 40 ′ as a component to an external electrical apparatus (not shown). The recess 88 ′ in the bottom die 42 ′ allows the second (top) die 46 ′ to be inset into the bottom die 42 ′, thus achieving a lower overall package height 67 ′. An adhesive element 66 ′ can be utilized to attach the second (top) die 46 ′ onto the bottom die 42 ′.
[0046] FIGS. 13-16 illustrate an embodiment of a process flow and method for forming the stacked die package 40 ′ of FIG. 12 .
[0047] FIGS. 13 and 15 depict simplified cross-sectional views of the mounting and bonding of the first (bottom) die 42 ′ in a flip chip attachment to the substrate 44 ′. As shown, the first die 42 ′ comprises a first (active) surface 70 ′ and a second (inactive) surface 72 ′. The active surface 70 ′ of the first die 42 ′ includes a plurality of bond pads with conductive bumps 90 ′ mounted thereon, which are arranged in a predetermined configuration. The conductive bumps 90 ′ typically comprise a metal or alloy such as copper, silver or gold, or a conductive polymer material, and can be formed by known methods in the art, for example, electroplating, metal stud bumping by wire bonders, and stenciling. The support substrate 44 ′ can be in a form as described, for example, with respect to the support substrate 44 (die package 40 ) ( FIGS. 6-11 ).
[0048] Prior to mounting, a recess 88 ′ can be formed in the second (inactive) surface 72 ′ of the first (bottom) die 42 ′, as shown in cross-section in FIG. 13 , and in a top perspective view in FIG. 14 . The recess 88 ′ is sized and configured to receive the second die 46 ′ therein in a subsequent step. The recess 88 ′ can be formed in any suitable shape, such as square, rectangular, oval, and circular. The recess 88 ′ can be formed to a predetermined depth and width to accommodate the placement of the second die therein using known methods in the art, for example, patterning and utilizing a chemical wet etch or dry etch, laser ablation, or other mechanical means of removing the second (inactive) surface 72 ′ of the die. Dry etchers are commercially available, for example, from SECON, having an etch rate of 25 μm/min. for an 8-inch wafer. The recess can be formed at the wafer level, the die level (i.e., singulated die), or on a strip level after the die 42 ′ is mounted on the substrate (e.g., strip).
[0049] The bottom die 42 ′ can be mounted on the support substrate 44 ′ by conventional flip chip methodology. As shown in FIG. 13 , the active surface 70 ′ of the bottom die 42 ′ is aligned with and facing the first (upper) surface 68 ′ of the support substrate 44 ′ prior to assembly. Traces and electrical connections (not shown) on the first surface 68 ′ of the support substrate 44 ′ are configured to correspond to the configuration of bond pads and the conductive bumps 90 ′ of the bottom die 42 ′. The conductive bumps 90 ′ in the form of solder bumps can be reflowed to physically and electrically bond with the traces or other conductive elements on the first (upper) surface 68 ′ of the support substrate 44 ′, or cured in the case of conductive polymer bumps, although other methods such as thermal compression can also be used. Terminal pads 52 b ′ on the first surface 68 ′ of the support substrate 44 ′ are exposed along the periphery.
[0050] Referring to FIGS. 15-16 , the second (top) die 46 ′ is then mounted in the recess 88 ′ of the bottom die 42 ′. The second (top) die 46 ′ comprises a first (active) surface 80 ′ with a plurality of bond pads 48 b ′ along the periphery thereof, and a second (bottom) surface 58 ′. As shown in FIG. 15 , the second (bottom) surface 58 ′ of the second (top) die 46 ′ is aligned with and facing the recess 88 ′ in the second surface 72 ′ of the bottom die 42 ′ prior to assembly.
[0051] The second (top) die 46 ′ can be attached to the bottom die 42 ′ by means of an adhesive element 66 ′. The adhesive element 66 ′ can be applied within the recess 88 ′ to the recess surface 92 ′ of the bottom die 42 ′, and/or to the second surface 58 ′ of the top die 46 ′ (as shown). The adhesive element 66 ′ can comprise any suitable adhesive material known in the art, for example, a tape adhesive or die attach adhesive, as described with respect to adhesive element 64 ′. The adhesive element 66 ′ can have a thickness such that it functions as a spacer to control the degree of insertion of the second die 46 ′ into the recess 88 ′. The first and/or second dies 42 ′, 46 ′ can be provided in a pre-taped form with an adhesive tape attached thereto, or an adhesive element 66 ′ can be applied to either or both dies during fabrication of the stacked die package 40 ′. The adhesive element 66 ′ can be applied by conventional methods known in the art.
[0052] As depicted in FIG. 16 , the bond pads 48 b ′ of the second (top) die 46 ′ are then electrically connected by wire bonds 50 b ′ to the terminal pads 52 b ′ on the support substrate 44 ′, for example, by wire bonding (as shown) or by TAB bonding.
[0053] The wire bonded stacked die assembly 78 ′ can then be partially or fully encapsulated with a dielectric encapsulation material 82 ′ using known methods in the art to form the encapsulated stacked die package 40 ′ shown in FIG. 12 .
[0054] External contacts 54 ′ (e.g., conductive solder balls can then be mounted on the second (bottom) surface 84 ′ of the support substrate 44 ′ for connecting the die package 40 ′ to a motherboard or other electrical apparatus (not shown).
[0055] Where applicable, a panel substrate comprising a plurality of dies (e.g., FIG. 8 , panel 74 ) can then be singulated into individual die packages 40 ′.
[0056] A further embodiment of a multiple chip die assembly package according to the invention is depicted in a cross-sectional, side elevational view in FIG. 17 . The die package 40 ″ incorporates features of the die packages 40 , 40 ′ depicted in FIGS. 4 and 12 .
[0057] As illustrated in FIG. 17 , the package 40 ″ comprises a first (bottom) die 42 ″ mounted onto a support substrate 44 ″ in a flip chip attachment, and a second (middle) die 46 ″ at least partially received within a recess 88 ″ in the bottom die 42 ″, similar to the die package 40 ′ ( FIG. 12 ). The package 40 ″ further comprises a third (top) die 94 ″ mounted on the first (active) surface 80 ″ of the second (middle) die 46 ″, similar to the die package 40 ( FIG. 4 ). Bond pads 48 b ″, 48 c ″ on the second (middle) die 46 ″ and the third (top) die 94 ″ are wire bonded ( 50 B″, 50 c ″) to terminal pads 52 b ″, 52 c ″, respectively, on the support substrate 44 ″. Substrate 44 ″ further includes external contacts 54 ″ (e.g., solder balls) for connecting the die package 40 ″ as a component to an electrical apparatus (not shown). A portion along the perimeter of the second (inactive) surface 96 ″ of the third (top) die 94 ″ is partially removed to provide a recessed edge 62 ″ to provide an opening 63 ″ for sufficient clearance of the bond wires 50 b ″ connecting the bond pads 48 b ″ on the second (middle) die 46 ″ to the substrate 44 ″, thus eliminating the need for a spacer between the two dies 46 ″, 94 ″. The recess 88 ″ in the bottom die 42 ″ allows the second (middle) die 46 ″ to be inserted (nested) therein. The recess features 62 ″, 88 ″ advantageously combine to achieve a lower overall package height 67 ″. Adhesive members 66 ″, 98 ″ can be utilized, respectively, to attach the second (middle) die 46 ″ to the bottom die 42 ″, and the third (top) die 94 ″ to the second (middle) die 46 ″.
[0058] The stacked die package 40 ″ of FIG. 17 can be fabricated utilizing the process steps described above in fabricating packages 40 , 40 ′.
[0059] Prior to mounting, the recesses 88 ″, 62 ″ can be formed in the first (bottom) die 42 ″ and the third (top) die 94 ″, respectively.
[0060] A recess 88 ″ can be formed in the second (inactive) surface 72 ″ of the bottom die 42 ″ ( FIG. 18 ), as described with respect to die 42 ′ (package 40 ) and as depicted in FIGS. 13-14 . The recess 88 ″ is sized and configured to receive the second (middle) die 46 ″ therein in a subsequent step, and can be suitably shaped to correspond with the shape of the second die.
[0061] A recessed edge 62 ″ along the perimeter 56 ″ of the second (inactive) surface 58 ″ of the third (top) die 94 ″ can be formed as described previously for the second die 46 of package 40 and as depicted in FIGS. 4-6 . A portion 60 ″ of the third (top) die 94 ″ is removed along the second (bottom) surface 58 ″ to provide a recessed edge 62 ″.
[0062] Similar to the mounting of the first die 42 ′ on the substrate 44 ′ shown in FIGS. 13 and 15 , the first (bottom) die 42 ″ is mounted on a support substrate 44 ″ using flip chip technology, with the terminal pads 52 a ″, 52 b ″ on the surface of the support substrate 44 ″ exposed along the periphery.
[0063] The second (middle) die 46 ″ is then mounted in the recess 88 ″ of the bottom die 42 ″, as depicted in FIGS. 15-16 . The second die 46 ″ comprises a plurality of bond pads 48 b ″ on a first (active) surface 80 ″, and a second (bottom) surface 58 ″. The bottom surface 58 ″ of the second die 46 ″ is mounted onto the recess surface 92 ″ of the bottom die 42 ″ by means of an adhesive element 66 ″, such as a tape or die-attach adhesive as described with respective to adhesive element 64 . The dies 42 ″, 46 ″ can be pre-taped or an adhesive element 66 ″ can be applied to the surface of either or both dies during fabrication of the package.
[0064] The bond pads 48 b ″ of the second die 46 ″ are then electrically connected to the terminal pads 52 b ″ on the support substrate 44 ″, for example, by wire bonding or by TAB binding, resulting in a structure similar to that shown in FIG. 16 .
[0065] Referring now to FIG. 18 , the third (top) die 94 ″ can then be mounted on the second (middle) die 46 ″ similar to the mounting of the second die 46 on the bottom die 42 shown in FIGS. 10-11 . The third (top) die 94 ″ is mounted onto the first (active) surface 80 ″ of the second die 46 ″ to form the stacked die assembly 78 ″, as depicted in FIG. 19 . The third (top) die 94 ″ comprises a first (active) surface 100 ″ with a plurality of bond pads 48 c ″ along the periphery thereof, and a second surface 96 ″ with recessed edge 62 ″. As shown in FIG. 18 , the second surface 96 ″ of the third (top) die 94 ″ is aligned with and facing the first (active) surface 80 ″ of the second (middle) die 46 ″ prior to assembly.
[0066] The third (top) die 100 ″ can be attached to the second die 46 ″ by means of an adhesive element 98 ″, for example, a tape or die attach adhesive, as described hereinabove with respect to adhesive element 64 . The dies 46 ″, 100 ″ can be provided in a pre-taped form or an adhesive element 98 ″ can be applied to either or both dies during mounting of the third die 94 ″ onto the second die 46 ″. The recessed edge 62 ″ of the third (top) die 94 ″ has a height (h″) to provide an opening 63 ′″ with sufficient clearance for the bond wires 50 b ″ extending from the second die 46 ″ to the support substrate 44 ″.
[0067] Referring to FIG. 19 , the bond pads 48 c ″ of the third (top) die 94 ″ are then electrically connected to the terminal pads 52 c ″ on the support substrate 44 ″, for example, by wire bonding ( 50 c ″) or TAB bonding.
[0068] The die assembly 78 ″ can be partially or fully encapsulated 82 ″ resulting in the die package 40 ″ depicted in FIG. 17 . External contacts 54 ″ in the form of conductive solder balls (or other suitable conductive material or form) are mounted on the second (bottom) surface 84 ″ of the support substrate 44 ″ to provide electrical connection of the die package 40 ″ to an electrical apparatus (not shown). Thereafter, a multi-die panel can be singulated into individual die packages.
[0069] Referring to FIG. 20 , another embodiment of a multiple chip die assembly package according to the invention is depicted in a cross-sectional, side elevational view. The package 40 ′″ comprises a first (bottom) die 42 ′″ mounted to a support substrate 44 ′″, and a second (top) die 46 ′″ mounted on the bottom die 42 ′″. The second die 46 ′″ comprises a first (active) surface 80 ′″ with bond pads 48 b ′″ along the periphery thereof, and a second (inactive) surface 58 ′″. As illustrated, the second die 46 ′″ is larger in size, i.e., a greater width (w) and/or length (l) than the bottom die (see FIG. 6 ). Bond pads 48 a ′″, 48 b ′″, on the first and second dies 42 ′″, 46 ′″ are wire bonded 50 a ′″, 50 b ′″ to terminal pads 52 a ′″, 52 b ′″ on the support substrate 44 ′″, which further includes external contacts 54 ′″ to connect the die package 40 ′″ to an electrical apparatus. Similar to the die 46 depicted and described with respect to FIGS. 4-6 , a portion of the second (inactive) surface 58 ′″ of the second (top) die 46 ′″ is removed to provide a recessed edge 62 ′″ for sufficient clearance for the bond wires 50 a ′″ mounted on the underlying bottom die 42 ′″. A cavity or recess 102 ′″ is also etched in the second (bottom) surface 72 ′″ of the bottom die 42 ′″, and is sized for receiving an adhesive element 104 ′″ therein to secure the bottom die 42 ′″ to the support substrate 44 ′″. The recess features 62 ′″, 102 ′″ combine to achieve a lower overall package height 67 ′″ for the package 40 ′″ by eliminating the need for a spacer between the top and bottom dies, and mounting the adhesive element 104 ′″ as an insert into the recess 102 ′″ in the bottom die 42 ′″ rather than as a distinct layer between the bottom die 42 ′″ and the substrate 44 ′″. In addition, the recess 102 ′″ contains a die-attach adhesive therein and limits the amount of adhesive (epoxy) bleed onto bond fingers and/or other components on the substrate adjacent to the die edge.
[0070] FIGS. 21-24 illustrate an embodiment of a method and process flow for forming the stacked die package of FIG. 20 .
[0071] Prior to mounting, the recesses 102 ′″, 62 ′″ can be formed in the first (bottom) die 42 ′″ and the second (top) die 46 ′″, respectively.
[0072] As shown in FIG. 21 , and in a bottom perspective view in FIG. 22 , a recess 102 ′″ is formed in the second (bottom) surface 72 ′″ of the first (bottom) die 42 ′″. The recess 102 ′″ is sized and configured to receive an adhesive member 104 ′″ therein for attachment of the die 42 ′″ to the substrate 44 ′″. The recess 102 ′″ can be formed in any suitable shape, such as square, rectangular, oval, and circular. The recess 102 ′″ can be formed using known methods in the art, for example, patterning and utilizing a chemical wet etch or dry etch, mechanical drilling or punching, and laser ablation of the second surface 72 ′″ of the die 42 ′″. The recess 102 ′″ can be formed at the wafer level or the die level (i.e., singulated die).
[0073] A recessed edge 62 ′″ along the perimeter 56 ′″ of the second (inactive) surface 58 ′″ of the second (top) die 46 ′″ can be formed as described previously for the second die 46 (package 40 ) depicted in FIGS. 4-6 . A portion of the die 46 ′″ is removed such that, when the second die 46 ′″ is then mounted onto the first die 42 ′″, the recessed edge 62 ′″ provides an opening 63 ′″ for sufficient clearance of the bond wires 50 a ′″ extending from the first die 42 ′″ to the terminal pads 52 a ′″ on the support substrate 44 ′″.
[0074] Referring to FIG. 21 , the second (bottom) surface 71 ′″ of the first (bottom) die 42 ′″ is aligned with and facing the first (upper) surface 68 ′″ of the support substrate 44 ′″ prior to assembly.
[0075] The first die 42 ′″ is attached to the support substrate 44 ′″ by means of an adhesive element 104 ′″. The adhesive element 104 ′″ can be applied to the recess surface 106 ′″ of the recess 102 ′″ of the first (bottom) die 42 ′″, and/or onto the first (upper) surface 68 ′″ of the substrate 44 ′″ and aligned with the recess 102 ′″ to be received therein. The adhesive element 104 ′″ can comprise an adhesive gel or tape, as described hereinabove with respect to adhesive element 64 (package 40 ). The first die 44 ′″ and/or the substrate 44 ′″ can be provided in a pre-taped form, or an adhesive element 104 ′″ can be applied to the surface of either or both the first die 42 ′″ and the substrate 44 ′″ during the attachment step. The first die 42 ′″ is attached to the substrate 44 ′″ such that the terminal pads 52 a ′″, 52 b ′″ on the surface of the substrate are exposed.
[0076] Referring to FIGS. 23-24 , the second (top) die 46 ′″ is then mounted onto the first (bottom) die 42 ′″ to form the stacked die assembly 78 ′″. As shown in FIG. 23 , the second surface 58 ′″ of the second (top) die 46 ′″ is aligned with and facing the first (active) surface 70 ′″ of the first (bottom) die 42 ′″ prior to assembly. The second (top) die 46 ′″ can be attached to the first die by means of an adhesive element 66 ′″, for example, with a tape or die attach adhesive, as described with respect to the adhesive element 64 (die package 40 ). Either or both of the first and second dies 42 ′″, 46 ′″ can be provided in a pre-taped form or the adhesive element 66 ′″ can applied to either or both dies during the mounting step.
[0077] As depicted in FIG. 24 , the bond pads 48 b ′″ of the second (top) die 46 ′″ can then be electrically connected to the terminal pads 52 b ′″ on the substrate 44 ′″. The recessed edge 62 ′″ of the second (top) die 46 ′″ has a height (h′″) sufficient to provide an opening 63 ′″ for adequate clearance of the bonding wires 50 a ′″ extending from the second die 46 ′″ to the substrate 44 ′″.
[0078] The wire-bonded stacked die assembly 78 ′″ can be partially or fully encapsulated with an encapsulant material 82 ′″ using known techniques in the art to form the encapsulated stacked die package 40 ′″ as depicted in FIG. 20 . Thereafter, external contacts 54 ′″ can be mounted on the second (bottom) surface 84 ′″ of the support substrate 44 ′″ for electrical connection of the die package 40 ′″ to an external electrical apparatus (not shown).
[0079] Singulation of a multiple die panel or strip can then be performed to provide individual die packages 40 ′″.
[0080] Referring to FIG. 25 , a further embodiment of a multiple chip die assembly package according to the invention, is depicted in a cross-sectional, side elevational view. The package 40 ″″ comprises a first (bottom) die 42 ″″ mounted in a flip chip attachment to a support substrate 44 ″″, and a larger sized, second (top) die 46 ″″ mounted on the first (bottom) die 42 ″″. Bond pads 48 b ″″ on the second (top) die 46 ″″ are wire bonded 50 b ″″ to terminal pads 52 b ″″ on the support substrate 44 ″″. External contacts 54 ″″ are mounted on the second (bottom) surface of the substrate 44 ″″ for connecting the package 40 ″″ to an external electrical apparatus (not shown). A portion of the second (bottom) surface 58 ″″ of the second (top) die 46 ″″ is removed to provide a recess 108 ″″ for receiving the bottom die 42 ″″ therein. The recess feature 108 ″″ helps achieve a lower overall package height 67 ″″ for the package 40 ″″ by nesting the first die 42 ″″ within the overlying second die 46 ″″.
[0081] FIGS. 26-29 illustrate an embodiment of a method and process flow for forming the stacked die package of FIG. 25 .
[0082] Prior to mounting, the recess 108 ″″ can be formed in the second (bottom) surface 58 ″″ of the second (top) die 46 ″″, as shown in FIG. 25 and in a bottom perspective view in FIG. 26 . The recess 108 ″″ can be formed at the wafer level or the die level. The recess 108 ″″ is sized and configured to receive the bottom die 42 ″″ therein, and can be formed in any suitable shape, such as square, rectangular, oval, and circular using known techniques in the art.
[0083] As depicted in FIG. 27 , the first (active) surface 70 ″″ of the first (bottom) die 42 ″″ is aligned with and facing the first (upper) surface 68 ″″ of the support substrate 44 ″″ prior to assembly. The active surface 70 ″″ of the first die 42 ″″ includes a plurality of bond pads with conductive bumps 90 ″″ mounted thereon, which are arranged in a predetermined configuration. The bottom die 42 ″″ can be mounted on the support substrate 44 ″″ according to conventional flip chip techniques, resulting in the structure shown in FIG. 28 .
[0084] The second (top) die 46 ″″ is then mounted onto the first (bottom) die 42 ″″ to form the stacked die assembly 78 ″″. The second die 46 ″″ comprises a first (active) surface 80 ″″ with bond pads 48 b ″″, and a second (inactive) surface 58 ″″. As shown in FIG. 28 , the second surface 58 ″″ of the second (top) die 46 ″″ is aligned with and facing the second surface 72 ″″ of the first (bottom) die 42 ″″ prior to assembly. The first (bottom) die 42 ″″ is received at least partially in the recess 108 ″″ and can be attached to the recess surface 106 ″″ of the second die 46 ″″ by means of an adhesive element 66 ″″ such as a tape or die attach adhesive as described with respect to the adhesive element 64 (die package 40 ). Either or both of the first and second dies 42 ″″, 46 ″″ can be provided in a pre-taped form, or the adhesive element 66 ″″ can applied to either or both dies during the mounting step.
[0085] Referring to FIG. 29 , the bond pads 48 b ″″ on the first (active) surface 80 ″″ of the second (top) die 46 ″″ can then be electrically connected to the terminal pads 52 b ″″ on the substrate 44 ″″.
[0086] Partial or full encapsulation of the die assembly 78 ″″ can be performed using known techniques in the art to form the encapsulated package 40 ″″ shown in FIG. 25 . External contacts 54 ″″ can then be mounted on the second (bottom) surface 84 ″″ of the substrate 44 ″″ to facilitate electrical connection of the component die package 40 ″″ to an external electrical apparatus (not shown).
[0087] Individual die packages of a multiple die panel (e.g., as shown with reference to panel 74 in FIG. 8 ) can be separated by a singulation technique.
COMPARATIVE EXAMPLE 1 AND EXAMPLE 2
[0088] A comparison of the package design shown in FIG. 2 (prior art) with the package design shown in FIG. 12 .
Bottom die, thickness 6 mils 6 mils Second die, thickness 6 mils 6 mils Bond line, thickness 1 mil 1 mil Slot (recess) depth — 4 mils Overall total thickness of the 13 mils 9 mils stacked dies
[0089] By utilizing a package design according to the invention, a lower package height can be achieved using thicker dies. In addition, thicker dies can be utilized to help reduce the number of cracked dies that occur during the assembly process.
[0090] In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents. | Semiconductor devices and stacked die assemblies, and methods of fabricating the devices and assemblies for increasing semiconductor device density are provided. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of ash removal and receiving devices.
2. Prior Art
There are many known devices used to remove ashes from a furnace, either while the furnace is being used or when it is cold. Generally speaking, the ash removal devices are either fixed or portable. Fixed devices include those that employ an auger device built into the furnace structure to transport the ashes from inside a furnace to outside the furnace. U.S. Pat. Nos. 426,038 (Miles); 1,039,352 (Bernotowicz); Re: 18,006 (Hall); 2,121,229 (Halter); 2,248,206 (Suman); 2,558,626 (Pfau); and 2,637,285 (Getz), for example, show such structures. The devices shown in these patents are permanently mounted with respect to furnaces and generally the ashes of the furnace simply fall into the auger and are transported out of the furnace by rotation of the auger in conjunction with a stationary auger housing. Various drive means are used to rotate the auger. The churning of the auger flights may cause loose dust within the firebox that may interfere with proper burning of the fire. Such resulting dust may be passed out the furnace stack to create enviornmental problems in the surrounding area. With these fixed auger structures, the firebox of the furnace must have a special configuration to divert the ash onto the auger.
Previously known portable ash removing devices have utilized a wide variety of pails, scoops, shovels and pans, none of which are entirely suitable in handling the dust developed during use of the devices. Also, they are generally quite slow to use and require multiple operations on the part of the user. In using these devices it is often possible to drop the hot cinders being collected. See U.S. Pats. Nos. 33,058 (Walker); 767,648 (Korjibsky); 1,767,312 (Russell); 4,411,253 (Devin); 4,416,252 (Blank, Jr.); 4,305,376; and 4,497,308 (Johnson).
It has been found that a hand held ash auger such as that disclosed in the present invention is preferable for many uses and that it is readily adapted to use with all types of furnaces and heaters while being particularly useful with the usual open, built-in fireplaces, free-standing fireplaces and fireplace inserts used to achieve more efficient room and house heating.
OBJECTS OF THE INVENTION
A principal object of the present invention is to provide a portable ash removal and collection system usable with all types of solid fuel burning furnaces, fireplaces and stoves.
Another object of the present invention is to provide an ash removal system that is easy to use and that will efficiently collect and return ash, without leaving dust residue and without adversely affecting the burning of a fire in the furnace, fireplace or heater.
Still another object of the present invention is to provide a portable ash removal system that is safe to use, even by relatively untrained persons.
Another object of the present invention is to provide an ash auger that is inexpensive to manufacture and easy to maintain.
FEATURES OF THE INVENTION
Principal features of the present invention include a heat and fire resistant housing forming an ash chamber, with an attached handle and with a tube opening into and projecting from the housing forming the chamber. The free end of the auger is angled to form a scoop and to reach into firebox corners. The auger, mounted to turn in the tube has a flight thereon that extends from the free end of the tube to proximate the chamber. An auger shaft on which the flight is turned extends through the housing and out a side opposite the tube. The auger shaft is journaled in the tube and at the point where it passes through the housing. The attached handle means on the housing allows for convenient operation of the auger. The handle on the main body permits the user to direct the auger into different locations in a firebox. Because ash can only enter at the end of the tube, a minimum amount of disturbance is generated and accordingly, the amount of dust generated during use of the device is maintained at a minimum.
The angled cut in the end of the auger tube exposes only a small portion of the auger, which portion contacts the ashes and when the auger is turning, directs them into the tube. The tube provides a full enclosure to minimize dust problems.
Other objects and features of the invention will become apparent from the following detailed description and drawing, disclosing what are presently contemplated as being the best modes of the invention.
THE DRAWING
In the drawings:
FIG. 1 is a side-elevation view of a first hand cranked embodiment of the ash auger of the invention with a portion broken away to show the mounting of the auger shaft;
FIG. 2, a top plan view of the invention, with portions broken away to show the auger and the interior of the housing; and
FIG. 3, a side-elevation view, partially cut-away to show the motor.
DETAILED DESCRIPTION
Referring now to the drawing:
In the illustrated embodiment of FIGS. 1 and 2, the ash auger of the invention is shown generally at 10. The ash auger includes an ash chamber 11 formed in a housing 12 that is preferably made of heat and fire resistant material such as suitably formulated, heat resistant molded plastic. A fireproof tube 13 with a diagonal cut at a free end thereof, has its other end extending through the wall of housing 12 and opens into the ash chamber 11. The housing 12 is preferably molded to provide an integral handle 14 that bridges a recess 15, formed in one side of housing 12. The side mounting of handle 14 allows the unit to be supported with one hand while the auger is operated by the other hand, either by turning of a crank handle or by operation of a control switch, as will be further described.
An auger shaft 16 is rotatably mounted to extend through a rear of the housing 12 and through a bearing 17 and/or bushing 18 mounted in the housing. A crank handle 19 is mounted on the projecting end of shaft 16. Handle 19 may be welded to the shaft or may be attached with other conventional means such as bolts (not shown), threaded into the end of the shaft. Knob 20 is rotatably mounted on handle 19 with bolts (not shown). In FIG. 2, the shaft 16 is shown journaled through a bearing 21 mounted in the wall of the housing 12. An auger 22 is comprised of a helical flight 23 secured to a portion of the auger shaft 16.
The auger shaft and flight 23, extend to the end of a angled opening in the free end of tube 13. Thus, a tip end 24 of the auger is exposed.
The ash auger of FIGS. 1 and 2 is operated by the user grasping handle 14 in one hand, placing the free end of the tube and the exposed tip end 24 of the auger into ashes in a firebox and turning the handle 19 in the clockwise direction (viewed from the handle end) with the other hand. This rotates the auger in a direction such that the flight engages the ashes and moves them along shaft 16 and through tube 13 into the ash chamber 11. The angled end of tube 13 will serve as a scoop as the end is moved through ashes to direct the ashes into the auger flight 23.
The clearance between the wall of tube 13 and the outer edges of flight 23a is made small so that the ashes are efficiently transported and dust from inside the tube cannot escape to atmosphere. The ash chamber 11 is fully enclosed and accordingly, displaced air must exit around auger 22. During rotation of the auger to colect ash only a small volume of dust escapes into the atmosphere since the free end of the tube is positioned in ashes in the firebox.
A heat insulating plate 25 may be provided to cover a portion of the housing 12 around and beneath handle 14. The plate 25, which may be made of any suitable material that will prevent heat transfer therethrough provides a shield to protect the user's hand as handle 14 is grasped.
Housing 12 is curved in all directions away from tube 13 and the ash chamber 11 is large enough to hold the ashes from several days use of a fire bed. Thus, the ashes are discharged from the housing by merely tipping the tube 13 downwardly so that the ashes in the housing will fall to the tube and then turning the auger counter-clockwise to discharge the ashes from the free end of the tube.
In the embodiment of the invention shown in FIG. 3, the ash auger, shown generally at 30, includes a housing 12 (like numerals being used to identify like components in the different embodiments), and an auger tube 13 having an auger 22 therein.
A reversible electric motor 31 is positioned in a compartment formed in housing 12 by a wall 32. An access panel 33 may be snapped to a portion of the wall of housing 14 to provide access to the compartment and the motor. Vent openings 34 through the access panel provide cooling for the motor and for a rechargeable battery unit 35 also positioned in the compartment. A plug 36 for the rechargeable battery is also mounted in the wall of housing 12.
Another handle 37 (additional to handle 14) is formed at the rear of housing 12 and a pivoting trigger switch 38 is adapted to be operated by a user grasping handle 37 to operate the reversible motor in either a forward or reverse direction. The auger shaft 16 is journaled through bearings 38 in the wall 32 and is coupled at 39 to the output shaft of motor 31.
In using the ash auger of FIG. 3, a user grasps handle 14 in one hand and handle 37 in the other. The tip end of tube 13 is positioned in the ashes of a firebox and the motor switch 39 is operated to turn the auger to move the ashes into the housing. In discharging the ashes the switch 39 is operated to reverse motor 31 and operation of the shaft and the housing is held tip down so that the ashes will move from the housing onto the auger for discharge.
Although a preferred form of our invention has been herein disclosed, it is to be understood that the present disclosure is by way of example and that variations are possible without departing from the subject matter coming within the scope of the following claims, which subject matter we regard as our invention. | A portable ash auger including a heat and fire resistant housing with an attached handle and with a fireproof tube that opens into and projects from the housing while surrounding an auger having a tip end extending beyond the tube and drive means for the auger. | 5 |
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 11/417,554, filed on May 3, 2006, pending, which is a continuation of U.S. patent application Ser. No. 11/301,456, filed Dec. 13, 2005, pending, which is a continuation of U.S. patent application Ser. No. 10/811,784, filed Mar. 29, 2004, now U.S. Pat. No. 6,991,076, which is a continuation of U.S. patent application Ser. No. 09/919,582, filed Jul. 31, 2001, now U.S. Pat. No. 6,722,678, which is a continuation of U.S. patent application Ser. No. 09/288,003, filed Apr. 6, 1999, now U.S. Pat. No. 6,267,400.
INCORPORATION BY REFERENCE
[0002] The entireties of U.S. patent application Ser. No. 11/417,554, filed on May 3, 2006, U.S. patent application Ser. No. 11/301,456, filed Dec. 13, 2005, U.S. patent application Ser. No. 10/811,784, filed Mar. 29, 2004, U.S. patent application Ser. No. 09/919,582, filed Jul. 31, 2001, and U.S. patent application Ser. No. 09/288,003, filed Apr. 6, 1999, are hereby expressly incorporated by reference herein and made a part of the present disclosure.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] This invention relates generally to the field of bicycle suspensions. More particularly, the invention relates to a damping enhancement system for a bicycle.
[0005] 2. Description of the Related Art
[0006] For many years bicycles were constructed using exclusively rigid frame designs. These conventional bicycles relied on air-pressurized tires and a small amount of natural flexibility in the frame and front forks to absorb the bumps of the road and trail. This level of shock absorption was generally considered acceptable for bicycles which were ridden primarily on flat, well maintained roads. However, as “off-road” biking became more popular with the advent of All Terrain Bicycles (“ATBs”), improved shock absorption systems were needed to improve the smoothness of the ride over harsh terrain. As a result, new shock absorbing bicycle suspensions were developed.
[0007] Two such suspension systems are illustrated in FIGS. 1 and 2 . These two rear suspension designs are described in detail in Leitner, U.S. Pat. No. 5,678,837, and Leitner, U.S. Pat. No. 5,509,679, which are assigned to the assignee of the present application. Briefly, FIG. 1 illustrates a telescoping shock absorber 110 rigidly attached to the upper arm members 103 of the bicycle on one end and pivotally attached to the bicycle seat tube 120 at the other end (point 106 ). FIG. 2 employs another embodiment wherein a lever 205 is pivotally attached to the upper arm members 203 and the shock absorber 210 is pivotally attached to the lever 205 at an intermediate position 204 between the ends of the lever 205 .
[0008] There are several problems associated with the conventional shock absorbers employed in the foregoing rear suspension systems. One problem is that conventional shock absorbers are configured with a fixed damping rate. As such, the shock absorber can either be set “soft” for better wheel compliance to the terrain or “stiff” to minimize movement during aggressive pedaling of the rider. However, there is no mechanism in the prior art which provides for automatic adjustment of the shock absorber setting based on different terrain and/or pedaling conditions.
[0009] A second, related problem with the prior art is that conventional shock absorbers are only capable of reacting to the relative movement between the bicycle chassis and the wheel. In other words, the shock absorber itself has no way of differentiating between forces caused by the upward movement of the wheel (i.e., due to contact with the terrain) and forces caused by the downward movement of the chassis (i.e., due to movement of the rider's mass).
[0010] Thus, most shock absorbers are configured somewhere in between the “soft” and “stiff” settings (i.e., at an intermediate setting). Using a static, intermediate setting in this manner means that the “ideal” damper setting—i.e., the perfect level of stiffness for a given set of conditions—will never be fully realized. For example, a rider, when pedaling hard for maximum power and efficiency, prefers a rigid suspension whereby human energy output is vectored directly to the rotation of the rear wheel. By contrast, a rider prefers a softer suspension when riding over harsh terrain. A softer suspension setting improves the compliance of the wheel to the terrain which, in turn, improves the control by the rider.
[0011] Accordingly, what is needed is a damping system which will dynamically adjust to changes in terrain and/or pedaling conditions. What is also needed is a damping system which will provide to a “stiff” damping rate to control rider-induced suspension movement and a “soft” damping rate to absorb forces from the terrain. Finally, what is needed is a damping system which will differentiate between upward forces produced by the contact of the wheel with the terrain and downward forces produced by the movement of the rider's mass.
SUMMARY OF THE INVENTION
[0012] A bicycle shock absorber for differentiating between rider-induced forces and terrain-induced forces including a first fluid chamber having fluid contained therein. A piston is configured to compress the fluid within the fluid chamber. A second fluid chamber is coupled to the first fluid chamber by a fluid communication hose and an inertial valve is disposed within the second fluid chamber. The inertial valve is configured to open in response to terrain-induced forces and provides communication of fluid compressed by the piston from the first fluid chamber to the second fluid chamber. The inertial valve does not open in response to rider-induced forces and prevents communication of the fluid compressed by the piston from the first fluid chamber to the second fluid chamber.
[0013] A preferred embodiment is a bicycle, including a bicycle frame, a wheel, and a shock absorber coupled to the bicycle. The shock absorber includes a primary tube having a fluid chamber. A piston rod supports a piston that is movable within the primary tube. A remote tube has a remote fluid chamber. An inertial valve is within the remote tube and is responsive to terrain-induced forces and not responsive to rider-induced forces. The inertial valve opens in response to the terrain-induced forces and fluid flows from the fluid chamber of the primary tube to the remote fluid chamber in response to movement of the piston rod and the piston into the primary tube. The inertia valve has a closed position wherein flow from the primary tube to the remote tube in response to movement of the piston rod and the piston into the primary tube is reduced. A floating piston in the remote tube moves in response to the flow of the fluid from the fluid chamber of the primary tube into the remote fluid chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] A better understanding of the present invention can be obtained from the following detailed description in conjunction with the following drawings, in which:
[0015] FIG. 1 illustrates a prior art rear suspension configuration for a bicycle.
[0016] FIG. 2 illustrates a prior art rear suspension configuration for a bicycle.
[0017] FIG. 3 illustrates one embodiment of the present invention.
[0018] FIG. 4 illustrates an embodiment of the present invention reacting to a rider-induced force.
[0019] FIG. 5 illustrates an embodiment of the present invention reacting to a terrain-induced force.
[0020] FIG. 6 illustrates the fluid refill mechanism of an embodiment of the present invention.
[0021] FIG. 7 illustrates another embodiment of the present invention.
[0022] FIG. 8 is an enlarged schematic view of an embodiment of the present invention wherein the primary tube is mounted directly to an upper arm member and the remote tube is connected to an upper arm member of a bicycle. An angled position of the remote tube is shown in phantom.
[0023] FIG. 9 is an enlarged schematic view of an embodiment of the present invention wherein the primary tube is mounted directly to an upper arm member and the remote tube and the primary tube are a single unit. An angled position of the remote tube is shown in phantom.
[0024] FIG. 10 is an enlarged schematic view of embodiment of the present invention wherein the primary tube is mounted to a lever and the remote tube is connected to an upper arm member of a bicycle. An angled position of the remote tube is shown in phantom.
[0025] FIG. 11 is an enlarged schematic view of an embodiment of the present invention wherein the primary tube is mounted to a lever and the remote tube and the primary tube are a single unit. An angled position of the remote tube is shown in phantom.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0026] A damping enhancement system is described which differentiates between upward forces produced by the contact of the bicycle wheel with the terrain and downward forces produced by the movement of the rider's mass. In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one of ordinary skill in the art that the present invention may be practiced without some of these specific details. In other instances, certain well-known structures are illustrated and described in limited detail to avoid obscuring the underlying principles of the present invention.
An Embodiment of the Damper Enhancement System
[0027] One embodiment of the present damper enhancement system is illustrated in FIG. 3 . The apparatus is comprised generally of a primary tube 302 and a remote tube 304 coupled via a connector hose 306 .
[0028] The damper enhancement system described hereinafter may be coupled to a bicycle in the same manner as contemporary shock absorbers (i.e., such as those illustrated in FIGS. 1 and 2 ). For example, the damper enhancement system may be coupled to a bicycle as illustrated in FIG. 1 wherein the upper mount 318 is pivotally coupled to the seat tube at point 106 and the lower mount 342 is fixedly coupled to the upper arm member 103 . Moreover, the damper enhancement system may be coupled to a bicycle as illustrated in FIG. 2 wherein the upper mount 318 is pivotally coupled to the seat tube at a point 206 and the lower mount 342 is fixedly coupled to a point 204 on lever 211 . These two constructions are illustrated in FIGS. 8-9 and FIGS. 10-11 , respectively.
[0029] In addition, depending on the particular embodiment of the damper enhancement system, the connector hose may be of varying lengths and made from varying types of material. For example, the connector hose 306 may be short and comprised of metal. In this case, the primary tube 302 and the remote tube 304 will be closely coupled together—possibly in a single unit. Such a construction is illustrated in FIG. 9 and FIG. 11 . By contrast, the connector hose may be long and comprised of a flexible material. In this case, the remote tube 304 may be separated from the primary tube 302 and may be independently connected to the bicycle (e.g., the remote tube may be connected to one of the wheel members such as upper arm member 103 in FIG. 1 ). FIG. 8 and FIG. 10 illustrate such a construction, wherein the primary tube 302 is coupled to upper arm member 103 and the remote tube 304 is connected to the upper arm member 103 by a connector. Regardless of how the remote tube 304 is situated in relation to the primary tube 302 , however, the underlying principles of the present invention will remain the same.
[0030] A piston 308 on the lower end of a piston rod 310 divides the inside of the primary tube 302 into and upper fluid chamber 312 and a lower fluid chamber 314 which are both filled with a viscous fluid such as oil. The piston rod 310 is sealed through the cap with oil seals 316 and an upper mount 318 connects the piston to the chassis or sprung weight of the bicycle (e.g., to the seat tube). A lower mount 342 connects the primary tube 302 to the rear wheel of the bicycle via one or more wheel members (e.g., upper arm members 103 in FIG. 1 or lever 205 of FIG. 2 ). Longitudinally extending passages 320 in the piston 308 provide for limited fluid communication between the upper fluid chamber 312 and lower fluid chamber 314 .
[0031] An inertial valve 322 which is slightly biased by a lightweight spring 324 moves within a chamber 326 of the remote tube 304 . The lightweight spring 324 is illustrated in a fully extended state and, as such, the inertial valve 322 is illustrated at one endmost position within its full range of motion. In this position, fluid flow from the primary tube 302 to the remote tube 304 via the connector hose 306 is blocked or reduced. By contrast, when the lightweight spring 324 is in a fully compressed state, the inertial valve resides beneath the interface between the remote tube 304 and the connector hose 306 . Accordingly, in this position, fluid flow from the primary tube 302 to the remote tube 304 through the connector hose 306 is enabled. In one embodiment, the inertial valve 322 is composed of a dense, heavy metal such as brass.
[0032] Disposed within the body of the inertial valve 322 is a fluid return chamber 336 , a first fluid return port 337 which couples the return chamber 336 to the connector hose 306 , and a second fluid return port 339 which couples the return chamber 336 to remote fluid chamber 332 . A fluid return element 338 located within the fluid return chamber 336 is biased by another lightweight spring 340 (hereinafter referred to as a “fluid return spring”). In FIG. 3 the fluid return spring 340 is illustrated in its fully extended position. In this position, the fluid return element 338 separates (i.e., decouples) the fluid return chamber 336 from the fluid return port 337 . By contrast, when the fluid return spring 340 is in its fully compressed position, the fluid return element 338 no longer separates the fluid return chamber 336 from the fluid return port 337 . Thus, in this position, fluid flow from the fluid return chamber 336 to the connector hose 306 is enabled. The operation of the inertial valve 322 and the fluid return mechanism will be described in detail below.
[0033] The remaining portion of the remote tube 304 includes a floating piston 328 which separates a gas chamber 330 and a fluid chamber 332 . In one embodiment of the present invention, the gas chamber 330 is pressurized with Nitrogen (e.g., at 150 p.s.i.) and the fluid chamber 332 is filled with oil. An air valve 334 at one end of the remote tube 322 allows for the gas chamber 330 pressure to be increased or decreased as required.
[0034] The operation of the damping enhancement system will be described first with respect to downward forces produced by the movement of the rider (and the mass of the bicycle frame) and then with respect to forces produced by the impact between the wheel and the terrain.
[0000] 1. Forces Produced by the Rider
[0035] A rider-induced force is illustrated in FIG. 4 , forcing the piston arm 310 in the direction of the lower fluid chamber 314 . In order for the piston 308 to move into fluid chamber 314 in response to this force, fluid (e.g., oil) contained within the fluid chamber 314 must be displaced. This is due to the fact that fluids such as oil are not compressible. If lightweight spring 324 is in a fully extended state as shown in FIG. 4 , the inertial valve 322 will be “closed” (i.e., will block or reduce the flow of fluid from lower fluid chamber 314 through the connector hose 306 into the remote fluid chamber 332 ). Although the entire apparatus will tend to move in a downward direction in response to the rider-induced force, the inertial valve 322 will remain in the nested position shown in FIG. 4 (i.e., it is situated as far towards the top of chamber 326 as possible). Accordingly, because the fluid in fluid chamber 314 has no where to flow in response to the force, the piston 308 will not move down into fluid chamber 314 to any significant extent. As a result, a “stiff” damping rate will be produced in response to rider-induced forces (i.e., forces originating through piston rod 310 ).
[0000] 2. Forces Produced by the Terrain
[0036] As illustrated in FIG. 5 , the damping enhancement system will respond in a different manner to forces originating from the terrain and transmitted through the bicycle wheel (hereinafter “terrain-induced forces”). In response to this type of force, the inertial valve 322 will move downward into chamber 326 as illustrated and will thereby allow fluid to flow from lower chamber 314 into remote chamber 332 via connector hose 306 . The reason for this is that the entire apparatus will initially move in the direction of the terrain-induced force while the inertial valve 322 will tend to remain stationary because it is comprised of a dense, heavy material (e.g., such as brass). Thus, the primary tube 302 and the remote tube 304 will both move in a generally upward direction and, relative to this motion, the inertial valve 322 will move downward into chamber 326 and compress the lightweight spring 324 . As illustrated in FIG. 5 this is the inertial valve's “open” position because it couples lower fluid chamber 314 to remote fluid chamber 332 (via connector hose 306 ).
[0037] Once the interface between connector hose 306 and remote fluid chamber 332 is unobstructed, fluid from lower fluid chamber 314 will flow across connector hose 306 into remote fluid chamber 332 in response to the downward force of piston 308 (i.e., the fluid can now be displaced). As remote fluid chamber 314 accepts additional fluid as described, floating piston 328 will move towards gas chamber 330 (in an upward direction in FIG. 5 ), thereby compressing the gas in gas chamber 330 . The end result, will be a “softer” damping rate in response to terrain-induced forces (i.e., forces originating from the wheels of the bicycle).
[0038] Once the inertial valve moves into an “open” position as described above, it will eventually need to move back into a “closed” position so that a stiff damping rate can once again be available for rider-induced forces. Thus, lightweight spring 324 will tend to move the inertial valve 322 back into its closed position. In addition, the return spring surrounding primary tube 302 (not shown) will pull piston rod 310 and piston 308 in an upward direction out of lower fluid chamber 314 . In response to the motion of piston 308 and to the compressed gas in gas chamber 330 , fluid will tend to flow from remote fluid chamber 332 back to lower fluid chamber 314 (across connector hose 306 ).
[0039] To allow fluid to flow in this direction even when inertial valve 322 is in a closed position, inertial valve 322 (as described above) includes the fluid return elements described above. Thus, as illustrated in FIG. 6 , in response to pressurized gas in gas chamber 330 , fluid in remote fluid chamber 332 will force fluid return element 338 downward into fluid return chamber 336 (against the force of the fluid return spring 340 ). Once fluid return element 338 has been forced down below fluid return port 337 , fluid will flow from remote fluid chamber 332 through fluid return port 339 , fluid return chamber 336 , fluid return port 337 , connector hose 306 , and finally back into lower fluid chamber 314 . This will occur until the pressure in remote fluid chamber 336 is low enough so that fluid return element 338 can be moved back into a “closed” position (i.e., when the force of fluid return spring 340 is greater than the force created by the fluid pressure).
[0040] The sensitivity of inertial valve 322 may be adjusted by changing the angle with which it is positioned in relation to the terrain-induced force. For example, in FIG. 5 , the inertial valve 322 is positioned such that it's movement in chamber 326 is parallel (and in the opposite direction from) to the terrain-induced force. This positioning produces the greatest sensitivity from the inertial valve 322 because the entire terrain-induced force vector is applied to the damper enhancement system in the exact opposite direction of the inertial valve's 322 line of movement.
[0041] By contrast, if the remote tube containing the inertial valve 322 were positioned at, for example, a 45 degree angle from the position shown in FIG. 5 the inertial valve's 322 sensitivity would be decreased by approximately one half because only one half of the terrain-induced force vector would be acting to move the damper enhancement system in the opposite direction of the valve's line of motion. Thus, twice the terrain-induced force would be required to trigger the same response from the inertial valve 322 in this angled configuration. FIGS. 8-11 illustrate the remote tube 304 positioned at an angle from the primary tube 302 (shown in phantom). With such a construction, the sensitivity of the inertial value 322 may be adjusted as described immediately above.
[0042] Thus, in one embodiment of the damper enhancement system the angle of the remote tube 304 in which the inertial valve 322 resides is manually adjustable to change the inertial valve 322 sensitivity. This embodiment may further include a sensitivity knob or dial for adjusting the angle of the remote tube 304 . The sensitivity knob may have a range of different sensitivity levels disposed thereon for indicating the particular level of sensitivity to which the damper apparatus is set. In one embodiment the sensitivity knob may be rotatably coupled to the bicycle frame separately from the remote tube, and may be cooperatively mated with the remote tube (e.g., with a set of gears). Numerous different configurations of the sensitivity knob and the remote tube 304 are possible within the scope of the underlying invention. The connector hose 306 of this embodiment is made from a flexible material such that the remote tube 304 can be adjusted while the primary tube remains in a static position.
[0043] Another embodiment of the damper enhancement system is illustrated in FIG. 7 . Like the previous embodiment, this embodiment includes a primary fluid chamber 702 and a remote fluid chamber 704 . A piston 706 coupled to a piston shaft 708 moves within the primary fluid chamber 702 . The primary fluid chamber 702 is coupled to the remote fluid chamber via an inlet port 714 (which transmits fluid from the primary fluid chamber 702 to the remote fluid chamber 704 ) and a separate refill port 716 (which transmits fluid from the remote fluid chamber 704 to the primary fluid chamber 702 ).
[0044] An inertial valve 710 biased by a lightweight spring 712 resides in the remote fluid chamber 704 . A floating piston 720 separates the remote fluid chamber from a gas chamber 718 . In response to terrain-induced forces (represented by force vector 735 ), the inertial valve, due to its mass, will compress the lightweight spring 712 and allow fluid to flow from primary fluid chamber 702 to remote fluid chamber 704 over inlet port 714 . This will cause floating piston 720 to compress gas within gas chamber 718 .
[0045] After inertial valve 710 has been repositioned to it's “closed” position by lightweight spring 712 , fluid in remote fluid chamber 704 will force fluid refill element 722 open (i.e., will cause fluid refill spring 724 to compress). Thus, fluid will be transmitted from remote fluid chamber 704 to primary fluid chamber 702 across refill port 716 until the pressure of the fluid in remote fluid chamber is no longer enough to keep fluid refill element 722 open. Thus, the primary difference between this embodiment and the previous embodiment is that this embodiment employs a separate refill port 716 rather than configuring a refill port within the inertial valve itself. | A bicycle shock absorber and methods for differentiating between rider-induced forces and terrain-induced forces includes a first fluid chamber having fluid contained therein, a piston for compressing the fluid within the fluid chamber, a second fluid chamber coupled to the first fluid chamber by a fluid communication hose, and an inertial valve disposed within the second fluid chamber. The inertial valve opens in response to terrain-induced forces and provides communication of fluid compressed by the piston from the first fluid chamber to the second fluid chamber. The inertial valve does not open in response to rider-induced forces. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to compressing information stored in a scene graph used in a multi-media presentation.
2. Related Art
MPEG-4 (Moving Pictures Expert Group) is a digital bit stream format used to broadcast or multicast (“netcast”) multimedia presentations. Elements such as HTML objects, Flash animations, audio/visual streams, Java scripts and similar objects can be included in an MPEG-4 scene. The MPEG-4 scene is constructed as a direct acyclic graph of nodes (also referred to as a scene graph) arranged in a hierarchical tree. Grouping nodes are used to construct the scene structure. Children of grouping nodes are used to represent the various multimedia objects in the scene. These children may also have siblings that such that each sibling is associated with a multimedia object. Each node includes a list of fields that define the particular behavior of the node. Taken together, the nodes in a scene graph represent the layout, presentation, interactions and animation of a multimedia scene.
One problem associated with using scene graphs to store information is that a scene graph for a relatively complex scene is very large. A correspondingly large memory is required to store all the scene graphs in a given presentation. The available bandwidth may not be sufficiently large, thus necessitating uncomfortably long download times.
One approach to solving this problem involves inserting a quantization parameter node at the top of the scene graph (that is, in a position that is relatively proximate to the root node) or at one or more other locations in the graph. A quantization parameter node is a specialized node that shows how scene parameters (such as color, angle, scale, rotation and others) are used to specify an aspect of the scene graph or a portion of the scene graph are to be quantized. However, the degree of compression that results from this approach in not optimal because the locations where the quantization parameter nodes are placed are not responsive to the values being quantized. For example, in very small scenes, the cost (as measured by the number of bits) of specifying quantization parameter may exceed the number of bits saved in the scene by including the quantization parameter node. In very large scenes, the degree of compression may be less than optimal because an insufficient number of quantization parameter nodes have been inserted, such that the quantization parameters include a maximum and minimum quantization range for extremely disparate values. In short, the problem of determining an efficient placement of quantization nodes, particularly with respect to an acceptable error range, remains unsolved.
SUMMARY OF THE INVENTION
In a first aspect of the invention, the size of a scene graph and the corresponding amount of memory required to store the scene graph can be reduced by selective placement of quantization parameter nodes in a scene graph. Unlike the prior art of placing the quantization parameter node at the top of the scene graph or at the top of each subtree, a technique is presented for traversing a scene graph so as to determine the most efficient placement of quantization parameter nodes.
The scene graph is traversed depth first to establish an order and then traversed in reverse order. At each node, a calculation relating to (1) the relative cost of inserting a quantization parameter node, and (2) the relative savings that result from insertion of a quantization node is performed. Quantization parameter nodes are selectively placed in response to a result of these calculations. Locations in the scene graph where subtrees of the graph include clustered values (that is, values that fall within a particular range) are identified and quantization parameters that are responsive to these clustered values are inserted. This selective placement of quantization parameters reduces the size of a scene graph substantially. The scene and all of it's various audio-visual components can be transmitted and presented using less memory because a small range of values is used for each portion of the graph controlled by a particular quantization parameter node.
In a second aspect of the invention, the maximum degree of acceptable error value (designated herein as e max ) is chosen for each quantization type. This error value limits the number of quantization parameter nodes that can be placed in a scene graph. While the insertion of quantization parameter nodes increases the error, this increase remains less than a preselected maximum acceptable value.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing a system for quantization and compression of information in a scene graph.
FIG. 2 is a block diagram showing a scene graph and quantization nodes that are selectively placed in optimal positions.
FIG. 3 is a flow diagram showing a method for using a system for quantization and compression of information in a scene graph.
FIG. 4 is a flow diagram of a method for traversing a scene graph used in a system for quantization and compression of information.
FIG. 5 is a block diagram showing an exemplary scene graph with two subtrees and potential quantization parameter nodes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the description herein, a preferred embodiment of the invention is described, including preferred process steps, materials and structures. Those skilled in the art would realize, after perusal of this application, that embodiments of the invention might be implemented using a variety of other techniques not specifically described, without undue experimentation or further invention, and that such other techniques would be within the scope and spirit of the invention.
Lexicography
The following terms relate or refer to aspect of the invention or it's embodiments. The general meaning of each of these terms is intended to be illustrative and in no way limiting.
Quantization—as used herein, the term “quantization” describes a process in which a range of values in a scene graph is represented using a fixed number of bits. The quantization process takes place prior to representing the scene graph in a compressed format. When the compressed scene graph is to be uncompressed, a reverse quantization process is used to return the parameter values to an approximation of their original values.
Quantization parameter node—as used herein, the phrase “quantization parameter node” refers to a special node in a scene graph that specifies how sections of the scene graph or subtrees in the scene graph are quantized.
Scene graph—as used herein, the term “scene graph” is a tree structure that includes a set of nodes that are placeholders for information regarding the display of an object in an MPEG-4 scene or other mixed media presentation. An exemplary scene graph may include a root node associated with an object and a set of dependent nodes associated with various properties of that object such as color, transparency and texture. Additional nodes and subtrees can also be included. Taken by itself, the scene graph is static and acts as a container for information.
Scene—as used herein, the term “scene” refers to a set of objects and other elements (for example, sprites) that are present at any one point in time during a multi-media display.
System Elements
FIG. 1 is a block diagram showing a system for quantization and compression of information in a scene graph.
A system 100 includes an originating server 110 , a terminal 120 and a communication link 130 .
The originating server 110 includes a binary scene encoder 112 , a rasterizer 114 , and a processor, a memory, and sufficient server software to transmit a media stream (such as an MPEG-4 presentation) to a terminal 120 .
The binary scene encoder 112 includes a computer program 113 for generating a scene graph, traversing that graph and determining a heuristically optimal placement of quantization parameter nodes. The term “heuristically optimal” means optimal to a degree possible using a particular technique for examining a set of possibilities that cannot be examined exhaustively.
The rasterizer 114 includes a processor and a computer program for generating a bit map and a set of pixels that are responsive to information generated by the computer program 113 . In a preferred embodiment, the drawing process implemented by the rasterizer 114 is optimized for rendering MPEG-4 data. Upon generating a set of pixels, the rasterizer 114 sends the set of pixels to the terminal 120 .
Although described herein as a single device, the rasterizer 120 and to the binary scene encoder 110 may be incorporated into multiple devices or may be situated at different originating servers 110 that are coupled by a communication link 130 .
The terminal 120 is under the control of a user 122 . The terminal 120 preferably includes a buffer for storing media and sufficient circuitry or software for presenting the media stream to a user 122 . The terminal 120 receives the media stream, buffers and decodes the stream, and presents it to the user 122 . In one embodiment, the terminal 120 may receive different media streams from rasterizer 114 . The different media streams are integrated at the terminal 120 so as to comprise a single presentation for a viewer 122 .
Various embodiments of the terminal 120 include a computer and monitor, or a television and set-top box, among others.
The communication link 130 can include a computer network, such as an Internet, intranet, extranet or a virtual private network. In other embodiments, the communication link 130 can include a direct communication line, a switched network such as a telephone network, a wireless network, a form of packet transmission or some combination thereof. All variations of communication links noted herein are also known in the art of computer communication. In a preferred embodiment, the originating server 110 and the terminal 120 are coupled by the communication link 130 .
FIG. 2 is a block diagram showing quantization parameter nodes that are selectively placed in optimal positions in a scene graph. System 200 includes a first scene graph 210 and a second scene graph 220 . The first scene graph 210 is converted into the second scene graph 210 using the computer program 113 for determining the optimal placement of quantization parameter nodes.
The first scene graph 210 is responsive to an MPEG-4 scene. It includes a set of nodes, shown here as nodes A-K. The scene graph 210 and set of nodes is exemplary. Other scene graphs may a different number of nodes or a different structure.
A node in a scene graph is a parent node if it has other nodes that descend from it. Thus, the parent nodes in scene graph 210 are nodes A, D, and E.
A node is a child node if it descends from a parent node. Thus, nodes B, C, and D are children of A. Nodes F, G, and H are children of D. Nodes I, J, and K are children of E.
A node may be designated as both a parent and a child if it descends from a node and has nodes that depend from it. Thus, nodes D and E are both parents and children.
Nodes are considered to be siblings if they descend from the same parent. Thus, nodes B, C, D, and E are siblings because they all descend from A. Similarly, nodes F, G, and H are siblings, as are nodes I, J, and K.
Each node in scene graph 210 is associated with a scene construct such as a rectangle. Each node also includes various other parameters such as may relate to color, position and other parameters shown in table 1.
None
This parameter is used when there is no
quantization.
Position3D
This parameter is used for 3D positions of
objects.
Position 2D
This parameter is used for 2D positions of
objects.
TextureCoordinate
This parameter is used to show texture
coordinates.
Angle
This parameter is used for angles.
Scale
This parameter is used for scales in
transformations.
Interpolator Keys
This parameter is used for interpolator keys
and MFFloat values.
Normals
This parameter is used for normal vectors.
Rotations
This parameter is sued to shown rotations
of objects.
ObjectSize3D
This parameter includes values for 3D
object sizes.
ObjectSize2D
This parameter includes values for 2D
object sizes.
Linear Quantization
This parameter includes values for the
maximum, minimum and number of bits.
Coord Quantization
This parameter includes lists of coordinates
of points, colors and texture.
Color
This parameter is used to show color and
intensity.
Table 1 shows the types of values that can be included in the nodes of a scene graph.
Scene graph 220 includes a set of nodes that correspond to the nodes in the first scene graph 210 . As with the first scene graph 210 , these nodes are designated as nodes A-K. Unlike scene graph 210 , scene graph 220 also includes two quantization parameter nodes. These quantization parameter nodes are designated as X and Y.
Similar to the first scene graph 210 , the nodes in the second scene graph 220 are associated with a type such as a rectangle. Each node also may include values relating to the parameters included in Table 1.
A quantization parameter node affects the siblings to the right of the quantization node and the children of those siblings. A node may be affected by only one quantization parameter node. Thus, in the second scene graph 220 , the quantization parameter node X affects nodes D, F, G, and H. Quantization parameter node Y affects nodes E, I, J, and K.
Computer program 113 transforms scene graph 210 into scene graph 220 by insertion of the quantization parameter nodes. The location for insertion of the quantization parameter nodes is chosen so as to result in the optimal savings of bits that can be achieved with respect to a predetermined maximum error. The predetermined error is chosen so the perceptible degradation in the visible presentation of media is negligible. Using a predetermined error allows an author to specify how much error is tolerable in the presentation. It is important to note that allowing quantization error does not imply that there will be visual degradation since the error may be imperceptible.
In one embodiment, the predetermined error may be derived from the screen resolution of a presentation element used in the presentation of the multi-media presentation. In other embodiments, the predetermined error may be a fixed percentage of the range of values for one or more quantization types, or a percentage of differences of successive related values.
A quantization parameter node includes maximum and minimum values for each quantization type included in the nodes that it affects. For example, if the nodes affected by quantization parameter Y include color, rotation, angle and scale, then the quantization parameter Y will include maximum and minimum values for color, rotations, angle and scale, along with a number of bits that are used to quantize the range of values between the maximum and minimum.
Method of Use
FIG. 3 is a flow diagram showing a method for using a system for quantization and compression of information in a scene graph.
A method 300 includes a set of flow points and a set of steps. In one embodiment, the system 100 performs the method 300 , although the method 300 can be performed by other systems. Although the method 300 is described serially, the steps of the method 300 can be performed by separate elements in conjunction or in parallel, whether asynchronously, in a pipelined manner, or otherwise. There is no particular requirement that the method 300 be performed in the same order in which this description lists the steps, except where so indicated.
At a flow point 310 , the system 100 is ready to begin performing a method 300 .
At a flow point 315 , an error value is selected for each quantization type that is used in the scene graph that is included in Table 1. Error values for quantization types that are not found in the scene graph are not selected.
As noted supra, the error value may be derived from a number of sources, including the screen resolution of a presentation element, a fixed percentage of the range of values for one or more quantization types, a percentage of differences of successive related values or some other standard.
At a step 320 , the scene graph is traversed depth first to determine an order of the nodes. After determining this order, the scene graph is traversed in the reverse of this order. The following step 325 is performed at each node during this reverse traversal. A detailed example of ordering and reverse traversal is shown in FIG. 4 .
At a step 325 , a pair of calculations for every pair of successive siblings in the scene graph is made. For these calculations, let C(T,QP) equal the cost of inserting a quantization parameter node QP before node T. Let t 1 and t 2 represent the first and second siblings, respectively, in a pair of successive siblings. Let QP 1 and QP 2 be quantization parameters nodes placed before t 1 and t 2 , respectively. Let QP 3 be a quantization parameter node that includes the maximum and minimum of values in both t 1 and t 2 . Given the foregoing, the calculations are:
A=C ( t 2 , QP 3 )
B=C ( t 1 , QP 1 )+ C ( t 2 , QP 2 )
In a step 330 , a sub-tree of a scene graph is quantized. The nodes of the sub-tree are examined and the maximum and minimum values for the quantization types are computed over the whole sub-trees. An error bound value for each of the quantization types is used to compute the number of bits of quantization which will result in a quantization error less than the bound.
The quantization process that takes place in this step involves inserting a quantization parameter node to the left of node t 1 if the value of A is greater than the value of B as determined in step 325 . This quantization node will affect all of the siblings to the right of QP 1 and all of the siblings children. After inserting QP 1 , the calculations are repeated for the next node in the tree. The order of the nodes for which this calculation is performed is described more fully in FIG. 4 .
If the value of A is less than the value of B, then steps 325 and 330 are repeated for the next pair of nodes in the reverse depth-first order. These steps are repeated and the process of comparing the relative cost of inserting quantization parameter nodes and inserting quantization parameter nodes continues until the entire scene graph is traversed.
The steps of the method 300 may be repeated for the remaining scenes in a multi-media presentation until quantization parameter nodes are inserted throughout the presentation where ever it is optimal to insert them.
FIG. 4 is a flow diagram of a method for traversing a scene graph used in a system for quantization and compression of information.
A method 400 includes a set of flow points and a set of steps. In one embodiment, the system 100 performs the method 400 , although the method 400 can be performed by other systems. Although the method 400 is described serially, the steps of the method 400 can be performed by separate elements in conjunction or in parallel, whether asynchronously, in a pipelined manner, or otherwise. There is no particular requirement that the method 400 be performed in the same order in which this description lists the steps, except where so indicated.
In a step 405 , the system 100 is ready to begin performing a method 400 . In one embodiment, the traversal begins with the root node of a scene graph. In other embodiments, the traversal can begin with anywhere in the scene graph.
In a step 410 , the scene graph is traversed to establish an order. The ordering begins with the left most node and proceeds through the siblings of that node moving from left to the right. If a sibling has children, the children of the sibling are traversed before moving on to the sibling. This process is continued until the nodes in the tree have been ordered.
Referring back to FIG. 2, the traversal order of the nodes in scene graph 210 would be A, B, C, D, F, G, H, E, I, J, and K.
In a step 415 , the scene graph is traversed in the reverse of the order that was determined in the previous step. In this reverse traversal, the last node in the order that was established in step 410 will be first and the first node in that order will be last.
Referring back to FIG. 2, the order of the reversal traversal of scene graph 210 would be K,J, I, E, H, G, F, D, C, B, A.
During this reversal traversal, a determination is made whether to insert a quantization parameter node to the left of the node being traversed. This determination is made for every node except for the right most node in a group of siblings.
The reversal traversal is continued until the scene graph is completely traversed. The process begins again at step 410 , when a new scene graph in the multi-media presentation is traversed to establish an order.
FIG. 5 is a block diagram showing an exemplary scene graph with two subtrees and potential quantization parameter nodes.
A system 500 shows a first scene graph 510 and a second scene graph 520 . These two scene graphs are exemplary scene graphs for the purpose of illustrating method 300 and method 400 .
Similar to the scene graph in FIG. 2, scene graph 510 and scene graph 520 are responsive to an MPEG 4 scene. As described in FIG. 2, they include parent nodes, child nodes, sibling nodes and quantization parameter nodes. Subtrees are designated t 1 and t 2 .
The first scene graph 510 includes a quantization parameter node designated as QP 3 . QP 3 affects all the nodes in t 1 and t 2 . The second scene graph 520 includes two quantization parameter nodes, designated as QP 1 and QP 2 . QP 1 affects all of the nodes in t 1 . QP 2 affects all of the nodes in t 2 . QP 1 , QP 2 and QP 3 show the potential location of quantization parameter nodes.
During the performance of methods 300 and method 400 , the cost of scene graph 510 is compared to the cost of scene graph 520 . As noted in step 335 of method 300 , the following calculations are made:
A=C ( t 2 , QP 3 )
B=C ( t 1 , QP 1 )+ C ( t 2 , QP 2 )
If A>B, QP 1 is inserted at the tree at t 1 . If A<B, then the traversal continues as shown in FIG. 4 and the process is continued. This pair of calculations is made for every pair of successive siblings in a scene graph (using the ordering described in FIG. 4) so as to determine a heuristically optimal placement of quantization parameter nodes based upon the relative cost of inserting a node at a particular location.
Alternative Embodiments
Although preferred embodiments are disclosed herein, many variations are possible which remain within the concept, scope and spirit of the invention; these variations would be clear to those skilled in the art after perusal of this application. | A technique wherein the number and position of a quantization parameter node is determined in response to the quantization parameters and a preselected error. The size of scene graph and the corresponding amount of memory required to store the scene graph can be reduced by selective placement of quantization parameter nodes in a scene graph. The scene graph is traversed depth first to establish an order and then traversed in reverse. At each node, a calculation relating to (1) the relative cost of inserting a quantization parameter node and (2) the relative savings that result from insertion of a quantization node is performed. Quantization parameter nodes are selectively placed in response to a result of these calculations. The maximum degree of acceptable error value is chosen for each quantization type. This error value limits the number of quantization parameter nodes that can be placed in a scene graph. | 7 |
This is a continuation of application Ser. No. 07/970,576, filed Nov. 3, 1992, now U.S. Pat. No. 5,473,767.
FIELD OF THE INVENTION
The present invention relates to the field of computers and computer systems, More specifically, the invention relates to features incorporated within a computer system or within a microprocessor for controlling clocking signals.
BACKGROUND OF THE INVENTION
The related technologies of computer and microcomputer design have made incredible advances in the past several decades. New architectural ideas combined with advances in integrated circuit technology have created a series of machines which achieve remarkable performance results.
One way that computer architects and designers can further improve the performance of their machines is by creating an apparatus or mechanism for stopping a processor regardless of the current instruction it is executing. Stopping a processors operation is useful, for example, when testing the state of the processor. One of the problems that has plagued previous technologies is that a processor's state could only be tested, and therefore guaranteed to be valid, when the internal clock signal was stopped and certain predetermined conditions were satisfied. By way of example, such conditions usually occurred during a HALT state or during an input/output (I/O) read. Under these conditions, the processors state was known, so that the processor could be tested at that point. The problem with this prior art approach, however, is obvious; namely, that testing a processor only when a certain number of predetermined conditions are satisfied is highly impractical.
The alternative to stopping a processor on predetermined conditions is to stop the processor asynchronously by disabling the externally-generated signal used as a reference to generate the internal clock rate of the device. The drawback to stopping the processor asynchronously in this manner is that the processing unit is very often in the middle of executing one of its instruction. In the middle of an instruction or micro-instruction, both internal and external buses are precharged. Stopping the processor in the middle of a bus cycle discharges the bus, with a resultant loss of the information being transferred.
Another problem with asynchronously disabling the external reference frequency generator involves the fact that most microprocessors and computer systems utilize a phase-locked loop (PLL) circuit to multiply the reference frequency by some factor to generate the system's internal clock rate. The internal clock signal is utilized by the central processing unit (CPU) of the computer during the execution of its various functions and instructions. The problem arises that if the clock is stopped externally, then the internal phaselocked loop circuitry is likewise disabled. Under such circumstances, reenabling the external reference frequency does not produce an instantaneous response from the PLL; that is, the PLL requires some fixed time period (e.g., several hundred milliseconds) to stabilize. During this start-up time period, spurious signals and glitches are commonly generated, leading to unpredictable results. Thus, starting and stopping of the processor's clock by disabling the external reference input frequency results in a loss of psuedoinstantaneous response.
What is needed then is a means for stopping the CPU's clock at any time, regardless of the instruction that the processor is presently executing, while guaranteeing that the processor is in a known state. As will be seen, the present invention allows the user to stop the clock of a processor within a computer system asynchronously, while still guaranteeing that the state of the processor is preserved. Guaranteeing the processor's environment just previous to stopping the processors clock allows the device to be tested in a manufacturing environment. Another advantage of the present invention is that the processor can be re-enabled without having to restart the system's PLL circuitry. This obviates the need to otherwise wait an inordinate length of time for a stable clock signal to be generated.
SUMMARY OF THE INVENTION
A computer system which includes a processor is described. The invention covers an apparatus and method of controlling the stopping of the clock utilized by a central processing unit (CPU) of a computer system. While stopping the clock, the invention also guarantees the state of the processor. In one embodiment, the invention comprises the use of a novel external pin which can be enabled to initiate a sequence of events that results in the halting of the internal clock signal coupled to the CPU.
In an exemplary embodiment, the invention includes a microcode engine coupled to receive the signal provided by the external pin in response, the microcode engine then executes a sequence of steps which stops the execution of the current instruction on an instruction boundary. The external pin is also coupled to a logic circuit which generates a signal that masks the CPU's clock. An interrupt mechanism is also utilized to prioritize the occurrence of the external stop -- clock signal among other system interrupts. The interrupt mechanism insures that the processor does not stop its clock in the middle of a bus cycle.
One of the added benefits of the present invention is that it may be utilized to emulate the division of the clock (e.g., divide by 2, 4 etc.) by throttling the clock signal on for a given time, and then off for another time period. This has a number of advantages. First, the PLL that generates the internal clock does not need to be modified to allow the division of clock cycles. This means that the present invention allows stopping and starting of the clock function without alteration of the system's phase-lock loop circuitry.
Furthermore, the present invention makes bus designs across multiple time domains much easier; that is, going from the local CPU bus to a standard frequency bus (e.g., like an 8 Mhz ISA bus) is greatly simplified. This result is achieved because of two primary reasons. First, because the clock is stopped on instruction boundaries, bus cycles are never accidentally extended. This means that slave logic coupled to the processor's bus need not be designed in a way that comprehends master extended bus cycles. The second reason simply has to do with the fact that the processor's bus always operates at the same frequency. In prior art designs where the processors clock signal was divided, as opposed to being throttled, logic coupled to the processor's bus had to comprehend not only the processor's maximum frequency, but all potential divided clock frequencies as well. On the other hand, devices coupled to a throttled processors bus only see bus cycles occurring at the maximum frequency.
Another advantage of the invention is that the bus connected to the CPU is made much easier to design since the CPU is not required to have its clock stopped in the middle of a bus cycle. Guaranteeing the state of the processor just prior to stopping the processor's internal clock signal makes the computer system highly testable in a manufacturing environment.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be understood more fully from the detailed description which follows and from the accompanying drawings, which however, should not be taken to limit the invention to the specific embodiments shown, but are for explanation and understanding only.
FIG. 1 illustrates prior art method of stopping the clock signal coupled to a central processing unit of a computer system.
FIG. 2 is a block diagram of one embodiment of the present invention.
FIG. 3 illustrates the relationship of the STPCLK pin to a set of instructions being executed within the execution unit of a computer system.
FIG. 4 is a timing diagram which illustrates the sequence of events which takes place within the computer system when the inventive STPCLK pin is asserted and then deasserted.
FIG. 5 is a flow chart depicting the sequence of events involved in stopping of a processor's internal clock signal.
FIG. 6 illustrates a laptop computer system with external logic for managing CPU power.
DETAILED DESCRIPTION
An apparatus and method for stopping the clock signal coupled to a central processing unit of a computer, regardless of the instruction the processing unit is presently executing, is described. In the following description, numerous and specific details are set forth such as specific event types, circuits, instruction types, etc., in order to provide a thorough understanding of the present invention. It will be obvious, however, to one skilled in the art that these specific details may not be needed to practice the present invention.
FIG. 1 illustrates a prevalent prior art technique for stopping or halting the clock signal coupled to a central processing unit (CPU) within a computer system. By way of example, the scheme illustrated in FIG. 1 is commonly found in such microprocessors as the 80286 microprocessor manufactured by Intel Corporation. As shown, an oscillator 11 provides a periodic signal coupled to CPU 10 through AND gate 12. The output of AND gate 12 represents the external frequency input (EFI) provided to CPU 10. The other input of AND gate 12 is coupled to a signal labeled STOP#, which provides a means for decoupling the EFI signal from CPU 10. If the STOP# signal is low, then the output of AND gate 12 will be low regardless of the signal provided by oscillator 11. On the other hand, if the STOP# signal is at a logical high level, then the output of oscillator 11 will be coupled directly to CPU 10.
As discussed above, there exists a variety of problems associated with the prior art scheme of FIG. 1. For instance, testing the CPU under such a scheme is difficult since it is virtually impossible to test the stopping of the clock on all combinations of instructions which might cause the product to fail. Another related problem is that stopping of the clock in the manner shown in FIG. 1 does not preserve the state of any of the buses in the computer system. This means that the clock could be stopped in the middle of a bus cycle, in which case the information associated with that bus cycle would be irretrievably lost.
With reference now to FIG. 2, a block diagram of the currently preferred embodiment of the present invention is shown. The present invention is preferably implemented on a single integrated circuit (IC) 20 which includes a CPU driven by an internal clock signal, labeled ICLK, on line 33. The internal clock signal of the CPU is generated by means of an external reference oscillatory signal which drives a phase-lock loop (PLL) circuit 21. PLL 21 multiplies the reference frequency by a predetermined factor to produce a clock signal along line 31, coupled to one input of AND gate 22. Note that line 31 is labeled CLK; it is this signal which provides the clock signal to the computer's circuits which cannot tolerate an interruption in the clock signal. For example, a constant clock signal is often required for various cache operations, snooping logic, hold, hold acknowledge operations and arbitration logic. Functions such as these receive the CLK signal.
In the current embodiment, it is only the ICLK signal which is interrupted or halted in accordance with the present invention. The ICLK signal, shown being provided on line 33, clocks the vast majority of CPU operations,. including program and instruction execution. As shown in FIG. 2, it is the ICLK signal that is selectively masked by AND gate 22. This masking operation is achieved by taking line 30 to a logical low potential, i.e., active low. Line 30 is labeled as STP -- MY -- CLK and is provided as an output from the STPCLK logic block 24. The STPCLK logic block 24 includes an ordinary state machine which is coupled to receive the CLK signal provided by PLL 21. In addition, STPCLK block 24 receives inputs from interrupt prioritizer 26 along line 29, from microcode engine 27, and also from the external STPCLK pin along line 28. Likewise, line 28 is also shown being coupled to microcode engine 27 and interrupt prioritizer 26.
It should be understood that the present invention represents a distinct change from the prior art approach in several respects. To begin with, instead of decoupling the external reference frequency signal from the processor--as shown in the prior art--the present invention utilizes an internal mechanism for decoupling the internal clock signal without disturbing the operation of the phase-lock loop. At the same time it guarantees that the clock is stopped in a known state (e.g., on an instruction boundary).
Note also that the embodiment shown in FIG. 2 includes an interrupt prioritizer 26. Prioritizer 26 controls events other than branches that change the normal flow of instruction execution. Interrupt prioritizer 26 operates by detecting interrupt conditions external to integrated circuit 20, and then granting a priority status to each of those interrupt events. By way of example, in FIG. 2 prioritizer 26 is shown receiving a plurality of interrupt signals, including a non-maskable interrupt signal (NMI). A NMI signal may, for instance, represent a parity error generated by system logic. Also shown are interrupt signals generated by the system management (SMI), and a RESET interrupt signal.
In the embodiment of FIG. 2, the STPCLK# signal is shown being routed to interrupt prioritizer 26 as well as to STPCLK logic block 24 and microcode engine 27. When the external STPCLK# signal is asserted, it generates an interrupt to microcode engine 27. This interrupt will be recognized on the next instruction boundary and is granted a high interrupt priority status by interrupt prioritizer 26. Microcode engine 27 includes a STPCLK microcode entry point and microcode program, designed to implement a number of specialized tasks associated with stopping of the internal clock. By way of example, when the STPCLK# signal is asserted, control is passed to the STPCLK microcode handler on the very next instruction boundary. The STPCLK microcode then waits until the prefetcher is idle and then sets an internal STPRDY bit. The STPRDY bit is shown coupled to STPCLK logic block 24. The STPRDY signal from the processor indicates that the ICLK signal is ready to be stopped. Engine 27 then initiates execution of a microcode loop which examines the STPCLK micro-flag (i.e., driven by the STPCLK# pin). When the STPCLK# signal becomes inactive, control then falls out of the STPCLK microcode loop and the processor begins executing the next instruction in the sequence of instructions given by the user code.
At this point of the process, the STPCLK logic block 24,--upon seeing both the STPCLK# and STPRDY signals active,--stops the internal clock to the CPU core by forcing line 32 to a low logic potential. With the STP -- MY -- CLK signal at a logical low potential, the internal clock signal, ICLK, becomes inactive. Finally, when the STPCLK logic block 24 recognizes that the STPCLK# signal is externally deactivated, it then restarts the clock to the processor by de-asserting the STP -- MY -- CLK signal.
It will be appreciated by practitioners in the art that the use of an interrupt prioritizer in the present invention insures that the processor will be testable, since every time the clock is stopped the processor will be in a known state. Internally, the STPCLK pin is treated as if it were any other interrupt generated by system logic. Externally, of course, the STPCLK# pin appears like any other external input to the processor. When the STPCLK# pin is asserted, the CPU halts its internal clock without interfering with either the external reference oscillatory signal or the operation of the internal PLL. When the STPCLK# pin is deasserted, the CPU then restarts its internal clock.
It should also be apparent from the above discussion that any user could assert the STPCLK# pin active so that internally the processor would stop its clock. In addition, the STPCLK microcode might include micro-instructions to generate a bus cycle which would acknowledge that the processor is in fact stopping its clock (i.e., an acknowledge bus cycle). For example, issuing an acknowledge bus cycle could be important at the system level.
One of the ways in which the present invention is especially useful is in laptop computer systems, such as system 60 shown in FIG. 6, in which power management is a primary consideration. In such a system, external logic 61 could be used to disable the internal clock function of CPU 20 when the computer system was idle or otherwise not in use. When the external logic detects an event that normally would wake up the processor, the STPCLK# pin would then be de-asserted so that the processor could then resume operating without the need for a lengthy start-up period.
With reference now to FIG. 3, there is shown an exemplary timing diagram illustrating the relation of the STPCLK# pin to a normal sequence of instructions being executed in the execution unit of a microprocessor. Essentially, FIG. 3 illustrates the STPCLK# pin transitioning from a logical high to a logical low level, where a logical low level represents an active state. As soon as the STPCLK# pin transitions low, a STPCLK interrupt signal is generated on the next instruction boundary. At this point, the microcode engine recognizes that a jump to the STPCLK microcode program is to occur. This activity is shown occurring in FIG. 3 by arrow 40. Note that in FIG. 3, the STPCLK# pin is asserted in the middle of a MOV instruction; however, the internal clock signal of the processor is not halted until the end of the current instruction, i.e., the instruction boundary before the next STO instruction.
The STPCLK microcode program performs several important functions in the current embodiment. To begin with, all of the pipelines within the processor are flushed and then idled. Preferably, the microcode would then indicate to the bus unit to execute a STPCLK acknowledge cycle. After that, the microcode then indicates to the STPCLK logic block 24 to stop the internal clock by asserting the STP -- MY -- CLK signal on line 30 (see FIG. 2). At this point, the microcode engine simply waits until the STPCLK# pin is deasserted; that is, it simply loops on itself until the user or system decides to restart the internal clock.
When the STPCLK# pin is de-asserted, the STPCLK logic block 24 automatically restarts the clock by deactivating the STP -- MY -- CLK signal. During the time that the internal clock signal is halted, PLL 21 remains active so that the CLK signal provided on line 31 is also active. After the STPCLK# pin has been deasserted, the microcode engine detects that the ICLK signal is now active and generates a return. Following the return, the next instruction in the normal sequence of instructions can begin execution.
The present invention ensures that the processor is testable because it is always in a known state (i.e., the STPCLK microcode stops execution on an instruction boundary) whenever the ICLK signal is stopped. Furthermore, all pipelines and instruction queues are flushed by the microcode program. Microcode control also guarantees that execution is never halted in the middle of a bus cycle. This eliminates any precharging problems associated with bus cycles or pipeline stages. Because the STPCLK pin provides control of the ICLK signal at a point in the circuit beyond the phase-lock loop, this also permits an overdrive strategy, where in a new processor can be inserted where the PLL is internally multiplying the clock by some factor (e.g., 2×). To better understand the operation of the present invention consider the example of FIG. 4 and the flowchart of FIG. 5. FIG. 4 illustrates the timing relationship of the sequence of events which typically occurs whenever the internal clock of the processor is to be'stopped. In FIG. 4, the execution unit (EU) is shown having three current instructions, I1, I2, and I3. These instructions may be part of a sequence of instructions currently being executed by the processor. The STPCLK microcode program is shown being run between instructions I2 and I3. In the example of FIG. 4, the STPCLK# pin is shown being asserted by the high-to-low transition 42 which occurs during the middle of instruction I2. The assertion of the STPCLK# pin is shown by eclipse 50 in FIG. 5. When the STPCLK# pin is asserted, it sets a microflag in the microcode engine, and also signals the state machine in the STPCLK logic block. Interrupt prioritizer 26 makes sure that the microcode engine recognizes this input as an interrupt to be asserted at the next instruction boundary. Note that FIG. 4 illustrates the STPCLK# signal being recognized on the instruction boundary following the execution of instruction I2. It is appreciated that there is an associated set-up time between the time that the STPCLK# pin is asserted, and the time that interrupt prioritizer 26 grants it priority status.
On the instruction boundary following the I2 instruction, the microcode engine determines that the STPCLK interrupt is pending and jumps to the STPCLK microcode program. The STPCLK microcode program then makes sure that the CPU is in a known and stable state prior to halting to the internal clock signal. This is shown occurring in FIG. 5 at decision block 51. Once the CPU is in a known state on an instruction boundary, the STPCLK microcode program empties the bus unit of any outstanding bus cycles, generates a stop -- clock acknowledge bus cycle, and then empties the internal pipelines. This is shown occurring in FIG. 5 by blocks 52, 53 and 54. The STPCLK microcode program also stops the prefetcher from prefetching. In a preferred implementation, once all bus activity has been halted, a STPCLK acknowledge bus cycle can be run. The STPCLK ACK bus cycle is shown occurring in FIG. 4 just prior to the bus unit being deactivated. What happens next is that the STPCLK microcode program tells the STPCLK logic block to assert the STP -- MY -- CLK signal, thereby masking the ICLK. FIG. 4 shows the STP -- MY -- CLK # signal going low just after the STPCLK ACK bus cycle is completed. At the same time, the ICLK signal is shown being deactivated. Once the STP -- MY -- CLK signal has been asserted, the ICLK signal to the CPU is halted and CPU logic operation ends. Assertion of the STP -- MY -- CLK signal is represented in the flowchart of FIG. 5 by block 55.
At this stage, the microcode program simply checks to see whether the STPCLK# pin is still active (e.g., decision block 55 in FIG. 5). Once the STPCLK# pin is de-asserted by external logic, the CPU clock is restarted and execution of the next instruction (I3) is returned. This is shown occurring at ellipse 57 in FIG. 5. Arrow 45 in FIG. 4 shows how the low-to-high transition of the STPCLK# pin initiates the sequence of events which results in de-assertion of the STP -- MY -- CLK signal and reactivation of the ICLK to the CPU. After ICLK is activated once again, bus activity also resumes.
Note that with the clock restarted, the microcode engine detects that the STPCLK signal has been deasserted and ends the STPCLK microcode sequence so that the CPU can execute the next instruction. If the CPU had stopped its clock from a HALT state, then it would be necessary to set the CPU's context (i.e., register states, etc.) so that upon leaving the STPCLK microcode program, the processor would reenter the HALT state.
Whereas many alterations and modifications to the present invention will no doubt become apparent to the person of ordinary skill in the art after having read the foregoing description, it is to be understood that the particular embodiments shown and described by way of illustration are in no way intended to be limiting. For example, although this disclosure has shown a particular list of events that may be included as part of a microcode program for stopping the internal clock of a processor, other means are also possible without detracting from the spirit or scope of the present invention. Therefore, reference to the details of the illustrated diagrams is not intended to limit the scope of the claims which themselves recite only those features regarded as essential to the invention. | An apparatus and method for controlling the stopping of the clock signal utilized by the processing unit of a computer system comprises the use of a novel external pin which can be enabled to initiate a sequence of events that results in the halting of the internal clock signal. The invention includes a microcode engine that responds to the assertion of the external pin by executing a sequence of steps which stops the current instruction on an instruction boundary. A logic circuit then generates a signal that masks the clock signal produced by the system's phase-locked loop. An interrupt mechanism is also utilized to prioritize the occurrence of the external signal among other system interrupts. The interrupt mechanism insures that the processor never has its clock stopped in the middle of a bus cycle. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a divisional of application Ser. No. 13/167,378 filed Jun. 23, 2011.
BACKGROUND OF THE INVENTION
The present invention relates generally to farm implements and, more particularly, to a commodity tank for an air seeder.
An air seeder is an agricultural implement that is commonly used to plant usually a seed crop in a large field. Air seeders typically have centrally located hoppers for seed and fertilizer which distributes them through an air stream to individual seed rows. It is convenient to fill, easy to clean out and move. Any crop that can be grown from seeds—which might vary is size from oilseeds to corn, can be sewn by an air seeder.
The seed and fertilizer hoppers are usually carried on a large cart located behind or in front of the seeder. The air stream is created by a high capacity fan mounted on the cart which blows air through conduits (pipes) connecting the hoppers and the row units. Seed and fertilizer are metered out from the hoppers by a meter wheel that is turning in a ratio set by the operator for the proper seed rate or seed density. The seeds enter the pipe in the airstream and follow the pipes which terminate in the seedbed. Openers pulled through the soil make the opening where the seeds are placed. They are typically made of steel in the shape of points, discs or cultivator shovels. Once placed in the seed bed, the air is blown out the opening in the soil and the seed and fertilizer remain. The seeder can then pack the soil tight to retain moisture near the seed and harrow the furrows so the field is not rough.
A typical air seeder has an agricultural commodity cart (“air cart”) comprising at least one, and commonly two, three or more tanks for carrying various agricultural products like seed and fertilizer, which are bolted or otherwise attached to the frame of the commodity cart. The tanks are typically made from either polyethylene, such as found on a CaseIHPrecision Air 3380, or steel such as found on the CaseIH Precision Air 3580.
There is a continued demand for larger capacity commodity tanks. Larger tanks are particularly desirable for wider seeding implements, such as the CaseIH Precision Air 3580. Wider seeding implements are capable of depositing more seed in a single pass. Wider seeding implements will consume seed more rapidly than smaller implements. Hence, there is a general desire to outfit wider seeding implements with larger capacity commodity tanks.
Larger capacity commodity tanks are typically assembled from planar sheet panels. The corners of the tanks are typically formed by separate corner pieces that are attached to a pair of sheet panels. Alternately, it is also common for the ends of adjacent panels to be bent to form an overlapping joint. Regardless of how the corners are made, as the commodity tanks are made larger, the sheet metal panels that collectively form the tanks are consequently larger, One of the drawbacks of larger sheet metal panels is the increased tendency for such panels to warp due to manufacturing processes such as welding or media blasting. One approach to reduce this warping has involved the intentional formation of a bend along the width of the sheet metal panel. Unfortunately, these bends make the connections to mating panels more difficult because basic shapes such as a single overlapping bend or a single bend corner cap cannot be used.
SUMMARY OF THE INVENTION
The present invention provides a method and apparatus for effectively fabricating larger commodity tanks that are formed from a series of sheet metal panels having a warp-reducing bend. To make the interface between panels with warp-reducing bends and planar mating panels at the corners of the commodity tank more effective, the present invention provides a commodity tank having square tubes at the corners.
The square tubes provide a large flat surface for the bent sheet panel to mate to as well as an expansive perpendicular surface to which the adjacent mating panel can be attached. Placing the tubes in the corners of the commodity tank also allows the square tubes to be used as structural members for interfacing with the frame of the air seeder. Additionally, the square tubes may be made hollow and used as ducting to introduce pressure from the air system of the air seeder into the commodity tank.
Therefore, in accordance with one aspect of the invention, a commodity tank for use with an air seeding implement includes a series of panels arranged to form an enclosure defining a volume configured to hold a supply of commodity. At least one or more of the panels has a warping-reducing bend formed therein. The commodity tank further has a series of tubular members with each tubular member located between adjacent and perpendicular panels to define a respective corner of the enclosure. In one embodiment, the tubular members are elongated square tubes.
In accordance with another aspect of the invention, a commodity tank for use with an air seeder includes a series of generally rectangular shaped panels of sheet metal interconnected by an equal number of corner members otherwise separate from the panels. The corner members are each comprised of an elongated square structural member.
The invention may also be embodied in a method. Accordingly, the present invention provides a method of manufacturing a tank for use with an air seeder. The tank includes a plurality of generally planar panels forming sides of the tank. The method includes attaching adjacent planar panels to an elongated corner piece having a generally square-shaped cross-section. The panels and the elongated corn eves collectively define an enclosure for holding a granular commodity.
Various other features, objects and advantages of the present invention will be made apparent from the following detailed description and the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings illustrate one preferred embodiment presently contemplated for carrying out the invention.
In the Drawings:
FIG. 1 is an isometric view of an air cart having a commodity tank according to one embodiment of the invention;
FIG. 2 is a top isometric view of a commodity tank according to one embodiment of the invention;
FIG. 3 is a section view of the commodity tank taken along line 3 - 3 of FIG. 1 ;
FIG. 4 is a section view of the commodity tank taken along line 4 - 4 of FIG. 1 ;
FIG. 5 is a partial cutaway end view of the commodity tank;
FIG. 6 is an enlarged isometric view of a divider plate and sidewall of the commodity tank connected to a connecting member according to one embodiment of the invention;
FIG. 7 is an isometric view of a sidewall of the commodity tank connected to a corner member according to one embodiment of the invention;
FIG. 8 is a rear isometric view of a end plate of the commodity tank connected to the corner member according to one embodiment of the invention;
FIG. 9 is an end view of a sidewall of the commodity tank;
FIG. 10 is an enlarged view of the sidewall of FIG. 9 shown connected to a corner member of the commodity tank according to an embodiment of the invention;
FIG. 11 shows a corner member according to another embodiment of the invention.
DETAILED DESCRIPTION
Turning now to FIGS. 1-4 , an air cart 10 having a pair of commodity tanks 12 , 14 mounted to a frame 16 is shown. The frame 16 is of generally conventional design and thus will not be described further herein. Additionally, it is understood that the commodity tank 12 could be mounted to different types of frames. The illustrated commodity tanks 12 , 14 have two hatches 18 , 20 and 22 , 24 , respectively. Hatches 18 , 20 open into a shared compartment 26 and hatches 22 , 24 open into separate compartments 28 , 30 , respectively. As best shown in FIGS. 3 and 4 , compartments 28 , 30 are separated from one another by a divider plate 32 , which is also shown in phantom in FIG. 1 . It is contemplated that the divider plate 32 may be a fixed mounting within tank 14 or may also be removably mounted. As also shown in FIG. 4 , each compartment has respective lower portions 34 , 36 , 38 that are flow coupled in a known manner to a commodity delivery system (not shown).
It is understood that the invention is not limited to a commodity tank having two separate compartments. Moreover, while the air cart 10 is shown having a pair of commodity tanks, it is understood that the invention is not so limited. Thus, in one embodiment of the invention, an air cart may be equipped with a single tank or could have more than two such tanks “stacked” on a frame to tailor an air cart for a specific sized implement or satisfy a particular consumer request.
For purposes of further describing the invention, commodity tank 14 will be described more fully below but it is understood that commodity tank 12 is similarly constructed. Moreover, as shown in FIG. 1 , multiple tanks can be mounted on a shared frame 16 to form an air cart 10 capable of holding larger volumes of grain, seed, granular chemicals, and the like.
Turning now to FIG. 2 , commodity tank 14 generally consists of an upper portion 40 and the aforementioned lower portions 36 , 38 . In most simple terms, the upper portion 40 defines the upper region of compartments 28 , 30 to each have generally rectangular volumes whereas the lower portions 36 , 38 are shaped so that the lower region of the compartments 28 , 30 each have generally frustoconical volumes.
The upper portion 40 is defined by a series of panels connected to one another using conventional assembling processes, such as welding. More particularly, the panels include upper end panels 42 , 44 (shown in FIG. 4 ) and upper side panels 46 , 48 , The upper end and upper side panels are connected to top panel 50 in which the hatches 22 , 24 are formed.
The panels further include end wall 52 and sidewalls 54 , 56 . End panel 42 is positioned opposite end wall 52 , as shown in FIG. 4 , and effectively functions as another end wall for commodity tank 14 . The sidewalls 54 , 56 connect to the end panel 42 and end wall 52 via corner members 58 , 60 , 62 , 64 . The interconnection with the corner members will be described more fully below. in a preferred embodiment, the panels are formed from sheet metal.
As shown in FIGS. 5, 6, 7, and 9 , the sidewalls 54 , 56 are bent to reduce warping. Sidewall 56 will be described but it is understood that sidewall 54 is similarly designed. Sidewall 56 generally consists of a panel of sheet metal that is bent in a conventional manner to form an inwardly extending bent portion 66 generally defined at the midpoint in the height of the panel. In this regard, the bent portion 66 segments the panel into an upper panel portion 68 and a lower panel portion 70 . In a preferred embodiment, the bent portion 66 extends along the entire width of the sidewall 56 . The sidewall 56 has upper edge 72 that abuts against upper side panel 48 and a lower edge 74 that fits over a top edge of a corresponding panel (not numbered) of the lower portion 38 . it is understood that the top and bottom edges of the sidewall 56 could be weld to the upper side panel 48 and the lower portion 38 , respectively.
With particular reference to FIG. 7 , the sidewall 56 has first and second side (lateral) edges 76 , 78 that are connected, i.e., weld, to respective corner members 60 , 62 . As best shown in FIG. 5 , corner members 58 , 60 are elongated square tubes that extend along the entire height of the sidewalls 54 , 56 and, as such, upright along their entire length. In contrast, corner members 62 , 64 have an upright portion 80 and an inclined portion 82 . Corner members 62 , 64 are also square shaped but have a slightly different orientation than corner members 58 , 60 to match the cut of the sidewalls 54 , 56 .
It will be appreciated that the square-shaped profile of the corner members provides relatively wide, planar surfaces to mate with the sidewalls 54 , 56 , the upper end panel 44 , and end wall 52 . Thus, rather than forming corners with a complimentary bent portion to match the bent portion of the sidewalk, the present invention provides a commodity tank having square tubular corner members that present a flat surface to which the bent portions can be connected in a conventional manner, such as welding.
Additionally, and as best shown in FIGS. 1, 5 and 8 , the configuration of the corner members 58 , 60 , 62 , and 64 provide planar lower surfaces that mate with frame brackets 84 , 86 , 88 , 90 , 92 , 94 for coupling the commodity tank to the frame 16 . In a preferred embodiment, frame brackets 86 , 92 are sized to mate with two corner members, i.e., the adjacent corner members of tanks 12 , 14 as shown in FIG. 1 .
FIG. 10 shows the mating of sidewall 56 with corner member 62 according to the present invention. It can be seen in the figure that the planar face 96 provides a wide seat for the lateral edge 98 of the bent portion 66 . The increased surface area of the planar face 96 enables the sidewall 56 to be weld to the corner member 62 . Similarly, the side face 100 , which is oriented ninety degrees from planar face 96 , provides a wide surface area for welding, or otherwise connecting, the upper end panel 44 to the corner member 62 . It will be appreciated that the other faces (not numbered) of the corner member 62 provide a similar benefit.
From the foregoing it will be appreciated that the present invention provides a commodity tank design having corner members with relatively large, flat surfaces for the bent sheet metal (sidewalk) to mate to while also providing relatively large, flat surfaces at perpendicular angles for the other walls or panels of the tank with which to mate. Additionally, by using the square tubes as corner members for the commodity tank, the square tubes can attached to mounting brackets for securing the tank to the frame. Further, it is contemplated that square tubes, which are preferably hollow, can be flow-coupled to the air system of the air seeder and used for ducting air from the air system into the tanks. Thus, for example, it is contemplated that vent holes 102 , as shown in FIG. 11 , may be formed in one or more of the interior surfaces of the corner members so that air may be ducted into the tank. In the illustrated example, each corner member has four (4) vent holes spaced at equal intervals along the length of the corner member. However, it is understood that more than four or less than four vent holes could be used. Similarly, it is contemplated that the position of the vent holes could be different from that shown. For example, the vent hole(s) could be placed near the upper end of the corner members.
It is further contemplated that the air flow through each vent hole could be the same or different. For example, it is contemplated that the size of the orifices forming the vent holes could vary within a single corner member to differentiate the velocity of air flow. It is also contemplated that conduits (not shown) could be run through the corner members and flow-couple with respective vents to provide dedicate air streams with potentially differing velocities to the several vent holes.
It is also contemplated that the orifices forming the vent holes could be formed to provide directional airflow. For example, the orifices could be shaped such that the air flow exits the orifices in along an upward or downward trajectory. It is further contemplated that the vent holes may be have corresponding covers that are mechanically linked, for example, to a control device that allows a user to open, partially close, or close a selected vent holes. Preferably, such control devices are accessible from outside the commodity tank and allow the vent holes to be open or closed even with a commodity is contained within the tank.
It is further contemplated that the airflow through one or more the vent holes could be sensed and used to provide manual or automated control of any fans, blowers, pumps, motors, and the like that drive air to the corner members through the vent holes. It is further contemplated that the vent holes may include screens to prevent the passage of commodity therethrough.
Alternatively, one or more of the corner tubes may have an open bottom flow-coupled to the air source and a (at least partially) open top that is open to the interior volume of commodity tank.
The present invention has been described in terms of the preferred embodiment, and it is recognized that equivalents, alternatives, and modifications, aside from those expressly stated, are possible and within the scope of the appending claims. | A commodity tank for use with an air seeding implement includes a series of panels arranged to form an enclosure defining a volume configured to hold a supply of commodity. At least one or more of the panels has a warping-reducing bend formed therein. The commodity tank further has a series of tubular members with each tubular member located between adjacent and perpendicular panels to define a respective corner of the enclosure. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application No. 60/383,822, entitled “Method and Apparatus for Insulated Gate Bipolar Transistor Converter Circuit Fault Diagnostics,” filed May 28, 2002, which is hereby incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the field of electronics, and more specifically to a method and an associated apparatus for measuring and diagnosing faulted insulated gate bipolar transistors (“IGBTs”).
2. Description of the Related Art
The bipolar junction transistor (“BJT”), including its extension, the Darlington device, and the metal oxide semiconductor field effect transistor (“MOSFET”) are commercially-available advanced electronics devices. Each device has characteristics that complement the other in some respects. Relative to MOSFETS, BJTs have lower conduction losses in the ON-state and larger blocking voltages, but also have lower switching speeds. In contrast, MOSFETs switch relatively faster, but have relatively larger conduction losses in the ON-state. In order to overcome these performance limitations of the BJT and the MOSFET, the IGBT was designed. This device has significantly superior characteristics for low and medium-frequency applications in comparison to the BJT and the MOSFET Specifically, the IGBT is a voltage control device that can turn ON and OFF at a very high speed, and can deliver very high current compared to conventional bipolar transistors. Furthermore, its power rating can be improved by increasing both current and voltage. For this reason, IGBTs are preferred in some applications over both BJTs and MOSFETs.
IGBTs presently serve a number of traditional markets, including motor drives and welding applications. However, with the emergence of new market segments, it is expected that IGBTs will continue to be a growing part of other industries, such as the semiconductor industry. In particular, the automotive and power supply markets, including uninterruptible power supplies (“UPSs”) and switch mode power supplies (“SPSs”), are expected to drive near term growth.
Due to the cost reduction and performance enhancement of the microprocessor, three-phase AC motor drives are becoming increasingly popular and may eventually replace conventional DC motor drives as the dominant motor drive. Presently, in the electric vehicle (“EV”) field, almost all EVs, including hybrid electric vehicles (“HEVs”) and fuel cell vehicles, use AC motor drives. One of the most important functions of the AC motor controller is to convert DC power to three-phase AC power. IGBTs are typically utilized to perform this conversion.
Referring to FIG. 1 , there is illustrated the structure of a typical IGBT 1 . This structure is very similar to that of a vertically-diffused MOSFET, featuring a double diffusion of a p-type region and an n-type region. An inversion layer may be formed under a gate 2 of the IGBT 1 by applying the correct voltage to the gate contact 3 , much like a MOSFET. The main difference between the MOSFET and the IGBT is the use of a p + substrate layer in the IGBT for a drain. Because of this, the IGBT 1 becomes a bipolar device as the p-type region injects holes into the n-type region.
The gate voltage, V G , controls the ON/OFF state of the IGBT 1 . If the voltage applied to the gate contact 3 with respect to the emitter 4 is less than a threshold voltage, V Th , then no MOSFET inversion layer is created and the device is turned OFF. In this instance, any applied forward voltage will fall across a reversed bias junction, J 2 . The only current to flow will be a small leakage current.
To turn ON the IGBT 1 , the gate voltage V G is increased to a point where it is greater than the threshold voltage V Th . This results in an inversion layer forming under the gate 2 , thereby providing a channel linking the source to the drift region of the IGBT 1 . Electrons are then injected from the source into the drift region, while at the same time junction J 3 , which is forward biased, injects holes into the n − doped drift region. Some of the injected holes will recombine in the drift region, while others will cross the drift region via diffusion and will reach the junction J 3 with the p-type region where they will be collected.
The p-type region exhibits a type of lateral resistance. If current flowing through this resistance is high enough, it will produce a voltage drop that will forward bias the junction with the n + region, turning ON a parasitic transistor that forms part of a parasitic thyristor. Once this happens, there is a high injection of electrons from the n + region into the p-type region, resulting in loss of all gate control. This is known as latch up, and usually leads to device destruction.
FIG. 2 is a circuit diagram illustrating a test structure 10 for performing diagnostics on IGBTs in a manufacturing facility. Six IGBTs, individually referenced as A+, A−, B+, B−, C+ and C−, are provided electrically coupled and drivable as a three-phase AC inverter 12 , which is to be tested. The test structure 10 includes a voltage source V dc , a tester 14 , an inverter drive 16 including a microprocessor (not shown in FIG. 2 ), a controlled area network (“CAN”) 18 , and a test circuit 20 . The tester 14 , located at the end of the manufacturing line, is coupled to the microprocessor of the inverter drive 16 via the CAN 18 for passing commands and data between the tester 14 and the microprocessor. The test circuit 20 includes five relays, individually referenced as Ra 1 , Ra 2 , Ra 3 , Ra 4 and Ra 5 , a current sensor 22 and a current limiter 24 . The tester 14 controls the relays Ra 1 , Ra 2 , Ra 3 , Ra 4 and Ra 5 , in the test circuit 20 , monitors the voltage of each of the IGBTs A+, A−, B+, B−, C+, C−, and makes decisions based upon production tests. The inverter drive 16 provides drive signals to the gates of the IGBTs A+, A−, B+, B−, C+, C−, which are synchronized with the states of the relays Ra 1 , Ra 2 , Ra 3 , Ra 4 and Ra 5 by the tester 14 to selectively turn each individual IGBT ON and OFF, one at a time, thereby controlling the current going through the IGBTs during testing. Two current sensing signals I a and I b provide the phase current to the microprocessor of the inverter drive 16 . The collector-emitter voltage V ce across the collector c and emitter e of each of the IGBTs, is measured during the testing of the IGBTs and provided to the tester 14 .
Testing of the IGBT switching circuits, for example, A+, requires control relays Ra 1 and Ra 5 to be closed. After the microprocessor of the inverter drive 16 commands IGBT A+ ON, current will travel through its collector and emitter terminals, c and e respectively, relay Ra 1 , current limiter 24 and relay Ra 5 . If IGBT A+ is not faulty, the collector-emitter voltage V ce across the IGBT A+ will be close to zero volts and the current feedback I a will be equal to a predetermined value. The microprocessor of the inverter drive 16 reads the phase current I a and sends that value to the tester 14 via the CAN 18 .
Further reference to FIG. 2 shows the absence of a current feedback sensor for the C phase, and hence, no current information available for the C phase. This is due to hardware limitations and cost. Accordingly, the two C phase IGBTs C+, C− can only be tested with a measurement of the respective collector-emitter voltages V ce . In order to test all six IGBTs A+, A−, B+, B−, C+, C−, at least six measurements are required. Among the six measurements, four require both current and voltage measurements, while two require only voltage measurements.
As illustrated above, the IGBTs have rather complicated gate drive circuits and can be easily damaged resulting in undiscovered errors. This makes the manufacture of IGBT based power circuits and drive circuits difficult and complex. Further, in the case of a faulted IGBT 1 in the field, diagnostics that pinpoint the exact faulted transistor are also difficult and challenging. Accordingly, there is a need for an improved method of detecting faulted IGBTs.
BRIEF SUMMARY OF THE INVENTION
By providing an improved testing method, both manufacturing test procedures and equipment may be simplified, and production time and cost may be reduced. Additionally, such a detection method may provide a diagnostic routine and equipment capable of locating a faulted IGBT in the field.
In the disclosed embodiments, the present invention may alleviate the drawbacks described above with respect to diagnosing faulted IGBT circuits. The present invention provides a method and apparatus for measuring the current across various IGBT circuits by connecting the output of an inverter to a three-phase resistor load having a common resistance value.
It should be understood that the present invention is not limited to uses related to EVs, or even AC induction drives, but is applicable to any inverter applications, including distributed power, such as fuel cells, micro-turbines and windmills, static/dynamic power quality converters, and so forth.
The beneficial effects described above apply generally to each of the exemplary descriptions and characterizations of the devices and mechanisms disclosed herein. The specific structures through which these benefits are delivered will be described in detail herein below.
In one aspect, a method for measuring fault diagnostics for an IGBT power converter circuit includes selectively turning ON a first, a second and a third IGBT, wherein each of the first, the second and the third IGBT may be either upper (A+, B+ or C+) or lower (A−, B− or C−) ones of IGBT pairs (i.e., first IGBT pair A+ and A−, second IGBT pair B+ and B−, and third IGBT pair C+ and C−). These upper and lower IGBTs are illustrated in FIG. 3 . One skilled in the art will readily recognize that the use of the terms “upper” and “lower” are for convenience in referring the relative electrical positions of the IGBTs in the electrically coupled pairs, and these terms do not imply any specific spatial orientation within a power converter, vehicle, other device, or with respect to any other spatial reference frame.
The method also includes measuring a current feedback of the first and the second IGBT and comparing the current feedback of the first and the second IGBT to a current value of the third IGBT, wherein the current value is determined by a resistor value. The method further includes determining a fault-state for the IGBTs and concluding that the IGBTs are either normal, open or shorted based upon the results of the comparison. When all the IGBTs are normal, no voltage measurements are required. The output of an inverter is connected to a multi-phase resistor load and when one faulty IGBT exists, a gate drive fault is generated at the faulty IGBT where the fault is an open fault. Where the fault in an IGBT is a short, a diagnostics circuit shuts down to protect the remainder of the IGBTs.
In another aspect, an apparatus for measuring fault diagnostics for an IGBT power converter circuit includes a plurality of IGBTs which may be selectively turned ON, wherein the plurality of IGBTs may be grouped in pairs and identified as either upper IGBTs (A+, B+ or C+) or lower IGBTs (A−, B− or C−) of each pair. The apparatus also includes a resistor load coupled to the plurality of IGBTs, a current sensor coupled to two of the three phase outputs and an inverter drive, wherein the inverter drive is operable for receiving current feedback from the plurality of IGBTs. The apparatus further includes a tester in communication with the inverter drive and a voltage source coupled to the plurality of IGBTs.
In another aspect, a fault determination method for assessing a condition of a power converter circuit, the power converter circuit having a number N of pairs of insulated gate bipolar transistors (“IGBTs”), each pair of IGBTs having an upper IGBT coupled to a first polarity of a DC power source and a lower IGBT coupled to a second polarity of the DC power source, includes but is not limited to: selectively placing in a conducting state at least one upper IGBT during a first time and selectively placing in a conducting state at least one lower IGBT during the first time; and determining a set of IGBT operational states in response to at least one of a magnitude and a direction of a current through a load between the at least one upper and the at least one lower IGBT during the first time.
In another aspect, a fault determination method for assessing a condition of a power converter circuit, the power converter circuit having a number N of pairs of (IGBTs), each pair of IGBTs having an upper IGBT coupled to a first polarity of a DC power source and a lower IGBT coupled to a second polarity of the DC power source, includes but is not limited to: during a first time interval, controlling at least one upper IGBT and at least one lower IGBT such that at least one first-time-interval expected current will flow through a part of a resistive network if the at least one upper IGBT and the at least one lower IGBT are normal, sensing at least one of a magnitude and a direction of at least one first-time-interval current through the part of the resistive network, comparing the at least one first-time-interval sensed current with the at least one first-time-interval expected current; and concluding a state of at least one IGBT in response to the comparing.
In another aspect, a fault determination method for assessing a condition of a power converter circuit, the power converter circuit having a number N of pairs of (IGBTs), each pair of IGBTs having an upper IGBT coupled to a first polarity of a DC power source and a lower IGBT coupled to a second polarity of the DC power source, includes but is not limited to: during a first time interval and in response to a motor indicating a fault, sequentially controlling at least one upper IGBT and at least one lower IGBT such that at least one first-time-interval expected current will flow through a part of motor windings if the at least one upper IGBT and the at least one lower IGBT are normal, sensing at least one of a magnitude and a direction of at least one first-time-interval current through the part of the motor windings; comparing the at least one first-time-interval sensed current with the at least one first-time-interval expected current and concluding a state of at least one IGBT in response to the comparing.
In one or more various embodiments, related systems include but are not limited to circuitry and/or programming for effecting the foregoing-referenced method embodiments; the circuitry and/or programming can be virtually any combination of hardware, software, and/or firmware configured to effect the foregoing-referenced method embodiments depending upon the design choices of the system designer.
The foregoing is a summary and thus contains, by necessity, simplifications, generalizations and omissions of detail; consequently, those skilled in the art will appreciate that the summary is illustrative only and is NOT intended to be in any way limiting. Other aspects, inventive features, and advantages of the devices and/or processes described herein, as defined by the claims, will become apparent in the detailed description set forth herein.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1 is an illustration of the structure of a typical IGBT as known in the art.
FIG. 2 is a circuit diagram of a test structure including a test circuit for testing IGBTs in a three-phase AC inverter.
FIG. 3 is a circuit diagram of a test structure for testing IGBTs in a three-phase AC inverter according to one illustrated embodiment of the present invention.
FIG. 4 is a functional block diagram of a portion of the test structure of FIG. 3 , illustrating the testing of one phase of the three-phase AC inverter according to one illustrated embodiment of the invention.
FIG. 5 is a circuit diagram of a test structure for in field testing of IGBTs in a three-phase AC inverter, such as for testing in a three-phase AC inverter mounted in a power conversion module of a vehicle, according to another illustrated embodiment of the present invention.
FIG. 6 is a flow chart showing the process of determining a state of an IGBT in response to a comparison of measured and expected currents.
DETAILED DESCRIPTION OF THE INVENTION
As required, detailed embodiments of the present invention are disclosed herein. However, it is to be understood that the disclosed embodiments are merely exemplary of the present invention that may be embodied in various and alternative forms. The figures are not necessarily to scale, e.g., some features may be exaggerated or minimized to show the details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention. Unless the context requires otherwise, throughout this specification and claims which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense, that is as “including, but limited to.”
FIG. 3 shows a test structure 30 including a voltage source V dc , a tester 32 , an inverter drive 34 having a microprocessor 36 (FIG. 4 ), a (CAN) 18 , and a test circuit 40 for testing an inverter 12 , according to one illustrated embodiment of the present invention. The inverter 12 may, or may not, be part of a power converter, for example for use in a vehicle or stationary power application. The test structure 30 may include an optional printer or display 41 for reviewing test results.
In contrast to the test circuit 20 of FIG. 2 , the output of the inverter 12 is connected to a three-phase resistor load 42 , of the test circuit 40 , formed by three resistors R 1 , R 2 , R 3 all having at least approximately the same value of resistance R. Two current feedbacks, I a and I b , are returned to the microprocessor 36 ( FIG. 4 ) of the inverter drive 34 , while a set of gate drive circuitries on a gate drive board 44 ( FIG. 4 ) monitor the voltages V ce across each IGBT A+, A−, B+, B−, C+, C−. This test structure 30 is simpler, and makes fuller use of the capabilities of the microprocessor 36 ( FIG. 4 ) than the test structure 10 of FIG. 2 , and in certain embodiments may eliminate the need for the tester 32 .
FIG. 4 is a functional block diagram of a portion of the inverter drive 34 , driving a single pair of the IGBTs A+, A− for testing a first phase A of the inverter 12 . The microprocessor 36 handles all the input signals and manages and controls the outputs based on control algorithms. Among the outputs, the microprocessor 36 provides three Pulse Width Modulation (PWM) output signals 46 A, 46 B, 46 C to a Logic Cell Array (LCA) 48 . The LCA 48 may take the form of an appropriately programmed Field Programmable Gate Array (“FPGA”). The LCA 48 is a programmable digital circuit that generates six IGBT gate control signals 50 A+, 50 A− (only two shown) based on the three PWM output signals 46 A, 46 B, 46 C from the microprocessor 36 . The LCA 48 also handles all of the fault signals collectively referenced as 52 coming from the circuitries on the gate drive board 44 . It should be noted that FIG. 4 only shows one of the three phases of the gate drive circuitry. It should also be noted that the phases are referred to as first, second and third phases for convenience only and such reference should not be interpreted as an enumeration or ordering the operation of the corresponding IGBTs A+, A−, B+, B−, C+, C−.
For every IGBT A+, A−, B+, B−, C+, C− there is an isolated control signal V ge for the gate control, and the forward voltage (or conducting or collector-emitter voltage) V ce is measured to detect a De-Saturation (DESAT) fault. When an IGBT is forward conducting, if there is a large current passing through the IGBT, the collector-emitter voltage V ce will increase as the conducting current increases. As soon as the collector-emitter voltage V ce reaches a certain voltage level (corresponding to a certain current level), the corresponding drive circuit on the gate drive board 44 will generate a fault 52 , called a DESAT fault, and shut down the gate control signals V ge .
The following are examples of six different situations, each illustrating the acts taken to test and diagnose all six IGBTs A+, A−, B+, B−, C+, C−.
All IGBTs Normal (i.e., Not Faulty)
Only two test measurements are needed to determine if all IGBTs A+, A−, B+, B−, C+, C− are normal. For example, the microprocessor 36 commands IGBTs C−, A+ and B+ ON at a same time. If all six IGBTs A+, A−, B+, B−, C+, C− are in a normal, non-faulty condition, the current I a flowing through the first phase upper IGBT A+ and the current I b flowing through the second phase upper IGBT B+ should be equal to the same predetermined value, I, the normal current flowing through when no fault exists, which is half of the value of the current flowing through, the third phase lower IGBT C−. Current value is determined by the resistance R. Likewise, commanding the third phase upper IGBT C+, the first phase lower IGBT A− and the second phase lower IGBT B− ON at a same time, current feedback I a and I b will have the same predetermined value I, but with opposite current direction to the first test. This is summarized in Table 1.
TABLE 1
Command ON
Current Feedback
Fault
Conclusion
A+, B+, C−
I a = I b = I
None
A+, B+ and C− are OK
A−, B−, C+
I a = I b = −I
None
A−, B− and C+ are OK
In the above measurements, even though no current feedback information is available for the C phase, the IGBTs C+, C− in the C phase can be viewed as normal if the correct current feedback values are observed in phase A and B. Furthermore, since the circuits of the gate drive board 44 monitor the voltage V ce between the collector c and the emitter e of the IGBT that is being turned ON, no voltage measurements by the tester 32 are required. Advantageously, measurement and testing time may be greatly reduced.
One Faulty IGBT in any Single Phase
At least three steps are required to determine the faulty IGBT in this scenario. Consider for example, the case of the first phase upper IGBT A+ being open or the first phase lower IGBT A− being shorted. When the upper IGBTs A+, B+ and C− are commanded ON, if the first phase upper IGBT A+ is faulty, i.e., A+ is open, the collector-emitter voltage V ce across the first phase upper IGBT A+ will be high, generating a gate drive fault 50 A+ sent to the microprocessor 36 . However, if the first phase lower IGBT A− is the faulty transistor, i.e., the phase lower IGBT A− is shorted but first phase upper IGBT A+ is normal, then when first phase upper IGBT A+ is commanded ON a large current will pass through the first phase pair of IGBTs A+, A− due to the shorted first phase lower IGBT A−. The DESAT circuit will shut down the inverter 12 to protect the IGBTs and generate a fault at 50 A+. Accordingly, the same fault signal will be generated for two different faults at two different places.
In order to be able to determine whether first phase upper IGBT A+ is open or first phase lower IGBT A− is shorted, and thereby determine where the fault occurred, only the third phase upper IGBT C+ needs to be turned ON. If the current feedback I a is equal to approximately −1.5 times the predetermined current I, then the first phase lower IGBT A− is shorted. If no current feedback is observed (i.e., I a is equal to I b is equal to zero), then the first phase upper IGBT A+ is open, and the first phase lower IGBT A− is not faulty.
To check and to determine if the second phase upper IGBT B+, the second phase lower IGBT B−, the third phase upper IGBT C+ and the third phase lower IGBT C− are normal with respect to predetermined current feed back I a and I b , the second phase upper IGBT B+ and third phase lower IGBT C− should be turned ON, followed by the turning ON of the second phase lower IGBT B− and third phase upper IGBT C+. In the case of the second phase upper IGBT B+ and third phase lower IGBT C− being turned ON, the current feedback I b should be the negative of 1.5 times the predetermined current I.
In a like manner, a single opened or shorted IGBT in phase B or C can be identified. Table 2 summarizes detection of one fault as described above.
TABLE 2 Current Command ON Feedback Fault Conclusion A+, B+, C− None A+ Either A+ open or A− shorted A−, B−, C+ I a = I b = −I None A−, B− and C+ OK; or A− shorted C+ I a = −1.5I or None A− is shorted and A+ may be OK I a = I b = 0 A+ is open and A− is OK B+, C− I b = −1.5I None B+ and C− OK B−, C+ I b = 1.5I None B− and C+ OK
One or Two Faulty IGBTs in Phase C
Consider the example of the fault(s) of C+ open and/or C− shorted. To perform the test, the first phase upper IGBT A+, second phase upper IGBT B+ and third phase lower IGBT C− are commanded ON by the microprocessor 36 . Similar to the previous example, if the third phase upper IGBT C+ is open, its current-emitter voltage V ce will be high, causing a corresponding gate drive fault signal (i.e., fault C+) to be sent out by the microprocessor 36 . However, if the third phase lower IGBT C− is shorted and the third phase upper IGBT C+ may or ma not be open, then when the first phase lower IGBT A−, the second phase lower IGBT B− and the third phase upper IGBT C+ are commanded ON in the next step of testing, a large current through the IGBTs due to the shorted C−. The DESAT circuit shuts down protecting inverter 12 and generates a fault 52 (i.e., fault C+). Again the same fault generated for two different faults at two different places.
The next step in the testing is to determine whether just one IGBT in a single phase is faulty, or both IGBTs in that phase are faulty. Here the microprocessor 36 commands ON both the first phase upper and the second phase lower IGBTs, A+, B−, respectively. If the results of the current feedback are I a is equal to 1.5 times the predetermined current I and I b is equal to−1.5 times the predetermined current I, then it may be concluded that the third phase upper IGBT C+ is open. If the results of the current feedback for both I a and I b is negative I, then it may be concluded that the third phase lower IGBT C− is shorted, and that the first phase upper and second phase lower IGBTs A+, B−, respectively, are normal. Further testing is still required to determine whether the first phase upper IGBT B− and the second phase upper IGBT A− are normal.
Determination of whether all the IGBTs have been checked can be made by commanding the first phase lower IGBT A− and the second phase upper IGBT B+ ON. If the results of the current feedback are I a is equal to −1.5 times the predetermined current I and I b is equal to 1.5 times the predetermined current I, then it may be concluded that the third phase upper IGBT C+ is open, and that the first phase lower IGBT A− and the second phase upper IGBT B+ are normal. If the results of the current feedback are I a is equal to −I and I b is equal to I, then it may be concluded that the third phase lower IGBT C− is shorted.
Table 3 summarizes detection of one or two faults in one phase as described above.
TABLE 3 Command ON Current Feedback Fault Conclusion A−, B−, C+ None C+ Either C+ open and/or C− shorted A+, B+, C− I a = I b = −I None A− and B− OK; C− may be shorted A+, B− I a = −I b = −1.5I None C+ open; A+ and B− may or be OK I a = −I b = −I C− shorted; A+ and B− may be OK A−, B+ I b = −I a = I None C− shorted; A− and B+ OK or C+ open; A− and B+ OK I b = −I a = 1.5I
One or Two Faulty Transistors in any Two Phases
Consider the example of the first phase upper IGBT A+ open and/or the first phase lower IGBT A− shorted, and the second phase upper IGBT B+ open and/or the second phase lower IGBT B− shorted. The same logic as shown previously applies, the microprocessor 36 commanding the first phase upper, second phase upper and third phase lower IGBTs A+, B+ and C−, respectively, ON. In this situation where there is one or two faulty IGBTs in any two phases, no current feedback will be detected, and a fault will be indicated in both the A and B phases. Accordingly, all that is known at this point of the testing is that first phase upper IGBT A+ is open and/or the first phase lower IGBT A− is shorted, and the second phase upper IGBT B+ is open and/or the second phase lower IGBT B− is shorted.
As before, the microprocessor 36 next commands ON the first phase lower, the second phase lower, and the third phase upper IGBTs A−, B− and C+, respectively. If the current feedback shows both I a and I b to be the opposite of the predetermined current I, then it may be concluded that either the first phase lower IGBT A−, the second phase lower IGBT B− and the third phase upper IGBT C+ are normal, or that the first phase lower IGBT A− and the second phase lower IGBT B− are both shorted. It is still unknown at this point whether the first and second phase upper IGBTs A+, B+, respectively, are open.
The next step indicates where the faults occurred in the A and B phases. To do so, the microprocessor 36 turns ON only the third phase upper IGBT C+. If the current feedback for both I a and I b is the opposite of the predetermined current I, then it is determined that at least the first and second phase lower IGBTs A−, B−, respectively, are faulty. The first and second phase upper IGBTs A+, B+, respectively, may or may not be faulty. If the current feedback for I a is both the opposite and 1.5 times the predetermined current I and no current feedback is given by I b then it is determined that at least first phase lower IGBT A− and the second phase upper IGBT B+ are faulty. The first phase upper IGBT A+ may or may not be faulty. If the current feedback for I b is both the opposite and 1.5 times the predetermined current I and no current feedback is given by I a , then it is determined that at least the second phase lower IGBT B− and the first phase upper IGBT A+ are both faulty. The second phase upper IGBT B+ may or may not be faulty. If no current feedbacks are both zero, then it may be concluded that both the first and the second upper IGBTs A+, B+, respectively, are open.
Table 4 summarizes detection of one or two faults in two phases, but not in phase C, as described above.
TABLE 4
Command ON
Current Feedback
Fault
Conclusion
A+, B+, C−
None
A+
A+ open and/or A− shorted
and/or
and/or
B+
B+ open and/or B− shorted
A−, B−, C+
I a = −I and/or
None
A−, B−, C+ OK; or
I b = −I
A− and/or B− shorted
C+
I a = −I and
None
A− shorted; A+ may be
I b = −I or
open or OK and
I a = −1.5I and
B− shorted; B+ may be
I b = 0 or
open or OK
I b = −1.5I and
A− shorted; A+ may be
I a = 0 or
open or OK and B+ open
I a = I b = 0
B− shorted; B+ may be
open or OK and A+ open
A+ and B+ are open
It should be noted that every IGBT has been tested through the current feedback signal except C−. However, since no fault signal is generated in the first test, it is understood that the correct voltage level has occurred at C−.
Table 5 illustrates the test procedure for the case of faulty transistors in two phases where one of the faults occurs in the C phase. Table 5 illustrates the steps followed and the possible results for the situation of third phase upper IGBT C+ open and/or third phase lower IGBT C− shorted, and first phase upper IGBT A+ open and/or first phase lower IGBT A− shorted.
TABLE 5
Command ON
Current Feedback
Fault
Conclusion
A+, B+, C−
None
A+
A+ open and/or A− shorted;
and B+ and C− OK; or
B+ open and/or C− shorted
A−, B−, C+
None
C+
C+ open and/or C− shorted;
and A− and B− OK; or
A− and/or B− shorted
B+
I a = −I and
None
A−, C− shorted; B+ OK
I b = 2I or
A− shorted; C+ open
I a = −1.5I = −I b
C− shorted; A+ open
or
C+ and A+ are open
I b = −1.5I,
I a = 0 or
I b = I a = 0
It should be noted that every IGBT has been tested through the current feedback signal except the second phase lower IGBT B−. However, since no fault signal is generated in the first test, it is understood that the correct voltage level has occurred at the second phase lower IGBT B−. Furthermore, the test cases with faulty IGBTs in phase B and C are similar to the above case.
A Faulty IGBTs in all Three Phases
Consider the situation of the first phase upper IGBT A+ open and/or the first phase lower IGBT A− shorted, the second phase upper IGBT B+ open and/or the second phase lower IGBT B− shorted, and the third phase upper IGBT C+ open and/or the third phase lower IGBT C− shorted. When the first phase upper IGBT A+, the second phase upper IGBT B+ and third phase lower IGBT C− are commanded ON, followed by commanding ON the first phase lower IGBT A−, the second phase lower IGBT B− and the third phase upper IGBT C+, faults will occur in every phase (A, B and C). In this situation, there is no need to continue testing as all power modules will be seen as faulty devices.
As seen from the above six situations, if there is no faulty IGBT in the inverter 12 , as is the instance in the majority of cases, only two tests are required to diagnose the same. Should any IGBT failure exist, up to five tests are required in order to locate the failed IGBT(s). Other than a three-phase resistor load, no extra hardware circuitry is required. Additionally, this method and apparatus for testing makes full use of the intelligent microprocessor 36 and extra information from the circuits of the gate drive board 44 .
IGBT Fault Detection With an AC Motor Connected
In the field, after a failure occurs on the inverter 12 , the microprocessor 36 generates a gate drive fault indicating that one of the IGBTs failed without the above described logic. However, due to the complexity of the gate drive circuit and the inaccessibility of each individual IGBT, the above described system and method is very difficult to determine which, if any, IGBT failed without the above described logic. With very minor changes to the above, the above described system and method may be used as an AC inverter field diagnostic tool. Referring to FIG. 5 , instead of utilizing the three-phase resistor load described above with reference to FIG. 3 , the stator windings 60 a , 60 b , 60 c of a three-phase motor 62 are used as the load. Such a diagnostics method and tool avoids the difficulty and problem of removing parts only to find that no IGBT has failed. The inverter 12 and test circuitry 30 may be part of a power module 64 for installation in a vehicle 66 .
AC motors 62 have very low impedance at stand still. Thus, in order to avoid huge current passing through the motor's windings, the IGBTs' ON time should be very short, i.e., pulsed. In other words, the IGBTs' ON time should be less than the switching period of the inverter 12 . Also, the turn ON signals for upper and lower IGBTs A+, B+, C+ and A−, B−, C−, respectively, of each phase should not overlap each other. The output may be configured as either an output compare or a (PWM) function so that the duty cycle is less than the switching period.
For example, when an ON signal for the first phase upper IGBT A+ is generated, normally it is a PWM signal. When testing occurs in a manufacturing facility, as illustrated in FIG. 3 , a resistor is generally available for limiting the current, with the current level determined by the resistance R and the DC bus voltage level. Typically, in a manufacturing facility environment, a power supply will be available for adjusting the DC voltage level. Accordingly, through the use of the resistor R 1 , R 2 , R 3 the current can be turned ON and kept ON without the concern of current overload.
However, in the case of an AC motor 62 in the field, for example in a vehicle 66 , the current cannot always be ON because it would be too high, overloading the IGBTs. Since there is no power supply available that can adjust the DC bus voltage level, a PWM signal is used that limits the ON time, or duty cycle, to a very short time. By adjusting the duty cycle, the current can be measured within a reasonable range.
The V ge shown in FIG. 4 is the gate control signal for controlling the IGBT and provided via the gate driving circuitry of the gate drive board 44 . The control voltage V ce signal is also connected with the gate drive board. This V ce signal, or DESAT signal, is measured. When there is a large current passing through, the voltage V ce will increase causing a fault signal to be generated, shutting down the IGBT.
Due to hardware constraints, only one output signal is available for controlling both IGBTs in a single phase. The gate drive circuitry of the gate drive board 44 constructs the two control signals based upon the output control signal from the microprocessor 36 . Therefore, if a short transistor ON time is required, both IGBTs of a phase will be turned ON within the one switching period. Typically, when an inverter 12 fails or generates a false fault signal (i.e., when there is no real fault), only one or, at most, two IGBTs have failed. Accordingly, the same principle as taught above can be used for detecting the failed IGBT(s). Following are three situations that further exemplify this.
Fault Signal Occurs at One Phase
Consider the example of a fault at the first phase upper IGBT A+. The motor 62 has indicated a fault in the A phase, but it is unknown whether the fault is with the first phase upper IGBT A+ transistor or with the first phase lower IGBT A−. Accordingly, the microprocessor 36 executes the following steps to determine where the fault occurred.
The second phase IGBTs B+, B− are first turned ON by the microprocessor 36 , the upper IGBT B+ followed by the lower IGBT B−. No fault should be indicated in the B phase. The microprocessor 36 confirms that the duty cycle is small enough that no high current is flowing through the IGBTs. If the phase A current is equal to the input current I m and the negative of the phase B current, then it may be concluded that first phase lower IGBT A− has shorted. If the phase A current is equal to the phase B current and both are equal to zero, then it may be concluded that there is no short, i.e., first phase lower IGBT A− is not faulty, and either the first phase upper IGBT A+ is open or not faulty.
In order to determine whether first phase upper IGBT A+ is open or not faulty, the microprocessor 36 turns ON first phase upper IGBT A+ and second phase lower IGBT B−, followed by first phase lower IGBT A− and second phase upper IGBT B+. If the phase A current is equal to the input current I m and the negative of the phase B current, then no fault will be generated and it may be concluded that both first phase IGBTs A+, A− are not faulty. However, if the phase A current is equal to the phase B current and both are equal to zero, then a fault will be generated for the A phase, indicating that first phase upper IGBT A+ is open. Table 6 summarizes the above steps.
TABLE 6 Command ON Current Feedback Fault Conclusion B+, then B− I a = −I b = I m or None A− shorted or I a = I b = 0 A− OK; either A+ open or A+ OK A+, B−; then I a = −I b = I m or None A+ and A− are OK A−, B+ I a = I b = 0 A+ or A+ is open
Fault Signal Occurs at Two Phases
Consider the example of a fault at both the first and third phase upper IGBTs A+, C+, respectively. In this example, the motor 62 has indicated a fault in both the A and C phases, but it is unknown where the fault has occurred in each phase. In order to determine which IGBT within each phase is faulty, the microprocessor 36 executes the following.
Initially the microprocessor 36 turns ON the B phase IGBTs B+, B−, the upper IGBT B+ followed by the lower IGBT B−, making certain that the duty cycle is small enough so that no high current is flowing through the IGBTs. With fault signals from both the A and C phases, one of three results should occur upon turning ON the B phase. If the phase A current is equal to the input current I m and the negative of the phase B current, then no fault will be shown indicating that no fault has occurred within the B phase. It may be concluded that first phase lower IGBT A− has shorted, and that the third phase lower IGBT C− may not be faulty.
If the phase B current is equal to twice the negative of the phase A current, then no fault has occurred within the B phase and it may be concluded that the first and third phase lower IGBTs A−, C−, respectively, have shorted. If the phase A current is equal to the phase B current and both are equal to zero, then no fault has occurred within the B phase and it may be concluded that either the first and the second upper IGBTs A+, C+, respectively, are open or are not faulty.
In the instance that no current feedback is provided, i.e., the phase A current is equal to the phase B current and both are equal to zero, the microprocessor 36 performs two further steps to determine whether the first and/or the second upper IGBTs A+, C+, respectively, are open or whether a false fault signal occurred. The microprocessor 36 first turns ON the first phase upper IGBT A+ and the second phase lower IGBT B−, followed by the first phase lower IGBT and the second phase upper IGBT in order to determine whether the first phase upper IGBT A+ is open or not. If the phase A current is equal to the feedback current I m and is the same as the negative of the phase B current, and no fault has occurred within the A phase, then it may be concluded that the first phase IGBTs A+, A− are not faulty. If the phase A current is equal to the phase B current and both are equal to zero, then a fault has occurred within the A phase and it may be concluded that first phase upper IGBT A+ is open.
In order to determine whether the third phase upper IGBT C+ is open or not, the microprocessor 36 turns ON the third phase upper IGBT C+ and the second phase lower IGBT B−, followed by the third phase lower IGBT C− and the second phase upper IGBT B+. If the phase B current is equal to the input current I m , then no fault has occurred within the C phase and it may be concluded that third phase IGBTs C+ and Care not faulty. If the phase A current is equal to the phase B current and both are equal to zero, then a fault has occurred within the C phase and it may be concluded that third phase upper IGBT C+ is open.
Table 7 summarizes the above, given the condition that the first and second phase upper IGBTs A+, C+, respectively, are identified as faulted in the first test.
TABLE 7 Command ON Current Feedback Fault Conclusion B+, then B− I b = −I a = I m or None A− shorted; C− may be OK I b = −2I a or None Both A− and C− are shorted I b = I m , I a = 0 or None C− shorted, A+ open, A− I a = I b = 0 None may be OK A+ and C+ open; or A+ and C+ OK A+, B−; then I a = −I b = I m or None A+ and A− are OK A−, B+ I a = I b = 0 A+ A+ is open C+, B−; then I b = I m or None C+ and C− are OK C−, B+ I a = I b = 0 C+ C+ is open
Fault Signal Occurs at all Three Phases
In such a situation, no test is needed as all power modules will be seen as faulty devices.
While there has been disclosed effective and efficient embodiments of the invention using specific terms, it should be well understood that the invention is not limited to such embodiments as there might be changes made in the arrangement, disposition, and form of the parts without departing from the principle of the present invention as comprehended within the scope of the accompanying claims.
All of the above U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the Application Data Sheet, are incorporated herein by reference, in their entirety.
From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the appended claims. | A method for diagnosing faults using a load. In the method IGBTs are controlled such that certain currents are expected. If the currents are not as expected, a fault may be diagnosed. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a multi-section Roots vacuum pump of the reverse flow cooling type with internal coolant water passages. The present invention is applicable to a reverse flow cooling type multi-section Roots vacuum pump which is operated at a high compression ratio in the range from atmospheric pressure to 10 -3 Torr at a relatively high temperature.
2. Description of the Related Arts
In general, in a Roots type vacuum pump in which rotor pairs rotating in a housing to draw in and discharge gas have a minute clearance from the housing which accommodates the rotor pairs therein, it is important that the clearance between the rotor and the housing be as small as possible in order to realize a pump having a high performance.
In a prior art multi-section Roots vacuum pump driven at a high compression ratio, the temperature will rise relatively high due to the compression heat during operation, and a jacket is arranged directly around the housing which accommodates the rotor pairs therein, to protect the pump from superheating by coolant water running through the jacket for cooling the pump by the radiation of compression heat to the open air. However, since the housing is directly cooled by coolant water, the temperature of the housing in the operating state of the pump becomes significantly low in contrast to the temperature of the rotor pairs inside the housing, thus the clearance between the housing and the rotor pairs is reduced because the amount of thermal expansion of the housing becomes smaller than the amount of thermal expansion of the rotor pairs, and there is a possibility of a contact between the housing and the rotor. To prevent such contact from occurring, the clearance between the housing and the rotor pairs should be preset larger than preferred. This situation is an obstacle to the realization of a pump having a high performance by minimizing the amount of gas leakage from the clearance mentioned above.
Further, as disclosed, in another prior art reverse flow cooling type multi-section Roots vacuum pump, the pump includes a connection pipe provided to connect the outlet passage of a specific pump section with the inlet passage of the following pump section, a cooler incorporated to the connection pipe, and a reverse flow pipe branched off from the connection pipe at the downstream side of the cooler and arranged to lead the reverse flow cooling gas to the preceding pump section. Reference can be made to Japanese Unexamined Patent Publication (Kokai) No. 59-115489, and Japanese Unexamined Patent Publication (Kokai) No. 63-154884.
In the reverse flow cooling type multi-section Roots vacuum pump, a plurality of external coolers is provided for cooling gas running through the connection pipe to protect the pump from superheating by radiating compression heat produced at each pump section. Further, an external piping arranged outside the pump consists of connection pipes for connecting the outlet of each pump section and the inlet of the following pump section, and reverse flow pipes branched off from the connection pipes for leading reverse flow of coolant gas to the preceding side pump section. Therefore, this relatively complicated structure of the external piping arrangement is not advantageous from the viewpoints of compactness of the pump and manufacturing cost of both the external cooler and the external piping. Accordingly, a realization of a small sized pump having a high operation performance has been strongly desired.
SUMMARY OF THE INVENTION
An object of the present invention is to improve the performance of a reverse flow cooling type multi-section Roots vacuum pump by minimizing the amount of gas leakage through the clearance between the housing and the rotor pairs, in which an appropriate reverse flow cooling is carried out to remove the compression heat of gas, and at the same time, to cool the pump to a temperature low enough to protect the pump from overheating, without using a special external cooler, and the temperature gradient between the housing and the rotor pairs located in the housing is kept to a minimum while the pump is running, and the difference between the amounts of thermal expansion of the housing and the rotors is reduced to a minimum, and thus the clearance between the housing and the rotors can be set at a practically minimal value, resulting in a minimal amount of gas leakage through the clearance, and accordingly to attain the high performance of a much improved reverse flow cooling type multi-section Roots vacuum pump.
Another object of the present invention is to realize a miniaturization of the pump and a significant reduction of the cost for manufacturing the pump, in which a cooler installed outside the pump, connection pipes for connecting the outlet of each pump section and the inlet of the following pump section arranged as a part of the external piping, and reverse flow pipes branched from the connection pipes to lead reverse flow cooling gas to the preceding side pump section are eliminated, thus eliminating the cost for manufacturing the external coolers and the piping.
In accordance with the present invention, there is provided a multi-section Roots vacuum pump having a plurality of pump sections each having rotors fixed to two common shafts, the pump including a housing in each of the pump sections having an inlet and an outlet for a gas to be pumped and enclosing the rotors, peripheral gas passages arranged around the housing, peripheral coolant water passages arranged around the peripheral gas passages in which the gas flowing through the inlet into the housing and delivered through the outlet is supplied to the peripheral passages to be cooled there, and at least a portion of the cooled gas is returned into the housing, and the remaining portions of the gas which are not returned into the housing in the pump sections except for the last pump section are supplied to the inlet of the next pump section through the peripheral gas passage.
The operation of the vacuum pump according to the present invention will be described below.
The gas drawn in through the inlet of each pump section to the housing is transmitted by the rotation of the rotors. In this case, gas is compressed in the housing at a temperature having only a minimal rise due to the effect of reverse flow cooling gas which passes through the peripheral gas passage and flows into the housing through the inlet for reverse flow cooling gas, and then the compressed gas is discharged to the peripheral gas passage through the outlet. The discharged gas flows through the peripheral gas passage while radiating heat to the outside wall of the peripheral gas passage which is sufficiently cooled by coolant water circulated in the coolant water passage, and maintaining the housing at an appropriate warm temperature. The discharged gas is then divided into two portions at the inlet for reverse flow cooling gas: one portion is for reverse flow cooling gas which returns into the housing, and another portion is for intake gas which is delivered into the next pump section. The intake gas continuously flows through the peripheral gas passage while radiating heat to the outside wall of the peripheral gas passage which is sufficiently cooled by coolant water circulating in the coolant water passage, and also maintaining the housing at an appropriate temperature, to the inlet of the next pump section.
In the reverse flow cooling type multi-section Roots vacuum pump according to the present invention, a sufficient flow of the reverse flow coolant gas is secured due to the pressure difference between the suction pressure and the discharge pressure of the pump sections. A circulation of the reverse flow cooling gas successively flowing through the inlet, inside of the housing, the outlet, and the peripheral gas passage, forms a cycle for alternating heat built-up due to the compression in the housing and heat radiation carried out in the peripheral gas passage so that compression heat produced in the housing is always removed to the outside of the housing while the housing is kept at an appropriate warm temperature, and thus the difference in temperature of the housing and the temperature of the rotors located in the housing is maintained at a minimum.
On the other hand, gas drawn through the inlet of the following pump section radiates heat to the outside wall of the peripheral gas passage when such gas flows through the peripheral gas passage located between the outside wall of the passage and the housing, and at the same time gas protects the housing from being directly cooled by coolant water so as to keep the housing at an appropriate warm temperature, and thus the difference of temperature of the rotors located in the housing and the temperature of the housing is maintained at a minimum, and gas is delivered to the inlet of the next pump section. The same operation is successively performed at each pump section.
BRIEF DESCRIPTION OF THE DRAWING
In the drawings,
FIG. 1 shows an example of a prior art Roots vacuum pump;
FIG. 2 shows an example of a prior art reverse flow cooling type Roots vacuum pump;
FIG. 3 shows a reverse flow cooling type three-section Roots vacuum pump according to an embodiment of the present invention;
FIG. 4 is a cross-sectional view of the pump taken along the plane represented by the line IV--IV in FIG. 3; and
FIGS. 5 to 7 are cross-sectional views taken along the planes represented by V--V, VI--VI, and VII--VII in FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Before describing the preferred embodiments of the present invention, a prior art Roots vacuum and a prior art reverse flow cooling type multi-section Roots vacuum pump are described with reference to FIGS. 1 and 2.
In particular, in the multi-section Roots vacuum pump shown in FIG. 1, driven at a high compression ratio, wherein the temperature will rise relatively high due to the compression heat during the operation, a jacket 103A, 103B for coolant water is provided at the peripheral portion of the housing 101 having rotor pairs 102 therein in order to radiate the compression heat to the open air, and the pump is cooled by coolant water W103 running through the jacket 103A, 103B.
Further, in general, a reverse flow cooling type multi-section Roots vacuum pump has been disclosed, in which the pump includes a connection pipe provided to connect the outlet passage of a specific pump section with the inlet passage of the following pump section, a cooler incorporated to the connection pipe, and a reverse flow pipe branched off from the connection pipe at the downstream side of the cooler and arranged to lead the reverse flow cooling gas to the preceding pump section.
In the 3-section Roots vacuum pump shown in FIG. 2, an outlet passage 214 of the first pump section 201 is connected to an inlet passage 243 of the second pump section 204 by connection pipes 231, 232, and 233, a cooler 236 is incorporated between connection pipes 231 and 232, and also reverse flow pipes 234 and 235 are branched off from the connection pipe 232 and are provided to lead reverse flow cooling gas to the housing of the first pump section 201. In the same manner, an outlet passage 244 of the second pump section 204 is connected to an inlet passage 273 of the third pump section 207 by the connection pipes 261, 262, and 263, a cooler 266 is incorporated between the connection pipes 261 and 262, and the reverse flow pipes 264 and 265 are branched off from the connection pipe 262 and are provided to lead reverse flow cooling gas to the housing of the second pump section 204. Likewise, the outlet pipes 281 and 282 are connected to the outlet passage 274 of the third pump section 207, with a cooler 285 incorporated between the outlet pipes 281 and 282, and the reverse flow pipes 283 and 284 are provided in a bifurcated manner from the outlet pipe 282 to the housing of the third pump section 207.
FIGS. 3 to 7 show a reverse flow cooling type 3-section Roots vacuum pump according to an embodiment of the present invention. FIG. 4 shows a cross-sectional view of the pump taken along the plane represented by IV--IV in FIG. 3. FIGS. 5 to 7 show the cross-sectional views taken along the plane represented by V--V, VI--VI, and VII--VII.
Referring to FIG. 3, the first pump section 1 and the second pump section 2 are separated by an intersection wall 4, and the second pump section 2 and the third pump section 3 are separated by an inter-section wall 5. As shown in FIG. 4, the first shaft 71 and the second shaft 72, supported by a bearing mechanism 74, pass through a specific pump section and are made to rotate in opposite directions by a timing gear mechanism 73. The first shaft 71 passes through a shaft sealing mechanism 75 and can be driven by an electric motor.
In FIGS. 3 and 5, the first pump section 1 includes a housing 11 having an inlet 13 and an outlet 14, and rotors 12A and 12B supported by a pair of shafts 71 and 72. A peripheral gas passage 16A, 16B is arranged around the housing 11, and the passage runs through an outlet 14 and inlets 15A, 15B which lead reverse flow cooling gas into the housing 11, and is bound for the next second pump section. A coolant water passage 9 is arranged around the peripheral gas passage 16A, 16B.
In FIGS. 3 and 6, the second pump section 2 includes a housing 21 having an inlet 23 and an outlet 24, and rotors 22A and 22B supported by a pair of shafts 71 and 72. Peripheral gas passages 16A, 16B and 26A, 26B are arranged around the housing 21, and the passage 16A, 16B runs from the previous first section to the inlet 23, and the passage 26A, 26B runs through the outlet 24 and inlets 25A, 25B which lead reverse flow cooling gas into the housing 21, and is bound for the next third pump section. A coolant water passage 9 is arranged around the peripheral gas passages 16A, 16B, 26A, 26B.
In FIGS. 3 and 7, the third pump section 3 includes a housing having an inlet 33 and an outlet 34, and rotors 32A and 32B supported by a pair of shafts 71 and 72. Peripheral gas passages 26A, 26B and 36A, 36B are arranged around the housing 31, and the passage 26A, 26B runs from the previous second pump section to the inlet 33, and the passage 36A, 36B runs through the outlet 34 and the inlet 35A, 35B which leads reverse flow cooling gas into the housing 31, and a coolant water passage 9 is arranged around the peripheral gas passages 26A, 26B, 36A, 36B. The coolant water inlet 91 is connected to the coolant water outlet 92 by the coolant water passage 9 arranged around the peripheral gas passages.
The operation of the pump is now described below with reference to FIGS. 3 to 7.
As shown in FIGS. 3 and 5, in the first pump section 1, intake gas G81 of the pump is drawn from the inlet 13 of the first pump section through the inlet 81 of the pump as intake gas G13, and transmitted by the rotation of the rotors 12A and 12B. In this case, gas is compressed in a reverse flow manner in the housing with only a minimal rise in temperature due to the effect of reverse flow cooling gas G15 which passes through the peripheral gas passage 16A, 16B and flows into the housing through the inlets 15A, 15B for reverse flow cooling gas, and then the compressed gas is discharged to the peripheral gas passage 16A, 16B through the outlet 14 as the discharged gas G14. The discharged gas G14 flows through the peripheral gas passage while radiating heat to the outside wall of the peripheral gas passage 16A, 16B which is effectively cooled by coolant water W9 circulated in the coolant water passage 9, and maintaining the housing 11 at an appropriate warm temperature. The discharged gas G14 is then divided into two portions at the inlet 15A, 15B for reverse flow cooling gas: one portion is reverse flow cooling gas G15 which returns into the housing 11, and another portion is intake gas G23 which is delivered through the inlet 23 of the second pump section.
The intake gas G23 flows through the peripheral gas passage 16A, 16B while radiating heat to the outside wall of the peripheral gas passage 16A, 16B which is effectively cooled by coolant water W9 circulated in the coolant water passage 9, and also maintaining the housing 11 and the housing 21 at an appropriate warm temperature, to the inlet 23 of the second pump section.
As shown in FIGS. 3 and 6, in the second pump section, the intake gas G23 is drawn through the inlet 23 and transmitted by the rotation of the rotors 22A and 22B. In this case, gas is compressed in a reverse flow manner in the housing 21 with only a minimal rise in temperature due to the effect of reverse flow cooling gas G25 which passes through the peripheral gas passage 26A, 26B and flows into the housing 21 through the inlets 25A, 25B for reverse flow cooling gas, and then the compressed gas G24 is delivered to the peripheral gas passage 26A, 26B through the outlet 24 as the discharged gas G24. The discharged gas G24 flows through the peripheral gas passage while radiating heat to the outside wall of the peripheral gas passage 26A, 26B which is effectively cooled by coolant water W9 circulated in the coolant water passage 9, and maintaining the housing 21 at an appropriate warm temperature. The discharged gas G24 is then divided into the reverse flow cooling gas G25 which returns into the housing 21, and the intake gas G33 which is delivered through the inlet 33 of the third pump section. The intake gas G33 flows through the peripheral gas passage 26A, 26B while radiating heat to the outside wall of the peripheral gas passage 26A, 26B which is effectively cooled by coolant water W9 circulated in the coolant water passage 9, and also maintaining the housings 21 and 31 at an appropriate warm temperature, to the inlet 33 of the third pump section.
As shown in FIGS. 3 and 7, in the third pump section, the intake gas G33 is drawn through the inlet 33 and transmitted by the rotation of the rotors 32A and 32B. In this case, gas is compressed in a reverse flow manner in the housing 31 with only a minimal rise in temperature due to the effect of reverse flow cooling gas G35 which passes through the peripheral gas passage 36A, 36B and flows into the housing 31 through the inlets 35A and 35B for reverse flow cooling gas, and then the compressed gas G34 is delivered to the peripheral gas passage 36A, 36B through the outlet 34 as the discharged gas G34. The discharged gas G34 flows through the peripheral gas passage while radiating heat to the outside wall of the peripheral gas passage 36A, 36B which is effectively cooled by coolant water W9 circulated in the coolant water passage 9, and maintaining the housing 31 at an appropriate warm temperature. Then the discharged gas G34 is divided at the outlet 34 into the reverse flow cooling gas G35 and the discharged gas G82 of the pump which is discharged out of the pump through the outlet 82 of the pump. The reverse flow cooling gas G35 flows through the peripheral gas passage 36A, 36B while radiating heat to the outside wall of the peripheral gas passage 36A, 36B which is effectively cooled by coolant water W9 circulated in the coolant water passage 9, and also maintaining the housing 31 at an appropriate warm temperature, into the housing 31 again through the inlets 35A and 35B for the reverse flow cooling gas.
As described above, in the reverse flow cooling type multi-section Roots vacuum pump according to the present invention, gas drawn through the inlet of each pump section to the inside of the housing is transmitted by the rotation of the rotors. In this case, gas is compressed in a reverse flow manner in the housing with only a minimal rise in temperature due to the effect of reverse flow cooling gas which passes through the peripheral gas passage and flows into the housing through the inlet for reverse flow cooling gas, and then the compressed gas is discharged to the peripheral gas passage through the outlet as the discharged gas. The discharged gas flows through the peripheral gas passage while radiating heat to the outside wall of the peripheral gas passage which is effectively cooled by coolant water circulated in the coolant water passage, and maintaining the housing at an appropriate warm temperature. Then the discharged gas is divided at the inlet of reverse flow cooling gas into the reverse flow cooling gas which returns into the housing and the intake gas which flows to the next pump section.
The intake gas flows through the peripheral gas passage which is effectively cooled by coolant water circulated in the coolant water passage, and maintaining the housing at an appropriate warm temperature, to the inlet of the next pump section. The operation described above is performed successively in each pump section.
A detailed description was given of a pump having three sections, but the reverse flow cooling type multi-section Roots vacuum pump according to the present invention may be constituted, not limited to three, but by 4 or more sections. Further, in the case of 4 or more sections, the first section should have the same constitution as shown in FIG. 5, and the final section should have the same constitution as shown in FIG. 7. | A multi-section Roots vacuum pump of the reverse-flow cooling type having a plurality of pump sections each having rotors fixed to two common shafts. The pump includes a housing in each of the pump sections having an inlet and an outlet for a gas to be pumped and enclosing the rotors, a peripheral gas passages arranged around the housing, and a peripheral coolant water passages arraged around the peripheral gas passages. The gas flowing through the inlet into the housing and delivered through the outlet is supplied to the peripheral gas passages to be cooled there, and at least a portion of the cooled gas is returned into the housing. The remaining portions of the gas which are not returned into the housing in the pump sections except for the last pump section are supplied to the inlet of the next pump section through the peripheral gas passage. | 5 |
CROSS REFERENCE TO RELATED DOCUMENT
This application is the U.S. national phase of PCT/EP00/05333, filed Jun. 19, 2000, which claims benefit German Application No. 199 26 900.9, filed Jun. 12, 1999.
FIELD OF THE INVENTION
The present invention relates to a process for producing a flat commutator and a commutator produced using this process. These commutators can be used especially in electric motors to drive a fuel pump which pumps fuels obtained from renewable raw materials.
BACKGROUND OF THE INVENTION
In the production process disclosed in WO 97/03486, a metallic, pot-shaped carrier body forms segment support parts and is shaped from a copper plate. The copper plate has been segmented beforehand by grooves and is extruded with a hub formed from an electrically insulating molding compound. The carrier body, on its side forming the contact surface for the carbon-containing annular disk, is then removed to such an extent that the segment support parts are electrically separated from one another by the grooves filled with the molding compound. Then, the annular disk is applied and subsequently, according to the segmentation of the carrier body, divided into segments, the separating slots projecting into the area of the grooves which is filled with the molding compound.
Since in using the known process the carrier body is segmented before the annular disk is applied, the process requires additional steps to make grooves in the carrier body and remove the carrier body into the area of the grooves. Moreover, the dividing must take place precisely in the area of the grooves to ensure resistance to a reactive environment.
DE 36 25 959 C2 shows a drum commutator and a process for its production, in which either on a cylinder produced by curling a base plate of a parent or base metal, copper, or on a hollow cylindrical tube piece, protective parts are applied by plating with a copper-nickel or silver-nickel alloy, at least on the surfaces which come into contact with the brushes. Furthermore, the parent metal of the commutator segments is provided on its surface with tin plating by electrolytic plating (column 13, lines 16 and 17) to prevent the copper body from being exposed to a fuel, such as gasohol, to prevent decomposition of the fuel. A mixture of unleaded gasoline and 10 to 15% ethyl alcohol is defined as gasohol in the patent.
DE 44 35 884 C2 shows a commutator for use in fuel pumps, with bars located around the periphery of the commutator and in sliding contact with a brush arrangement, of a wear-resistant copper-magnesium alloy. The magnesium portion of the bars is between 0.05 and 2.00 percent by mass.
In contrast to this invention, JP 58 075440 A does not disclose a flat commutator, but a drum commutator. Furthermore, this document is directed at the prevention of fuel oxidation (“to prevent the oxidation of gasoline”). To this end, a plate (sheet 8) resistant to fuel is connected with the not yet burnished copper plate forming the carrier body.
FR2 330 169 A also discloses a drum commutator (cf. FIGS. 1 to 3 ) and hence a nongeneric subject. The layer with reference numbers 11 a and 11 b depicted in FIG. 5 of this document is a layer produced by oxidation.
U.S. Pat. No. 5,175,463 discloses a flat commutator with segment support parts separated by radial slots. A compound with low melting point of different metals is used in the connection of the carbon-containing annular disk with the metallic segment support parts.
DE 29 03 029 C2 represents the proximate state of the art and discloses among others a process for producing a flat commutator in which a copper plate with a disk-shaped sheet of silver or silver alloy invulnerable to gasoline is applied. The copper plate is sloted at regular intervals. The denuded copper parts of the commutator bars are covered with a galvanically applied electroplated layer of silver or tin.
SUMMARY OF THE INVENTION
Objects of the present invention are to provide a process for producing a flat commutator which eliminates the disadvantages of the prior art, which in particular is more economical, and which still ensures sufficient resistance of the finished commutator in a reactive environment. In addition, the coating will be relatively thick, especially in undercuts and/or grooves which may be present as a result of dividing the carrier body, and will be as uniform as possible. In any case, it will be possible to apply the coating to form a cohesive layer. The present invention permits use of electric motors for driving a pump for fuels obtained from renewable raw materials.
The surfaces of the metallic segment support parts, which are exposed by dividing, are covered with a coating which is resistant to a reactive or aggressive environment. The resistance relates especially to protection of the carrier body and/or the segment support parts and the connection to the annular disk against breakdown, relates to electrical conductivity with respect to the contact resistance between the commutator contact surface formed by the annular disk and the pertinent segment support part or between it and the commutator brush, and relates to the adhesion of the coating on the metallic segment support part. Also, insulation must be ensured between the segment support parts. The segment support parts preferably and essentially consist of copper and have high electrical conductivity and ductility. The carrier body is produced, for example, from a punched-out copper plate which is then formed into a pot and is extruded with a molding mass forming the hub. The carbon-containing annular disk in particular is resistant in a reactive environment, for example in a hydrocarbon-containing liquid. The annular disk and/or the carrier body is/are divided preferably by abrasive cutting, sawing or laser working.
The process steps of forming the grooves and removing the carrier body are eliminated by the carrier body being divided into segment support parts after joining to the annular disk.
Production is further simplified by the annular disk and the carrier body being divided in one step. Alternatively, it is possible in a first step to divide the carrier body, provided with the hub and formed into a pot, into segment support parts by first slots. Then, the annular disk is applied. Finally, the annular disk is divided by two slots into annular segments, the second slots preferably being smaller than the first slots and being located within the first slots. The coating of the surfaces of the segment support parts exposed by dividing the carrier body can be done before or after the application of the annular disk. To the extent the coating takes place before applying the annular disk, the applied layer can be used at the same time as a joining layer to the annular disk.
Because coating takes place by deposition, the metallic carrier body can be coated with any material. Both chemical and also physical and mixed deposition processes can be used, for example deposition from the gaseous phase (Chemical Vapor Deposition, CVD), optionally plasma- or laser-supported, cathode beam atomization (sputtering), vapor deposition, etc. Vossen, Kern (publisher): Thin Film Processes I and II, 1991, surveys possible deposition methods.
Because deposition takes place from a solution or suspension, a large number of commutator elements can be coated in one step, and thus, economically and with good coverage and layer quality. The layer material is in a preferably an ionic solution or suspension and can be deposited electrolytically (galvanically) or currentlessly on the segment support parts.
Because deposition takes place currentlessly from the solution or suspension, i.e. without applying an external voltage, coverage of the elements even on inaccessible locations, for example in the dividing slots formed by division, is good. The temperature and concentration of the solution or suspension are chosen such that complete coverage with sufficient thickness is ensured in as short a time as possible.
Because coating takes place selectively only on surfaces of the segment support parts, the annular disk and especially the hub are not coated, preventing the detachment of the layer from these locations, for example due to poor adhesion, and the associated problems in later operation of the commutator. The selectivity of deposition can be adjusted by the corresponding choice of the process parameters during deposition, for example the deposition temperature, concentration of the solution or suspension, deposition duration, etc., depending on the material to be deposited and/or the carrier body to be coated.
Because coating takes place with tin, silver or chromium, good coverage and adhesion as well as sufficient resistance especially to fuels obtained from renewable raw materials is also ensured with economical materials. Tin in particular offers good contact properties, and is also advantageous for joining the winding ends to the segment support parts.
Because the layer thickness is between 0.1 and 10 μm, especially between 1 and 3 μm, reliable coating and good adhesion as well as sufficient resistance are guaranteed. These layer thicknesses arise especially in currentless deposition from a solution or suspension after comparatively short deposition intervals and ensure pore-free coverage of the carrier body.
In a commutator produced using the process of the present invention, the hub in the area of the division, especially on the side of the segment support parts facing away from the commutator contact surface and/or the surfaces adjoining the surfaces exposed by the division of the carrier body, also adjoins the carrier body. Thus, reliable coverage of the metallic carrier body is also ensured in this area. This coverage prevents scouring of the carrier body and the segment support parts in a reactive atmosphere.
Because the hub forms a complete cover of the cylindrical boundary surface of the central hole of the carrier body, the cylindrical inside of the carrier body is also covered relative to the reactive atmosphere. Also, the resistance of the commutator is further increased.
Because the coating is resistant to the fuel to be pumped, commutators produced using the process of the present invention can also be used in fuel pumps. Especially, tin as the coating material has proven resistant to fuels obtained from renewable raw materials, for example alcohol-based fuels or diesel fuels obtained from rapeseed oil.
Other objects, advantages and salient features of the present invention will become apparent from the following detailed description, which, taken in conjunction with the annexed drawings, discloses preferred embodiments of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring to the drawings which form a part of this disclosure:
FIG. 1 is a block diagram of a production process according to a first embodiment of the present invention;
FIG. 2 is a block diagram of a production process according to a second embodiment of the present invention;
FIG. 3 is a bottom plan view of a segmented commutator according to the present invention;
FIG. 4 is a side elevational view in section taken along line IV—IV through the commutator of FIG. 3;
FIG. 5 is a partial side elevational view of the commutator of FIG. 3 taken from line V—V; and
FIG. 6 is a partial side elevational view of a commutator produced using the production process of FIG. 2, which view corresponds to that of FIG. 5 .
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a first embodiment of the production process of the present invention. A copper plate is punched out of a copper sheet 50 and a pot-shaped carrier body 51 is then formed from it. The bottom surface of the pot forms the contact surface for the annular disk to be applied. The bottom surface is not presegmented. However, the cylindrical jacket surface of the pot has already been segmented by punching-out. Likewise, hook elements for attaching the coil windings and anchor elements which fit into the hub are made by punching-out. The hub is formed by extrusion 52 of the pot-shaped carrier body by means of an electrically insulating molding compound which is temperature-resistant according to the respective requirements. Optionally the hub and the contact surface of the carrier body can be worked 53 , with respect to the hub. Especially, precision machining of the hub hole which holds the shaft of the rotor is carried out. With respect to the contact surface of the carrier body, planarizing and optionally pretreatment take place for subsequent application 54 of the annular disk.
The annular disk preferably contains carbon or consists completely of sintered carbon which has the morphology and grain composition necessary with respect to electrical conductivity, abrasion resistance and resistance. The inside diameter of the annular disk is preferably larger than the diameter of the hole in the hub. Dividing 55 of the annular disk and of the carrier body into segments is done, preferably by a single machining process, for example by abrasive cutting or sawing. The cut slot extends through the annular disk and the bottom of the pot-shaped carrier body, and into the molding compound which follows the carrier body and adjoins it. Division yields the separation of the segments of the commutator in electrical terms, i.e., the electrically conductive connections between the segments are cut through. As before, the segments are mechanically joined securely to one another via the molded-on hub.
Coating 56 of the carrier body takes place with a material resistant to a reactive environment, for example with tin, silver, or chromium in a layer thickness of 0.1 to 10 μm, preferably 1 to 3 μm. Here preferably all exposed surfaces of the carrier body are coated, especially the surfaces of the metallic segment support parts exposed by the division of the carrier body. Coating takes place preferably by currentless deposition from a solution or suspension, i.e., without a voltage being applied from the outside between the carrier body to be coated and the solution or suspension. Before actual coating, chemical and/or mechanical cleaning takes place, for example in an ultrasonic bath in order to remove impurities and residues on the surface of the segment support parts and to prepare the surface for coating. The essentially copper-containing segment support parts can then be pretreated in a reducing atmosphere. The actual coating takes place preferably at a temperature which has been elevated compared to the ambient temperature. In the corresponding solutions or suspensions for example with deposition intervals of less than one hour, layer thicknesses between 1 and 3 μm can be achieved. A plurality of commutator elements can be coated in one process. After coating the commutators are rinsed and dried.
FIG. 2 shows a second embodiment of the production process of the present invention. After extrusion 152 of the carrier body with the formation of a hub, the carrier body is divided into segment support parts 155 A. Then, as described above, coating 156 of the segment support parts is carried out. Alternatively, coating can also take place galvanically or electrolytically, for example with silver in a layer thickness of roughly 5 μm. The annular disk is then applied 154 and then divided into annular segments 155 B. The cut slots in the annular disk are preferably narrower or equally wide compared to the cut slots in the carrier body, in any case located within the annular disk. Alternatively or in addition to coating 156 of the segment support parts immediately after division 155 A of the carrier body, the segment support parts can also be coated as described above only after dividing 155 B the annular disk into annular segments.
FIG. 3 shows a plan view of the segmented annular disk of a commutator 1 produced using the process of the present invention. FIG. 4 shows section IV—IV through the commutator 1 of FIG. 3 .
The annular disk is divided into eight annular segments 2 . Likewise, the carrier body is divided into eight segment support parts 4 . A hub 6 formed by extrusion is molded onto the segment support parts 4 of the carrier body and forms a central hole 6 a for holding the shaft (not shown) of the rotor of a motor or generator. The segment support parts 4 on their outer peripheral surface 4 a have a hook 4 b for electrical connection of a rotor winding. In addition, the segment support parts 4 each have at least one anchor element 4 c for fixed connection to the hub 6 . The outer peripheral surface 4 a corresponds in its diameter to the outer peripheral surface 2 a of the annular segments 2 formed from the annular disk. The diameter of the inner peripheral surface 2 d of the annular segments 2 corresponds essentially to the inner peripheral surface 4 d of the segment support parts 4 or is slightly larger.
The joining layer and especially the solder layer 10 between the segment support part 4 and the annular segment 2 is, for example, 50 μm thick. When the annular disk and the carrier body are divided, cut slots 12 are formed which project into the area of the hub 6 . The surfaces 14 of the essentially copper segment support parts 4 which are exposed by dividing the carrier body are covered with a coating which is resistant to a reactive environment. Preferably, the outer peripheral surface 4 a and the hooks 4 b of the segment support parts 4 are also coated. This enables better joining of the segment support parts to the rotor windings, especially easier contact bonding of the segment support parts over the outer peripheral surface 4 a when welding the winding ends to the hooks 4 b . Conversely, preferably neither the flat surfaces 2 b which are used as the brush contact faces nor the surfaces 2 c of the annular disk which have been exposed by dividing are coated. The joining layer 10 between the segment support parts 4 and the annular segments 2 is thus coated both on its surfaces 10 b which are exposed by dividing and also on its inner and outer peripheral surface 10 a.
The cut slot shown enlarged in FIG. 5 compared to FIG. 4 was produced by abrasive grinding or sawing of the combination of the hub 6 , the carrier body which forms the segment support parts 4 , and the annular disk which forms the annular segments 2 , in one process. The slot is typically a few tenths of a millimeter wide and a few millimeters deep. In particular, by coating using currentless deposition from a preferably tin-containing solution or suspension, a relatively resistant, thick and dense selective coating of the surfaces 14 of the segment support parts 4 exposed by division and optionally of the joining layer 10 can be achieved.
FIG. 6 shows a view of a commutator produced using the alternative production process from FIG. 2, a view which corresponds to FIG. 5 . The carrier body was initially divided into segment support parts 104 with a first, wider slot 112 a . The annular disk is then applied by means of the joining layer 110 . Then the annular disk is divided into annular segments 102 by a second, narrower slot 112 b aligned with the first slot. The coating (not shown) of the surfaces 114 of the segment support parts 104 exposed by dividing and optionally that of the exposed surface 110 b of the joining layer 110 can take place either before or after application of the annular disk. Alternatively, the joining layer 110 does not end flush with the annular segments 102 , but ends flush with the segment support parts 104 .
While various embodiments have been chosen to illustrate the invention, it will be understood by those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention as defined in the appended claims. | A method for producing a flat commutator includes forming a metallic supporting body with segment supporting parts and forming a hub of an electrically insulating material. The supporting body is connected in an electrically conductive and mechanically fixed manner to an annular disc resistant in a reaction-promoting environment. The supporting body is divided into segment support parts. The annular disc is divided into annular segments. The surfaces of the metallic segment supporting parts which are bare as a result of the division of the supporting body are coated with a coating that is resistant to the environment. The coating is carried out by currentless deposition. The commutator produced according to this method has the hub adjacent to the supporting body in the vicinity of the division. | 8 |
FIELD OF THE INVENTION
[0001] The invention relates to a technology of adaptation rates of multiple data streams transmitted via a multi-line configuration of a telecommunication system.
BACKGROUND OF THE INVENTION
[0002] The related prior art refers to telecommunication systems that comprise a group of communication links (so-called bonded links) used together for transmitting quite heavy data traffic. Bonding of communications links or paths into a higher-bandwidth, logical communications path is widely used, and a problem of bandwidth allocation or rate adaptation between the communication links in such systems is being discussed in the related art.
[0003] Various solutions for policing data traffic are known in the art.
[0004] US published patent application US 2004/0218530 A1 describes a system and a method for transmitting data streams subject to crosstalk. An adjustable parameter, preferably data rate, is adjusted using feedback of performance characteristics (for example signal-to-noise ratio (SNR) and line attenuation) for maximizing total throughput of the data streams. The system comprises a) a plurality of communication links, wherein each communication link has a respective performance characteristic and at least one communication link has an adjustable parameter; (b) a mechanism for measuring the performance characteristics; and, (c) a mechanism for adjusting the mentioned adjustable parameter in response to the mechanism for measuring the performance characteristics. The solution is applicable to inverse multiplex (IMUX) systems, where total throughput is more important than the throughput of any individual data stream.
[0005] When the problem is not achieving the maximal throughput via the plurality of communication lines, but distributing traffic in case of a faulty or a degrading condition of a particular line, solutions may differ from the above-mentioned one.
[0006] An ITU-T standard recommendation G.992.3 suggests a mechanism of rate adaptation to be used in xDSL (Digital Subscriber Line) technologies, which is suitable for so-called DMT (discreet multi tone) technologies. The mechanism is intended for relocating traffic bits originally located in a particular bin of a DSL line (where a bin is a spectral slice typically of 4.3125 khz), to other bins of this same line, say, due to Signal to Noise Ratio degradation in the particular bin of the line. In general, the mechanism comprises procedures for OLR (On Line Reconfiguration), and in particular—a method of SRA (Seamless Rate Adaptation), and these procedures are defined in G.993.2 chapter 9.4 (management procedures) in subclause 9.4.1.1 “On line reconfiguration command”. The Seamless Rate Adaptation (SRA) mechanism is used to reconfigure the total data rate (in a single line) (ΣLp) by modifying the frame multiplexor control parameters (Lp) and modifications to the bit and fine gain (bi, gi) parameters, wherein bi indicates the number of bits allocated in bin (i) on a specific line, gi indicates the gain applied to bin (i).
[0007] Two additional relevant mechanisms are described in the same standard recommendation G.992.3, one is a DRR (Dynamic Rate Repartitioning) mechanism, and the other as a Bit Swap mechanism.
[0008] It should be emphasized that the OLR mechanism recommended in ITU-T G992.3 is designed and applicable to changing bit allocation between different bins in a single DSL line.
[0009] To the best of the Applicant's knowledge, no adequate technology has been described by now which would be suitable for fine grain re-allocation (redistribution) of traffic information between multiple bonded transmission lines.
OBJECT AND SUMMARY OF THE INVENTION
[0010] It is therefore the object of the present invention to provide a new technique of rate adaptation in a telecommunication system comprising multiple bonded transmission lines, the technique being such to allow fine granularity relocation (redistribution) of traffic load between these multiple transmission lines.
[0011] The above object can be achieved by providing a method for rate adaptation in a telecommunication system comprising a group of bonded transmission links including at least a first link and a second link for carrying together a binary traffic stream, wherein each of said bonded transmission links is adapted to carry binary information allocated in a number of bins; the method comprises transmission of the binary traffic stream via the group of bonded transmission links and performing bit re-allocation (i.e., reallocation with the granularity of a single bit) between different bonded transmission links of said group in case of change of one or more conditions in one or more bins of at least one bonded transmission link in said group.
[0012] Speaking more specifically, each of said bonded links is adapted to carry a sub-stream of binary information in a number of bins, wherein the sub-stream is part of said traffic stream;
[0000] the transmission comprises transmitting a first sub-stream of binary information via the first transmission link, while allocating said first sub-stream in one or more of bins of the first transmission link so that each bit of the first sub-stream is allocated in a specific bin of said first link;
the bit re-allocation is by allocating one or more bits of information, previously allocated in a bin of said first link, into a bin of the second transmission link, thereby adapting rate in one or more of said bonded transmission links to current conditions of said one or more links.
[0013] The mentioned conditions may constitute one or more of the following predetermined conditions selected from a non-exhaustive list comprising: transmission conditions such as Signal to Noise Ratio SNR affecting capacity of the link in one or more specific bandwidth slices (bins), link conditions such as dispersion etc., up to a fault of the link, time factor—for example, expiration of a predetermined time limit, user's instructions/requirements—for example, such as ceasing transmission via the link, reserving one or more bits in one or more bins in the link to be used in case of a fault in other bonded links, etc.
[0014] The method may further comprise an additional step of allocating information previously located in one bin of the first link, into another bin of the same first transmission link.
[0015] In other words, the method allows bits allocation transfer between bins being carried by different bonded transmission links, whenever the conditions change at least in one of the links in the group. Yet in other words, the proposed method comprises shifting bits from one link to another link in the group of multiple bonded links. Since the minimal granularity of the allocation transfer is a single bit, the method enables performing a really seamless and dynamic rate adaptation (redistribution) between different bonded transmission links and their bins.
[0016] Preferably, the bonded links are wire-line transmission links adapted to carry communication traffic according to DMT (Discreet Multi Tone) technology: such as links of DSL, ADSL, ADSL2, ADSL2plus, VDSL1, VDSL2, and the like.
[0017] However, Embodiments of the present invention can be applied not only to bonded different physical links (e.g., xDSL over twisted pairs), but also to “bonded” different channels on the same physical line, or even different channels or frequencies in a wireless communications network.
[0018] The discussed bonded transmission links should be understood as communication links provisioned in the telecommunication system and currently available for transmitting the traffic stream there through by at least partially utilizing their capacity (or bandwidth).
[0019] It should be understood that in a specific link of the group, some bandwidth slices (bins) may be idle—and thus the bandwidth and the capacity of the link is used partially. Idle bins can be reserved for further use.
[0020] It should also be noted that that if some bins in the link are not fully packed with information bits, both the bin and the link capacity are not fully utilized. In the case when a bin is used not fully, its remaining capacity can be reserved (the bin thus becomes partially reserved) and then utilized.
[0021] For carrying the mentioned traffic stream, the bonded transmission links should be currently operable in the same direction of transmission from a transmitting end to a receiving end, thus enabling the bit allocation transfer there-between and further merger of the sub-streams at a receiving end of the bonded links.
[0022] It goes without saying that each of the links may be a bi-directional link, i.e., be capable of transmitting information also in the opposite direction. It is also understood that during a different time period a specific bonded link may be used as a link transmitting traffic in the opposite direction only.
[0023] Moreover, at least part of the bandwidth available on a provisioned bonded link may be selectively used for traffic transmission in one or another direction as required (i.e. bandwidth which, regularly or conventionally, is not used). It is suggested that such bandwidth be used for the proposed bit re-allocation, for example with preliminarily reserving the mentioned “non-conventional” bandwidth.
[0024] The communication system is preferably a DMT system where, on each of the bonded links, the information is separated across the bins being relatively narrow frequency channels (or bit rate channels): for example, 256 downstream or 32 upstream possible bins, with 4.3125 kHz spacing between the adjacent bins. For example, bin 64 is a narrow channel at 276 kHz.
[0025] Another example could be: 2098 bins allocated with the spectrum spacing of 8.625 kHz.
[0026] The change of predetermined conditions in one of the links may, for example, mean that transmission conditions in that link either decrease or improve. It may also mean that the link has just failed, has been switched off by an outside command or—to the opposite—has been provided with additional bandwidth/capacity according to any internal or external reasons.
[0027] Therefore, the operation of shifting bits from the bin(s) of the first link (or more bonded links) to the bin(s) of the second link (or more bonded links) is performed to effectively use bandwidth and capacity of the bonded transmission links.
[0028] In view of the above, said second transmission link may be the link where said conditions have changed in the meaning that its bandwidth/capacity has increased (for example its transmission conditions have improved).
[0029] Alternatively, or in addition, the first transmission link may be the link where said conditions have changed in the meaning that its bandwidth/capacity has decreased (for example, its transmission conditions have deteriorated).
[0030] There may even be a case when one or more conditions change in a transmission link of the group, being neither the first link nor the second link; however, as a result of such change of conditions, the first and the second links may participate in relocation of traffic bits.
[0031] Change in conditions may manifest themselves, for example, by a change in one or more predetermined measured/monitored parameters, for example by expiring a specific time limit detected by a timer, a change of a signal to noise ratio (SNR) in a specific link or in a particular bin of the specific link, etc.
[0032] The method should preferably comprise a step of monitoring, in real time, said predetermined conditions, including the transmission conditions and the link conditions of said multiple bonded transmission links.
[0033] The predetermined transmission conditions and link conditions can be monitored by continuously or periodically measuring said one or more parameters in a number of bins of the bonded links (preferably, in every bin of every one of said links), followed by reporting a value of the one or more parameters, or a change of said one or more parameters in comparison with respective predetermined reference values.
[0034] According to one version of the method, the step of monitoring the conditions of interest should be provided in such a manner as to ensure synchronized reporting concerning every one of said bonded links, and when applicable—concerning at least a number of bins (if not every bin) of said bonded links, to synchronize the allocating step.
[0035] The next step would be to actually change a current specific bit-to-bin relationship by reallocating one or more bits between at least two of the transmission links, based on the above reported information.
[0036] According to another version of the proposed method, it preferably comprises:
preliminarily reserving bandwidth in at least one link among said bonded transmission links, by at least partially reserving one or more selected bins in said at least one link, and, in case of degradation of predetermined conditions in one or more other links of said bonded transmission links, using said at least partially reserved bins for transferring to them allocation of the traffic information from bins of said one or more degraded transmission links.
[0039] It should be kept in mind that at least partially reserving of a bin can be provided: either by not allocating traffic information in a particular bin (fully reserved bin), or by allocating traffic information in the bin using only part of the bin's capacity (partially reserved bin), or by freeing at least partially some selected bin or bins.
[0040] In this second version, the main purpose of the monitoring is to learn whether some predetermined conditions have degraded drastically (say, an alarm of a fiber cut is received). In the absence of such events, the rate adaptation is based on monitoring/reporting conditions in bins of the bonded lines.
[0041] In view of the explanation concerning changes of predetermined conditions, presented in the present description, degradation of such conditions in a bonded link may include failure or degradation of the link, deterioration of its transmission conditions fully or in a number of bins, decrease of its bandwidth due to any internal or external reasons such as switching it off, etc.
[0042] The above-mentioned version of the invention can be further used for protecting traffic information transmitted via one or more of the bonded transmission links, preliminarily agreed to be protected, wherein
said one or more links, where the bandwidth and/or capacity is preliminarily reserved by at least partially reserving one or more bins, constitute protecting links, and wherein in case of degradation of the predetermined conditions in said one or more links to be protected, said at least partially reserved bins are used for transferring to them allocation of the traffic information from said one or more degraded links to be protected, thereby compensating bandwidth and/or capacity lost in said links.
[0045] The reserving can be performed using either a “1:1” protection principle (one protecting link to one protected link) or a “1:n” protection principle (one protecting link to “n” protected links—so called shared protection).
[0046] The proposed method will enable a finer protection granularity than that available in the presently known systems, since the user may allocate resources for protection in a per bit resolution and thus to achieve the really seamless and dynamic rate adaptation.
[0047] The method preferably comprises modifying the mechanism of On Line Reconfiguration (OLR) known for xDSL systems and described in ITU-T G.992.3, and utilizing the OLR mechanism for performing transfer of bit allocation between different links of DMT bonded transmission links.
[0048] In a specific case, the method comprises modifying the Seamless Rate Adaptation (SRA) mechanism.
[0049] Preferably, the method may comprise the following steps for utilizing and modifying the known OLR (say, SRA) algorithm to shift bit allocations between different bonded transmission links:
[0050] providing a common OLR (say, SRA) modified software unit for serving the group of bonded transmission links, and registering in the common modified OLR unit initial bit allocation values and initial said conditions of all the bins of all the links in a common list (in the common list, each bin may have its individual number different from numbers of other bins);
[0051] ensuring updating the modified OLR software unit about changes in said conditions including link conditions, time factor, users instructions, transmission conditions in at least some selected bins of at least some selected links in the group, performing logical re-allocation of bits within said list by the common OLR software unit;
[0052] based on the logical re-allocation, performing real re-allocation of bits between different bonded links.
[0053] The selected bins should be understood as those selected, for any reasons, to be monitored; for example, these bins may be considered critical for bit allocation from the point of conditions' changes, considered most exposed to the condition's changes, etc.
[0054] Of course, it is better to perform the monitoring and updating the modified OLR unit about conditions in all bins of all the links; however, the updating can be performed at least concerning those bins where one or more of the predetermined conditions change essentially in comparison with predetermined reference value(s).
[0055] Another version of the method may comprise providing a modified OLR (say, SRA) software unit per at least two bonded links of the bonded group, wherein the modified OLR unit registers all the bins of said at least two links in a combined list;
[0056] the group is thereby served by a number of the modified OLR software units, wherein the number of the OLR units being smaller than the quantity of the bonded links in the group. In such a manner, the bit-reallocation are performed, for example, between a pair of bonded links which are preliminarily assigned to protect each other
[0057] Alternatively, the method may comprise:
providing a modified OLR software unit per each of said links; providing a centralized control unit CCU for said modified OLR software units; accumulating in said centralized control unit CCU actual information (i.e., updating the CCU) about changes in said conditions (for example: alarms on a link conditions, transmission conditions in a link, timers, users instructions, transmission conditions in bins) and processing the information to obtain a list of at least selected so-called perspective bins of all of said links, where either the predetermined conditions have improved or one or more bit allocations have been reserved, enabling bi-directional communication between said CCU and each of said modified OLR software units, selectively providing said information from the centralized control unit CCU to one or more of said OLR software units; enabling each said modified OLR software unit associated with a particular transmission link to receive from the CCU and process said information about the perspective bins as information about additional (fictitious) bins of said particular transmission link; in case of deciding, by any of said modified OLR software units, to re-allocate one or more bits to said additional bins, informing said centralized control unit CCU for performing the re-allocation operation into real suitable said perspective bins of one or more other bonded transmission links. performing re-allocation in the traffic stream under control of said CCU and based on information collected from said bonded links.
[0066] Preferably, the CCU should obtain not only the information about the perspective bins, but also about so-called non-perspective bins where either the predetermined conditions have deteriorated or the reserved one or more bit allocations have been used.
[0067] The information about the non-perspective bins may be used for selecting, at the CCU, to which links and about which perspective bins the information from the CCU should be sent.
[0068] According to a second aspect of the invention, there is proposed a computerized system for rate adaptation in a traffic stream (preferably a DMT technology stream) whenever transmitted on a group of bonded transmission links by allocating traffic bits in a plurality of bins on each of said links; the system is capable of performing bit re-allocation between different links of the group in case of a change of one or more conditions in one or more bins of at least one link in said group.
[0069] The system may comprise:
[0000] one or more monitoring means, wherein each of said monitoring means being capable of monitoring one or more predetermined conditions in a specific link of said bonded transmission links, the one or more monitoring means being in communication with a centralized conditions' monitoring and control unit CMCU capable of:
storing and updating data about bit allocations in the bins of said bonded transmission links; collecting information from said monitoring means on said predetermined monitored conditions in said transmission links; determining changes in the monitored conditions based on the collected information, making decisions about transferring bit allocations between different said transmission links based on the determined changes of said conditions and using the data at least about one specific bin to which one or more bits can be allocated, controlling bit re-allocation between different said bonded transmission links according to the decision;
the system also comprising a Bandwidth (rate) adaptation block BAB for performing said bit re-allocation under control of the CMCU.
[0075] The monitoring means preferably monitor at least selected bins of said bonded transmission links and feed to the CMCU the suitable information.
[0076] The above-mentioned stored and updated data about bit allocations can be, for example, information about at least partially reserved bins i.e., about preliminarily reserved “bit places” in one or more bins of one or more said links.
[0077] Preferably, the CCU should be capable to store and update both the data abut bit allocations in all bins of all said bonded links of the group, and the information about the conditions in all bins of all the links. In this case the monitoring means should be operative to perform massive or total per bin monitoring, and also the synchronized reporting of the monitored data to the CMCU.
[0078] The system preferably comprises at least one modified OLR software unit in the CMCU, the OLR being capable of receiving and processing information about said conditions in bins of different bonded transmission links, and capable of making decisions of transferring bit allocations between bins of said different transmission links.
[0079] The invention will be described in more details as the description proceeds.
[0080] There is also provided a software product comprising computer implementable instructions and/or data for carrying out the method described above. The software product preferably comprises computer implementable instructions of a modified OLR mechanism (say, a modified SRA algorithm). Further, there is provided a carrier medium accommodating the software product.
BRIEF DESCRIPTION OF THE DRAWINGS
[0081] The invention will further be described with reference to the following non-limiting drawings, in which:
[0082] FIG. 1 a (prior art) schematically illustrates an exemplary graph of a Signal to Noise Ratio distribution for a sequence of bins of ADSL2 transmission line.
[0083] FIG. 1 b (prior art) schematically shows another exemplary graph of an SNR distribution for a sequence of bins in a VDSL transmission line.
[0084] FIGS. 2 a , 2 b (prior art) are schematic block diagrams illustrating DMT bonded transmission links, where each of the links is adapted to have a number of bins in which traffic portions are allocated, and where rate adaptation is performed per link, within the bandwidth available in the link.
[0085] FIGS. 3 a , 3 b are block diagrams of the bonded transmission links, schematically illustrating how the rate adaptation can be performed between different transmission links, according to the invention.
[0086] FIGS. 4 a and 4 b are schematic block diagrams illustrating two exemplary embodiments of a monitoring and control system operative to perform the proposed inventive method.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0087] FIG. 1 a (prior art) shows how bandwidth of an DMT, for example ADSL (Asymmetric Digital Subscriber Loop) transmission line can be divided into narrow spectrum slices (bins). ADSL bandwidth comprises 256 downstream bins with spacing of 4.3125 kHz there-between. Each bin of the operating transmission line is characterized by its current Signal to Noise Ratio (SNR). The SNR value of a particular bin “i” is directly proportional to the number of information bits Bi which can be successfully transmitted in that particular bin. The number of bits Bi depends on some additional parameters, for example on a value of a specific fine gain gi which can be reached for this specific bin.
[0088] FIG. 1 b (prior art) illustrates an exemplary graph of a VDSL (Very High frequency Digital Subscriber Loop) transmission line, where the total bandwidth spectrum is much broader and a specific bin can be also wider.
[0089] It is understood, that conditions in the line (of FIG. 1 a , or of FIG. 1 b ) may change, the curve may therefore acquire another shape, and the number of bits Bi (Bj) which can be safely transmitted in each specific bin may also change. In order to transmit the required amount of data via the line, bits may be re-distributed between bins of the line when conditions of the line (and/or of the transmission) change. One of the known methods for coping with that—On Line Reconfiguration (OLR), and one of its particular versions—Seamless Rate Adaptation (SRA)—have been mentioned in the background of the invention.
[0090] FIGS. 2 a and 2 b (prior art) illustrate the known principle of bit rate adaptation in bonded transmission lines. FIG. 2 a illustrates the links and the initial schematic allocation of bits between bins in each of the links (by the moment of time t 1 ). FIG. 2 b illustrates results of re-allocation of bits after some conditions in the bonded links have changed by time moment t 2 . For example, each of the three illustrated links: L 1 , L 2 and LN are ADSL bonded links. In each of them, control of bit allocation in different bins is performed separately from the other link, with the aid of a specific associated Bit Allocation Block which is schematically shown as a block 10 ( 12 , 14 ) switched in the link. In this example, these blocks are marked as OLR i , to indicate that the bit allocation procedure is performed according to the known OLR method.
[0091] It is quite understood that the links are usually bi-directional.
[0092] For one specific direction (say, the west-east direction) each of the links (say, link 1 ) transmits its specific traffic stream having a predetermined specific bit rate (D 1 ). The link is provided with a separate bit allocation block at the transmitting end (for example, block OLR 1 ) which performs bit allocation to different bins in view of conditions in the link and changes of these conditions. In the links L 1 , L 2 , LN, schematic spectrum diagrams 16 , 18 and 20 (similar to that shown in FIG. 1 a ) respectively show how initial allocation of bits is performed according to initial conditions in the links. Black columns in each of the diagrams 16 , 18 , 20 show specific bins where transmission bits are allocated.
[0093] Each link usually comprises an operational embedded channel which is used for transmitting to the receiving end information about the performed bit allocations in the link, including the time of its changes if any. All of the bonded links pass a section of transmission Lg where they are considered a bonded group. At the receiving end, a second bit allocation block (in our example, marked OLR 1 ′) receives the necessary information concerning bit allocations and outputs the traffic stream with the same bit rate D 1 . The block OLR 1 ′ will perform the function of bit allocation when the traffic is transmitted in the east-west direction over the link L 1 .
[0094] FIG. 2 b illustrates how conditions in the links may change with time, and which changes in bit allocations may be caused by the condition changes in each of the links. Schematic spectral diagrams 17 , 19 and 21 show that, by the time moment t 2 , transmission conditions in different bins in links L 1 and L 2 have changed, while in link LN they remain the same. The diagrams 17 , 19 illustrate that the bit re-allocation in links L 1 , L 2 is performed within the bandwidth currently available in each specific link.
[0095] Note that the bit rates in the links respectively remain the same, namely: D 1 , D 2 and DN.
[0096] FIGS. 3 a and 3 b schematically illustrate a group of bonded links (say, of DMT technology), where rate adaptation is performed on the level of the group, i.e. in such a manner that bit rate in each of the bonded links does not have to remain constant, while the total bit rate of the resulting traffic stream remains constant. Indeed, in FIG. 3 a bit rates in link L 1 and link L 2 are respectively d 1 and d 2 . . . , while the total bit rate of the bonded group is D=(D 1 +d 2 + . . . d 10 +d 12 ). The new proposed method of bit rate adaptation is performed by schematically shown blocks 11 and 13 , called blocks of Group Bandwidth Allocation (GBA).
[0097] Spectral diagrams 22 , 24 , 26 and 28 schematically show initial distribution of bits between bins in the respective transmission links L 1 , L 2 , L 3 . . . LN (i.e., for conditions at the time period t 1 ).
[0098] In FIG. 3 b (upon some changes, say, in transmission conditions in links L 1 , L 2 and link LN) the bit rates in these links become respectively d 20 , d 21 , d 30 and d 31 (=0) while the total bit rate of the traffic stream remains equal to D.
[0099] Let in links L 1 and L 2 transmission conditions have changed so that, for a time moment t 2 , SNR has become maximal for bins which were not the best for transmitting traffic bits during time period t 1 , and vise versa.
[0100] The traffic bits may be re-allocated between different links, and it is schematically shown by dotted arrows between spectral diagrams 23 and 25 .
[0101] The present application proposes performing the described rate adaptation by controlling bit allocation in the group, for example, by monitoring predetermined conditions in each bin of each of the bonded links and re-allocating bits freely between different links of the bonded group. Of course, signaling about changes in the bit allocations, and synchronization marks are to be ensured and introduced in a kind of an embedded operational channel in each of the links.
[0102] In FIGS. 3 a and 3 b , the bit allocation control function is assumed to be performed by the two blocks GBA 11 and 13 , being common for the group of bonded links and being respectively placed at the transmitting end and at the receiving end of the bonded links group.
[0103] FIGS. 3 ( a, b ) may also illustrate how the proposed invention can be utilized for traffic protection in a group of bonded transmission links.
[0104] In one specific case, traffic via one of the transmission links may be “protected” by another transmission link.
[0105] For example, if link L 3 is agreed to be a protecting link to link LN, and link LN suddenly fails, link L 3 should be capable to undertake the whole traffic of link LN (say, d 31 =0, and d 30 =d 10 +d 12 ). For this purpose, at least some “space” in bins of link L 3 may be reserved and run idle while link LN still operates. In link L 3 , some of the bins of the available bandwidth are shown reserved (marked by two circles in the spectral diagrams). The block GBA 11 , whenever receives data about failure of link LN, should be prepared for that and should re-allocate the binary information from all bins of link LN, where it was previously allocated, to the reserved spaces in bins of link L 3 . FIG. 3 b shows that bits previously allocated in link LN, are transferred to these reserved bins of the link L 3 .
[0106] It should be noted that the bins must not be allocated/reserved completely, both the allocation and the reserving can be provided with the minimal granularity of one specific bit.
[0107] Neither monitoring of predetermined conditions (transmission conditions, link conditions, user commands, timers), nor receiving any alarms is shown in FIGS. 3 a and 3 b . Only schematic upper arrows at the blocks 11 and 13 symbolize that the monitoring and the updating are performed.
[0108] FIG. 4 a illustrates an exemplary simplified structure of the block GBA 11 ( 13 ) shown in FIGS. 3 a and 3 b . In order to perform free bit re-allocation between different links of the group of bonded transmission links (say, of the DMT technology), the Inventor proposes monitoring the link and the transmission conditions, and other conditions which are planned to be taken into account, in at least some selected bins of the transmission links. Preferably, the transmission conditions are monitored in each bin and in each link of the bonded group. The monitoring function is performed by a number of monitoring means M 1 , M 2 . . . , respectively associated with different bonded links. Two of the monitoring means are shown in FIG. 4 a and marked 40 and 42 . The monitoring means are in communication with a Conditions Monitoring and Control unit CMCU ( 44 ). In one embodiment, the CMCU 44 stores information about previous state of all bins in all of the bonded links from the point of the predetermined conditions. The CMCU 44 is also informed if any bins or parts of them are to be reserved, or if any of the reserved bins can be used (see arrow 45 ). Using the monitoring means, the CMCU 44 unit updates its information about the monitored bins of different transmission links and reports the complete updated information to its internal block 46 of modified software OLR, which may constitute a modified SRA software module. The SRA module “perceives” the received information like it was information about one “combined” fictitious link having numerous fictitious bins, and then performs logical re-allocation of bits between these bins. Actually, the SRA module 46 may store information about the previous state of all bins of the bonded links, and CMCU 44 only reports its new findings from the monitoring means to the SRA module 46 . A result of the logical bit allocation performed in the modified OLR software is then used for controlling a Bandwidth (or rate) adaptation block 48 (BAB), which performs the real rate adaptation, when dividing the data stream D into sub-streams d 1 , d 2 , . . . dn.
[0109] FIG. 4 b illustrates another embodiment of the rate adaptation system for bonded transmission links. In this embodiment, the Group Bandwidth Adaptation block GBA 110 comprises more than one CMCU units (CMCU1 unit 50 and the CMCU2 unit 54 are shown), all in communication with the Bandwidth Adaptation Block BAB 58 . Each of the CMCU units is responsible for a sub-group of bonded links (two sub-groups are indicated, comprising links with rates d 1 . . . dn and dk . . . dm). Each of the CMCU units collects information from a number of monitoring means in its sub-group and, based on that information, performs logical re-allocation of bits within the sub-group using its associated OLR modified software block. Real bandwidth (rate) adaptation is performed by the block BAB 58 , when collecting data from all sub-group CMCUs (in this example, from blocks 50 and 54 ).
[0110] The proposed embodiment can be effectively used for traffic protection in the group of bonded links.
[0111] It should be appreciated that other embodiments of the system and other versions of the method could be proposed for implementation of the inventive concept; such modifications are to be considered part of the invention being generally defined by the claims that follow. | A method is described for rate adaptation in a telecommunication system comprising a group of bonded transmission links carrying together a binary traffic stream, wherein each of the bonded links is adapted to carry a sub-stream of binary information allocated in a number of bins. In case of changing conditions in at least one bin of at least one bonded link among the group, bit re-allocation is performed between different bonded links in the group, thereby adapting rate in one or more of the bonded transmission links to the current conditions. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of co-pending U.S. application Ser. No. 12/908,761 (the “'761” Application), now U.S. Pat. No. 8,636,123, entitled “Luggage Panel With Integrated Carry Handle For Soft-Side Type Luggage Cases”, and filed on Oct. 20, 2010, which claims the benefit under 35 U.S.C. §119(e) to U.S. provisional application No. 61/253,242 (the “'242” Application), entitled “Lightweight Top and Side Panel Carry Handle Construction for Soft-Side Type Luggage Cases” and filed on Oct. 20, 2009. The '761 and '242 Applications are hereby incorporated herein by reference in their entireties.
FIELD OF INVENTION
[0002] The field of invention generally relates to luggage.
BACKGROUND
[0003] Luggage cases or the like may include two or more wheels mounted on or next to the bottom panel of such luggage cases to facilitate transportation of the luggage cases by dragging or pushing the luggage cases. Even when such luggage cases include this convenient wheeling system, it may be necessary to lift or carry the case by hand. For example, placing the luggage case in the trunk or passenger compartment of a vehicle or transferring the luggage to or from a luggage carousel in an airport or the like may require the luggage case to be lifted or carried. Any handles or grips for such purposes should be quite strong since each handle must support the weight of the luggage case when it is filled with a traveler's belongings. Also, for a structured soft-side luggage case, the panel to which the carry handle is attached must be sturdy enough to not significantly distort the shape of the case when the filled luggage is carried by the handle.
[0004] Another challenge for making such luggage cases is that the purchaser often lifts luggage cases when shopping for luggage to determine the sturdiness and weight of the luggage case. Of course these luggage cases on display in the luggage shop are empty. Also one measure used by luggage retailers and manufacturers to sell luggage is the empty weight of the luggage case expressed in kilograms or pounds. Thus, a criteria for buying a luggage case is the weight of the luggage case, even though the empty weight of the luggage case usually amounts to a small percentage of the weight of the case when packed for travel.
[0005] Also, when lifting the empty luggage case to judge its weight, the prospective luggage purchaser must decide whether the luggage construction is sturdy enough to withstand the rigors of travel. It is this conflict or dichotomy, the lightness of an empty luggage case and perceived robustness or durability of the case, that luggage manufacturers have grappled with for decades.
SUMMARY
[0006] One embodiment of a luggage case may include a panel with a carry handle integrated therewith. The panel may include a generally flat sheet of flexible laminar body material that constitutes the bulk of the outside surface of the soft-side luggage case, The luggage case may further include a resilient hoop positioned around the perimeter of the panel. A resilient hoop may be firmly attached to the flexible laminar body material. In some embodiments, this body material is firmly attached to at least a majority of the hoop. Two side portions of the flat sheet may be reduced in dimension to form a handle grip located generally in the center of the sheet. Beneath this grip may be a second sheet of a flexible laminar material, preferably also of body material, affixed at its edges to the remaining portions of the perimeter wire hoop exposed by the narrowed portion of laminar body material that defines the handle grip.
[0007] Another embodiment of a luggage case may include a first panel. The first panel may include a perimeter edge. The first panel may define at least a portion of an outer surface of the luggage. The first panel may include a first textile body. The first textile body may define at least a portion of an outer surface of the first panel. The first textile body may further define at least a portion of the perimeter edge of the first panel. The first textile body may include a grip portion defining a grip for a carry handle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a perspective view of an upright luggage case showing top and side panels, each incorporating a carry-handle formed from the material defining the outer surfaces of the panels.
[0009] FIG. 2 is a top view of the luggage case shown in FIG. 1 , showing the top panel with the carrying handle and a telescopic wheel handle.
[0010] FIG. 3A shows an elevation view of the luggage case shown in FIG. 1 , showing one possible way to form a first textile body for the side panel.
[0011] FIG. 3B shows an elevation view of the luggage case shown in FIG. 1 , showing another possible way to form a first textile body for the side panel.
[0012] FIG. 4 shows, through the open main packing door, interior surfaces of the luggage case shown in FIG. 1 .
[0013] FIG. 5 is a schematic exploded view of the structural components of the side panel for the luggage case shown in FIG. 1 .
[0014] FIG. 6 is a partial perspective view of the luggage case of FIG. 1 , showing the wheels mounted on the lower end of the luggage case.
[0015] FIG. 7 is another partial perspective view of the luggage case of FIG. 1 , showing the telescopic wheel handle in an extended position.
[0016] FIG. 8 is a partial perspective view of the luggage case of FIG. 1 , showing an interior view of the bottom panel to which is mounted the wheels shown in FIG. 6 .
[0017] FIG. 9 shows the upper telescopic wheel handle mounting housing as seen from the inside of the luggage case.
[0018] FIG. 10 shows a top view of a panel for a luggage case, showing another version of incorporating a handle into the panel.
[0019] FIG. 11 shows a top view a luggage case similar to the luggage case shown in FIG. 1 , showing a top panel that has both an integrated carry handle and rivets.
[0020] FIG. 12 shows a side view a luggage case similar to the luggage case shown in FIG. 1 , showing a side panel that has both an integrated carry handle and rivets.
[0021] FIG. 13 shows a schematic, partial cross-section view of one embodiment of a carry handle, viewed along line 13 - 13 in FIG. 2 .
[0022] FIG. 14 shows a schematic, partial cross-section view of another embodiment of a carry handle, viewed along line 14 - 14 in FIG. 2 .
[0023] FIG. 15 shows a picture of a luggage case that is cut apart to show some of the materials or components that may be positioned between first and third textile bodies defining a carry handle.
[0024] FIG. 16 shows another picture of the luggage case shown in FIG. 15 , which is cut apart to show some of the materials or components that may be positioned between the first and third textile bodies defining the carry handle.
DETAILED DESCRIPTION
[0025] Described herein are methods for making structured but essentially soft-sided luggage cases, and products created using such methods. These cases are usually formed from textile panels, leather panels or simulated leather panels. These cases may include other components, such as frames, boards, and so on, that are intended to hold the otherwise flimsy panels in a generally flat rectangular shape to form a luggage case with an overall parallelepiped shape. More particularly, described herein is a particularly lightweight construction for those panels that also serves to mount a carry handle for manually carrying or towing the luggage case during travel, etc. The construction methods include making rectangular, or other shaped, panels with integrated carrying handled for luggage cases, such as upright or spinner type cases, or the like (e.g., duffel bags, backpacks, and so on) where one mode for transporting the luggage case is to drag or push the luggage case on two or more wheels mounted on or next to the bottom panel of such luggage case. In constructing such panels, minimal or no rigid stiffening structures may be used to reduce to weight of the style luggage case. Such a light construction may contribute to the overall light weight of the empty case, while demonstrating that the case is robust and dimensionally stable.
[0026] In describing the components of the luggage and alternative versions, or embodiments, of some of these components, the same reference number may be used for elements that are the same as, or similar to, elements described in other versions or embodiments.
[0027] Turning to FIGS. 1-4 , a luggage case 100 may include one or more sides 105 . In some embodiments, the luggage case may include six sides 105 a - c (e.g., top, bottom, left, right, front and back sides). Other embodiments of the luggage case 100 may include more or less than six sides. The sides 105 of the luggage case 100 may define a main packing compartment. Each side 105 may have a generally rectangular shape to form a generally parallelepiped luggage case 100 . In some embodiments, the sides 105 may have other shapes to define a luggage case 100 with a desired shape other than generally parallelepiped. The luggage case 100 may further includes wheels 110 , glides, edge piping 115 to help protect the outer surface of the luggage from scuffs and abrasions, and a main door 120 with a perimeter zipper 125 for access to at least the main packing compartment.
[0028] Each side 105 of the luggage case 100 may be formed using one or more panels 130 . In some embodiments, each side 105 of the luggage case 100 may be formed using a single panel 130 . In other embodiments, two or more panels 130 may be used to form a side 105 of the luggage case 100 . At least some of the panels 130 forming the sides 105 of the luggage case 100 may define at least a portion of the outer surface 135 of the luggage case 100 . For example, with reference to FIG. 1 , the side and top panels 130 a,b define a portion of the outer surface 135 of the luggage case 100 . At least some of the panels 130 may be joined to an adjacent panel 130 proximate a perimeter edge 140 of the panel 130 . For example, with reference to FIG. 1 , a first panel 130 a (e.g., a side panel) may be joined a second panel 130 b (e.g., a top panel) proximate a perimeter edge 140 of the first panel 130 a (e.g., the upper edge of the side panel).
[0029] The luggage case 100 may further include carry handles 145 integrally joined with the one or more panels 130 that define the sides 105 of the luggage case 100 . With reference to FIG. 1 , the side panel 105 a and the top panel 105 b of the luggage case may each include a carry handle 145 a,b integrally joined with its respective panel 130 a,b. While the carry handles 145 are shown as integrally joined with the top and side panels 130 , a carry handle 145 may be integrally joined with any panel 130 defining a side 105 of the luggage case 100 .
[0030] The following description of forming the carry handle 145 on a panel 130 will be described with respect to the side panel 130 a. However, this description should be understood as applicable for the top panel 130 b, or any other panel 130 , that incorporates an integral handle. With reference to FIGS. 1 , 3 A and 5 , the side panel 130 a may include perimeter edge 140 to which one or more other panels 130 may be attached. While the other panels 130 are typically attached to the side panel 130 a by sewing, any suitable connection method may be used to join the panels 130 together. A reinforcement assemblage may be positioned proximate the perimeter edge 140 of the side panel. The reinforcement assemblage may include an edge beading 150 and a generally rectangular frame or hoop 155 of a resilient, tough steel wire or similar material. The hoop 155 may be resilient, flexible and resistant to compression but may also be bendable and flexible, especially along its longer straight sides unless constrained. The hoop 155 may be positioned within a substantially enclosed space defined by the edge beading.
[0031] The side panel 130 a may include the perimeter edge 140 , an outer surface 160 and an inner surface 165 . The perimeter edge 140 may define a rectangular shape, or any other desired shape. The outer surface 160 may be constructed using a first textile body 170 and a second textile body 175 . The first and second textile bodies 170 , 175 may be formed from a robust woven textile, such as nylon, polyester, Ramie or the like.
[0032] The first textile body 170 may be generally rectangular in shape, or any other shape that generally matches at least a portion of the shape defined by the perimeter 140 edge of the side panel 130 a. A central or grip portion 180 of the first textile body 170 may define a relatively narrow band of material between first and second portions 185 , 190 of the first textile body 170 . The relatively narrow band of material defines the grip for the carry handle 145 a. The first and second portions 185 , 190 may be formed at end or outer portions of the first textile body 170 . The central or grip portion 180 may be smoothly and integrally joined to the first and second portions 185 , 190 of the first textile body 170 by way of curved edges. Each first and second portion 185 , 190 of the first textile body 170 may widen from a relative narrow dimension proximate the central or grip portion 180 to the full width dimension of the generally rectangular side panel 130 a.
[0033] In some embodiments, the central or grip portion 180 of the first textile body 170 defines a handle grip with a longitudinal axis that is relatively transverse to an edge defining the width of the first and second portions and/or the panel. Such a configuration is shown, for example, in FIGS. 2 , 3 A and 3 B. In other embodiments, the handle grip may have a longitudinal axis that is positioned at an angle relative to the edge defining the width of the first and second portions and/or the panel. Such as configuration is shown, for example, in FIG. 10 . The foregoing examples are merely illustrative of how the handle may be positioned relative to the first and second portions 185 , 190 of the first textile body 170 and/or the side panel 130 a. Other configurations of the handle relative to the first and second portions 130 a,b of the first textile body and/or the panel may be defined in the central or grip portion 180 of the first textile body 170 so long as the handle is formed from a first textile body 170 that defines at least a portion of the outer surface 135 of the side panel 130 a.
[0034] As shown, for example, in FIGS. 1 and 5 , the first textile body 170 in some embodiments may be made from a single piece of textile material. In such embodiments, the central or grip portion 180 may be formed by cutting material within the central or grip portion 180 of the single piece of textile material to define the narrow band of material. The cut edges created in the central or grip portion 180 may be finished either by folding the edges or by applying an edge beading or trim. In other such embodiments, the first, second and central (or grip) portions 180 , 185 , 190 could be defined when creating the piece of textile material used for the first textile body 170 .
[0035] In some embodiments, the first textile body 170 may formed using two or more pieces of textile material. For example, with reference to FIG. 3A , two pieces of textile material joined by a seam 195 positioned proximate a centerline of the central or grip portion 180 may be utilized to form the first textile body 170 . Such a construction for the first textile body 170 may result in an overall saving in textile material compared to forming the first textile body 170 from a single piece of textile material. As another example, with reference to FIG. 3B , three pieces of textile material may be joined by seams 195 to form the first textile body 170 . One piece may be used to form the central or grip portion 180 of the first textile body, and the other two pieces may be used to form the first and second portions 185 , 190 of the first textile body 170 . Such a construction may result in further material savings compared to using a single piece of material and also would permit the use of a contrasting color or texture choice for the central or grip portion 180 of the first textile body 170 . Such a contrasting material choice may have aesthetic and functional advantages.
[0036] The foregoing examples are merely illustrative of some ways that the first textile body 170 may be formed, and are not intended to limit how the first textile body 170 may be formed. Further, while described as being formed using one, two or three pieces of textile material, any number of pieces of textile material may be use to created the first textile body 170 .
[0037] The first and second portions 185 , 190 of the first textile body 170 may be joined to the edge beading 150 . The first and second portions 185 , 190 may be joined to the edge beading 150 by stitching the first and second portions 185 , 190 along at least a portion of their edges to the edge beading 150 , or by using any other suitable connection method, including, but not limited to, adhering or bonding the first and second portions 185 , 190 to the edge beading 150 . This joining of the first and second portions 185 , 190 of the first textile body 170 to the edge beading 150 functions to operatively connect the first textile body 170 with the hoop 155 .
[0038] The second textile body 175 may be generally square or rectangular in shape. The second textile body 175 may be positioned underneath the central or grip portion 180 of the first textile body 170 . The second textile body 175 may include two edges, which may be referred to as first and second edges 200 , 205 , that each span the width of the first and second portions 185 , 190 of the first textile body 170 , and two other edges, which may be referred to as third and fourth edges 210 , 215 , that span at least the length of the central or grip portion 180 of the first textile body 170 . In some embodiments, the third and fourth edges 210 , 215 may end proximate the perimeter edge 140 of the side panel 130 a. The first and second edges 200 , 205 may be joined to the first textile body 170 by a suitable connection method, such as stitching or bonding. The third and fourth edges 210 , 215 may be joined to the perimeter edge 140 of the panel 130 a by a suitable connection method, such as stitching or bonding. Together, the first and second textile bodies 170 , 175 may define substantially the entire outer surface 135 of the side panel 130 a. Portions of the edges of the first and second textile bodies 170 , 175 may also collectively define the perimeter edge 140 of the side panel 130 a.
[0039] The inner surface 165 of the panel may be formed using a lining material 220 . This lining material 220 may be a textile material that is fairly light and smooth to give a pleasing interior texture and finished look to the luggage case 100 . The lining material 220 is not necessary from a structural standpoint. Thus, the lining material 220 may be omitted, if desired. In such embodiments, the first and second textile bodies 170 , 175 may define the inner surface 165 of the side panel 130 a.
[0040] Once constructed, the lifting force from the handle grip (i.e., the central or grip portion 180 of the first textile body 170 ) may transferred by way of the first and second portions 185 , 190 of the first textile body 170 to the perimeter edge 140 of the side panel 130 a. In particular, the lifting force may result in horizontal and vertical forces being imposed on the perimeter edge 140 of the side panel 130 a. The horizontal forces may generally result in compressive forces applied along the longitudinal axes of the hoop 155 . The vertical forces may generally result in the rest of the luggage case and its contents hanging from the hoop 155 . Thus, the hoop 155 helps to minimize the distortion of the side panel 130 a with the integrated carry handle 145 a. This, in turn, helps to maintain the overall shape of the luggage case 100 when carried by the carry handle 145 a. Both the horizontal and vertical forces applied to the hoop 155 may be relatively uniform, which may further help to minimize the distortion of the side panel 130 a with the integrated carry handle 145 a.
[0041] Because of the lack of further rigid structures under it, the panels 130 that incorporate the integrated carry handle 145 are relatively light. As a result of this construction, the prospective purchaser may perceive the luggage case 100 to be strong enough to withstand the rigors of travel, while also appreciating it as being lighter than conventional luggage constructions.
[0042] In some embodiments, a relatively rigid material, such as a polypropylene or polyethylene board, may be positioned under the first and second textile bodies 170 , 175 to help maintain the shape of the panel 130 . In such embodiments, the first textile body 170 may be joined to the relatively rigid material to transfer at least some of the forces imposed upon the carry handle 145 to the relatively rigid material. With reference to FIGS. 11 and 12 , when the panel 130 includes a relatively rigid material positioned under the first textile body 170 , the first textile body 170 may be joined by mechanical fasteners 225 , such as rivets, screws, staples, and so on, or by any other suitable joining method, including, but not limited to, by bonding or gluing.
[0043] FIGS. 13 and 14 show schematic partial cross-section views of additional examples of possible ways to form the carry handle 145 . While these views only show one edge 300 of the carry handle 145 , the edge of the carry handle 145 that is distal this edge 300 may be formed in a similar manner. Thus, the following description is applicable to edge of the carry handle 145 distal the edge 300 shown in FIGS. 13 and 14 .
[0044] With reference to FIG. 13 , the carry handle 145 may be formed using the first textile body 170 and a third textile body 305 . The first textile body 170 may define a first outer surface 310 , such as the upper surface, of the grip for the carry handle 145 , and the third textile body 305 may define a second outer surface 315 , such as the lower surface, of the grip for the carry handle 145 . As described above in more detail, the first textile body 170 may further include first and second end portions 185 , 190 that define at least portions of the perimeter edge 140 of the panel 130 . Further, as described in more detail above, the panel 130 associated with the first textile body 170 may include the second textile body 175 . The second textile body 175 in conjunction with the first textile body 170 may collectively define the outer surface 160 of the panel 130 .
[0045] The third textile body 305 may include a grip portion 320 to define, in conjunction with the first textile body 170 , the grip of the carry handle 145 . The grip portion 320 for the third textile body 305 may correspond to, or otherwise match in shape, the grip portion 180 of the first textile body 170 . The third textile body 305 , like the first textile body 170 , may further include first and second portions (not shown) with the grip portion 320 positioned between the first and second portions. The first and second portions of the third textile body 305 , when present, may generally correspond to, other otherwise match, the shape of the first and second portions of the first textile body 170 . In some embodiments, however, the first and second portions of the third textile body 305 may extend only under a portion of the respective first and second portions 185 , 190 of the first textile body 170 . In such embodiments, one or more edges of the first and second portions of the third textile body 305 may not extend to the perimeter edge 140 of the panel 130 .
[0046] With continued reference to FIG. 13 , an edge fabric 325 may be positioned along each edge 330 , 335 of at least the grip portions 180 , 320 of the first and third textile bodies 170 , 305 . The edge fabric 325 could also be positioned along at least portion of the edges of the first and second portions of either, or both, of the first and third textile bodies 170 , 305 . The edge fabric 325 may be configured to define a substantially enclosed space for receiving a stiffening element 340 (which may also be considered as a rigid or semi-rigid element), such as a polyvinyl chloride (PVC) pipe, a steel or carbon fiber wire, and so on. The stiffening element 340 may help to maintain the shape of the grip of the carry handle 145 defined by the first and third textile bodies 170 , 305 .
[0047] With continued reference to FIG. 13 , the edge fabric 325 may be folded into a C- or U-shape to define the enclosed space for the stiffening element 340 . The ends 345 of the edge fabric 325 may be positioned between the inner facing surfaces 350 , 355 of the first and third textile bodies 170 , 305 . A portion of the edge fabric 325 may extend beyond the edges 330 , 335 of the first and third textile bodies 170 , 305 . This portion may include the enclosed space that receives the optional stiffening element 340 . The end portions of the first and third textile bodies 170 , 305 , proximate the edge fabric 325 , may be folded into a C- or U-shape to define the curved edges 330 , 335 for the first and second textile bodies 170 , 305 . With these end portions of the first and third textile bodies 170 , 305 folded, the stiffening element 340 (if any) positioned within the enclosed space, and the ends 345 of the folded edge fabric 325 positioned between the inner facing surfaces 350 , 355 of the first and third textile bodies 170 , 305 , the edge fabric 325 , the first textile body 170 , and the third textile body 305 may be sewn together, or otherwise suitably joined. Like the first and second textile bodies 170 , 175 , the third textile body 305 and the edge fabric 325 may be formed from a robust woven textile, such as nylon, polyester, Ramie or the like.
[0048] FIG. 14 shows a handle construction similar to the construction shown in FIG. 13 . Like the construction in FIG. 13 , the carry handle 145 shown in FIG. 14 includes the first textile body 170 , the third textile body 305 , and an edge fabric 325 . The primary difference between these two carry handles 145 arises from how the edge fabric 325 is joined to the first and third textile bodies 170 , 305 . In the embodiment shown schematically in FIG. 14 , the edge fabric 325 is folded into a C- or U-shape, similar to the edge fabric 325 in FIG. 13 . The ends 345 of the edge fabric 325 , however, are positioned over the outer facing surfaces 360 , 365 of the first and third textile bodies 170 , 305 . Thus, the edges 330 , 335 of the first and third textile bodies 170 , 305 are positioned between an inner facing surface 370 of the edge fabric 325 . Further, unlike the construction shown in FIG. 13 , the end portions of the first and third textile bodies 170 , 305 are not folded (i.e., they remain straight). Once the edges 330 , 335 of the first and third textile bodies 170 , 305 are positioned as shown in FIG. 14 , the edge fabric 325 , the first textile body 170 , and third textile body 305 may be sewn together, or otherwise suitably joined. While no stiffening element 340 is shown in FIG. 14 , a stiffening element 340 could be positioned within the curved portion of the edge fabric 325 , if desired.
[0049] While the foregoing examples demonstrate some potential ways to construct the carry handle 145 using textile fabrics, these examples are intended only to be illustrative and not limiting. As such, other techniques or constructions may be used to create the carry handle 145 when formed using at least the first textile body fabric.
[0050] Additional materials or components may be placed between the first and third textile bodies 170 , 305 , if desired. These additional materials or components may be used to help maintain the shape of the carry handle 145 , to provide additional structural support for the handle, or to enhance the comfort for a user. FIGS. 15 and 16 show pictures of a luggage case that is cut apart to show some of the materials or components that may be positioned between the first and third textile bodies 170 , 305 . For example, ethylene vinyl acetate (EVA) foam 400 may joined to the inner facing surfaces of either, or both, of the first and third textile bodies 170 , 305 . The EVA foam 400 may create a more comfortable grip for a user. The EVA foam 400 may be joined to the first and third textile bodies 170 , 305 by adhering the EVA foam 400 to the textile bodies 170 , 305 or by any other suitable connection method. In some embodiment that include EVA or other foam, the foam may be positioned between the first and third textile bodies 170 , 305 without joining the foam to the textile bodies 170 , 305 .
[0051] As another example, a rigid or semi-rigid board 405 , such as a high-density polyethylene (HDPE) board, may be positioned between the first and third textile materials 170 , 305 . The board 405 may extend from one end of the grip to the opposite end of the grip. Within the grip, the board may be shaped to correspond to the shape of the grip portions 180 , 320 for the first and third textile bodies 170 , 305 . The board 405 may help to maintain the shape for the handle and/or may provide structural support for the handle. If desired, the board 405 may be mechanically fastened with fasteners (such as screws, rivets, and so on), or otherwise joined, to other underlying materials to maintain the relative position of the board to the first and third textile bodies 170 , 305 .
[0052] As yet another example, a rigid or semi-rigid plate 410 , such as a steel plate, may be positioned between the first and third textile materials 170 , 305 . Like the board 405 , the plate 410 may extend from one end of the grip to the opposite end of the grip. Also like the board 405 , the plate 410 may help to maintain the shape for the handle and/or may provide structural support for the handle.
[0053] The foregoing examples are merely illustrative of some components or materials that may be positioned between the first and third textile bodies. Some or all of these materials may or may not be positioned between the first and third textile bodies. Further, other materials or components may or may not be positioned between the first and third textile bodies, such as cardboards, foams other than EVA foams, other fabrics, and so on. Further, in some embodiments, there may be no additional components or materials positioned between the first textile bodies.
[0054] Reducing the weight of the luggage may be further enhanced with other modifications to the luggage case 100 . More particularly, the luggage case 100 may constructed of materials that further enhance its lightweight impression. For example, in contrast with conventional luggage cases, the down tubes 230 (shown in FIG. 8 ) that hold the telescoping rods 235 for the telescopic handle 240 may be made aluminum instead of the typical steel, which saves a certain amount of weight. Also the bottom board 245 may be a single honeycomb polymer board. This polymer board may be attached to a monolithic wheel bracket and kick plate 250 . With reference to FIG. 9 , the housing 255 used to hold the grip portion of the telescopic handle 240 may be a punctured wheel housing type. Such a housing 255 may result in a light luggage case since it may weigh less than the typical, more complex attachment mechanisms used in conventional luggage cases.
[0055] Lastly, a higher quality steel may be used to form the thin perimeter wire hoops 155 around the carry handle-bearing panels and around the other panels 130 of the luggage case 100 . This permits the diameter of that wire to be reduced, resulting it in a further incremental weight saving. Other materials and constructions may also be used to make the hoop 155 , such as an extruded polymer bent into the hoop shape during extrusion or in a post-forming step. The hoop 155 may also be made of one piece, such as by injection molding or stamping from a preformed sheet so long as the sheet panel is sufficiently stiff to resist collapse when subjected to the pulling forces from the first textile body attached to the perimeter of the stiff panel. Alternately, the perimeter hoop could be made of different separate pieces (e.g., injection molded corners with straight pultruded sides).
[0056] The above-described constructions may reduce the weight of the upright luggage case compared to conventionally constructed luggage cases. In particular, all things being equal, it is believe that the incorporating a handle into a textile body that forms at least a portion of the outer surface of a panel (e.g., a side panel and/or a top panel) may contribute to a substantial weight saving over an equivalently sized but conventionally constructed case with rigidifying perimeter or corrugated or honeycomb frame members.
[0057] All directional references (e.g., upper, lower, upward, downward, left, right, leftward, rightward, top, bottom, above, below, vertical, horizontal, clockwise, and counterclockwise) are only used for identification purposes to aid the reader's understanding of the embodiments of the present invention, and do not create limitations, particularly as to the position, orientation, or use of the invention unless specifically set forth in the claims. Connection references (e.g., attached, coupled, connected, joined, and the like) are to be construed broadly and may include intermediate members between a connection of elements and relative movement between elements. As such, connection references do not necessarily infer that two elements are directly connected and in fixed relation to each other.
[0058] In some instances, components are described with reference to “ends” having a particular characteristic and/or being connected with another part. However, those skilled in the art will recognize that the present invention is not limited to components which terminate immediately beyond their points of connection with other parts. Thus, the term “end” should be interpreted broadly, in a manner that includes areas adjacent, rearward, forward of, or otherwise near the terminus of a particular element, link, component, part, member or the like. In methodologies directly or indirectly set forth herein, various steps and operations are described in one possible order of operation, but those skilled in the art will recognize that steps and operations may be rearranged, replaced, or eliminated without necessarily departing from the spirit and scope of the present invention. It is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative only and not limiting. Changes in detail or structure may be made without departing from the spirit of the invention as defined in the appended claims. | Luggage cases of the soft-side construction are perceived to be lighter than hard-side cases. However, many rigidifying elements in soft-side cases tend to add to the weight of a soft-side luggage case. This reduces its weight advantage over molded shell luggage cases. Using a textile body in the luggage case to form both the grip of a carry handle and a portion of the outer surface of the luggage helps reduce the weight of the luggage. The textile body may be attached to a thin resilient wire hoop to resist distortion of the luggage case when is it lifted by the handle. This construction saves weight in comparison to conventional luggage case constructions. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a console for storing or containing various items in a vehicle. More particular, the present invention relates to a reconfigurable, modular storage console having an easily operable latch mechanism.
2. Description of the Prior Art
Various types of storage containers are well known for use in a vehicle including as a center console. Vehicle storage containers and organizers continue to be very popular in all types of vehicles. One reason for the increase in popularity is that storage containers afford a vehicle driver or passenger increased organization and utilization of interior space. Additionally, a storage console can add to driver and passenger convenience and comfort since they can hold beverage cups, cans and bottles as well as numerous other types of objects, equipment, tools, gear and items. However, despite being aware of the above, vehicle designers and manufacturers continue to provide very simple and basic storage compartments.
It is common for a vehicle to have a single storage compartment, typically located in a center console positioned on the floor, and having a single door for accessing the interior of the storage container. These types of console systems are relatively inaccessible or unusable, thereby undesirably preventing access to the items stored in the containers by a driver or passenger within the passenger compartment. Thus, a driver or passenger seeking a particular item must use one entry into a single compartment storage container where items are stored one on top of another with little organization. Further, if any item is set on top of the entry door, it must be moved before entry may be made into the storage container's interior.
The above attributes of existing storage containers increase the likelihood of not easily finding a particular item as well as the likelihood of items in the container shifting during travel, which can lead to damage. While some solutions have provided for the inclusion of a separately located cup-holder feature or pocket or even multiple compartment consoles, these additions add to the size of the footprint of the storage container.
FEATURES AND SUMMARY OF THE INVENTION
It is an object of the present invention to improve a console assembly for a vehicle and to provide a console assembly that includes convenient and accessible storage compartments as well as a place to hold a beverage container and a useable work surface which all can be reconfigured to obtain advantageous results. The present invention provides a console assembly with a lower storage module and a tray mounted within a track in the lower storage module and movable thereon.
The present invention further provides a console assembly with an upper storage module mounted within a separate track in the lower storage module and movable with respect to the lower module and the tray which includes a latch member mounted on the upper module for selectively moving the upper module with respect to the lower module and the tray.
Additionally, the present invention provides a console assembly having the above advantages, and is capable of having an attractive, integrated appearance within the vehicle interior.
The console assembly accordingly to the present invention includes a lower module for storing items, a tray mounted within a track in the lower module and movable thereon, an upper module mounted within a second track and movable with respect to the lower module and the tray, and a latch member mounted on the upper module for selectively moving the upper module with respect to the lower module and the tray.
The console assembly of the present invention has the advantage of providing multiple storage containers within a confined footprint while allowing easy access and reconfiguration of the storage compartments and the tray. The tray and upper module are selectively positionable to provide access to the storage interior of the lower module. Further, the upper module is provided with storage area as well as beverage container holder and a separate cover for the upper module. The cover for the upper module is also usable as a work surface when the upper module is located proximal the rear of the console. This provide closer and more convenient access to the items to a driver or passenger of the vehicle as well as occupants of the rear of the vehicle. The console assembly can be produced using known materials and processes.
The following description of the preferred embodiment is merely exemplary in nature, and is in no way intended to limit the invention, any application of the invention or its uses. Accordingly, alternatives to the features of the invention will be apparent to those skilled in the art after reviewing the present application, such alternatives falling within the scope of the present invention if they fall within the scope of the claims which follow.
BRIEF DESCRIPTION OF THE DRAWINGS
Further features and advantages of the invention will become apparent from the following discussion and accompanying drawings, in which:
FIG. 1 is a perspective view of the console assembly according to a preferred embodiment of the present invention in a first configuration;
FIG. 2 is a perspective view of the console assembly according to a preferred embodiment of the present invention in a second configuration;
FIG. 3 is a perspective view of the console assembly according to a preferred embodiment of the present invention in a third configuration;
FIG. 4 is an exploded view of the console assembly of a preferred embodiment of the invention;
FIGS. 5 and 6 are perspective views of the console assembly of a preferred embodiment of the invention;
FIG. 7 is a perspective view of the latch module of a preferred embodiment of the invention;
FIG. 8 is a partial cross-sectional view of the console assembly of a preferred embodiment of the invention;
FIG. 9 is a perspective view of the track of a preferred embodiment of the invention; and
FIG. 10 is a side view of the release member of the latch module of a preferred embodiment of the invention.
FIG. 11 is a partial, sectional side view of the console assembly of a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As generally shown in the FIGS. 1 through 11 and as best shown in FIGS. 1, 2 and 11 , the console assembly 10 of the preferred embodiment of the invention includes an upper module 12 , a lower module 14 , a storage module 16 , and a guide track 18 . Although the console assembly 10 of the invention is preferably located between a driver-side seat 20 and a passenger-side seat 22 of a vehicle interior 24 , the console assembly 10 may alternatively be located in other suitable locations within the vehicle interior 24 .
As shown in FIGS. 3 and 4, the upper module 12 , which functions to provide an armrest surface and to contain particular objects, preferably includes a substrate member 26 , an exterior member 28 , and a slide member 30 . The substrate member 26 , which functions as a base for the upper module 12 , preferably includes a cupholder 32 and an ashtray 34 . The substrate member 26 may alternatively include other cargo compartments, such as a coin slot or a cell phone slot. The substrate member 26 is preferably made from a stiff material, such as a plastic material and from conventional methods, but may alternatively be made with other suitable materials and from other suitable methods.
The exterior member 28 of the upper module 12 , which functions to cover and decorate the substrate member 26 , is preferably fastened to the substrate member 26 with multiple screws, but may alternatively be fastened with other suitable devices, such as adhesives or snap-together parts. In the preferred embodiment, the exterior member 28 includes a cupholder lid 36 and an ashtray lid 38 and functions as a writing surface when the cupholder lid 36 is in the closed position. The cupholder lid 36 and the ashtry lid 38 are preferably moveable from a closed position (shown in FIGS. 1 and 2) and an open position (shown in FIG. 3 ). In the closed position, the cupholder lid 36 and ashtray lid 38 effectively covers the cupholder 32 and the ashtray 34 , while in the open position, the cupholder lid 36 and ashtray lid 38 allow access through the exterior member 28 to the cupholder 32 and the ashtray 34 . In an, alternative embodiment, the exterior member 28 may include other devices, such as a coin slot lid or a cell phone slot lid. The exterior member 28 is preferably made from a material pleasing to the eye and the hand, such as a fabric or leather material, and with conventional methods, but may alternatively be made from other suitable material and with other suitable methods. Further, the exterior member 28 may be integrally formed with the substrate member 26 .
The slide member 30 of the upper module 12 functions to allow sliding of the upper module 12 on the guide track 18 relative to the storage module 16 . The slide member 30 is preferably fastened to the substrate member 26 with multiple screws, but may alternatively be fastened with other suitable devices, such as adhesive or snap-together parts. Further, the slide member 30 may be integrally formed with the upper module 12 . In the preferred embodiment, the slide member 30 extends outwardly from the substrate member 26 to engage the guide track 18 . In an alternative embodiment, the slide member 30 may extend inwardly towards the substrate member 26 to engage a differently configured guide track. The slide member 30 is preferably made from a material with an appropriate surface friction, such as a plastic material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods.
The lower module 14 , which functions to cradle thin objects such as loose change, sunglasses and portable phones or other similar items, preferably includes a recessed portion 40 , a slide portion 42 , and a simple latch 44 . The recessed portion 40 functions to prevent these particular objects from rolling out of or falling from the lower module 14 during operation of the vehicle. The slide portion 42 , like the slide member 30 of the upper module 12 , functions to allow sliding of the lower module 14 on the guide track 18 relative to the storage module 16 . The slide portion 42 is preferably made from a material with an appropriate surface friction, such as a plastic material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods. The simple latch 44 functions to engage a portion of the storage module 16 and hold the lower module 14 in the rearward position. The simple latch 44 is preferably made from conventional materials and with conventional methods but may alternatively be made from other suitable materials and with other suitable methods.
The storage module 16 , which functions to hold larger objects, preferably includes an interior compartment 46 and an exterior panel 48 . The interior compartment 46 preferably includes a front section 50 and a rear section 52 . In the preferred embodiment, the interior compartment 46 includes a storage partition 54 between the front section 50 and the rear section 52 to divide the interior compartment 46 into distinct sections. In an alternative embodiment, the interior compartment 46 may include multiple storage partitions, or may not include any storage partitions. The interior compartment 46 preferably includes multiple slots 56 for compact discs or cassettes, but may alternatively include other suitable devices. The interior compartment 46 is preferably made from a stiff material, such as a plastic material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods.
The exterior panel 48 of the storage module 16 , which functions to cover and decorate the interior compartment 46 , is preferably fastened to the interior compartment 46 with multiple screws, but may alternatively be fastened with other suitable devices, such as adhesives or snap-together parts. The exterior panel 48 preferably includes a left section 58 facing the driver-side seat, a right-section 60 facing the passenger-side seat, and an end extension 62 facing in a rear direction. Preferably, the left section 58 and the right section 60 include map pockets 64 and the end section 62 includes a vent 66 and an electrical outlet 68 . Alternatively, the exterior panel 48 may include other suitable devices. The exterior panel 48 is preferably made from a material pleasing to the eye and the hand, such as a fabric or leather material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods.
The guide track 18 functions to allow independent sliding of the upper module 12 and the lower module 14 relative to the storage module 16 . The guide track 18 preferably includes a left track 70 and a right track 71 shown in FIG. 8 . Both the left track 70 and the right track are preferably fastened to the storage module 16 with multiple screws, but may alternatively be fastened with other suitable devices, such as adhesives or snap-together parts. Both the left track 70 and the right track preferably include an upper rail 72 and a lower rail 74 . The upper rail 72 preferably engages the slide member 30 of the upper module 12 , while the lower rail 74 preferably engages the slide portion 42 of the lower module 14 . In this manner, the upper module 12 is slidable between a forward position (shown in FIG. 1) and a rearward position (shown in FIG. 2 ), while the lower module 14 is slidable between a rearward position (shown in FIG. 1) and a forward position (shown in FIG. 2 ). Because the upper module 12 extends substantially upward from the slide member 30 and because of the distance between the upper rail 72 and the lower rail 74 , the upper module 12 and the lower module 14 are slidable relative to each other. The guide track 18 is preferably made from a stiff material, such as a plastic material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods.
With the upper module 12 in the forward position and the lower module 14 in the rearward position (shown in FIG. 1) or with the upper module 12 in the rearward position and the lower module 14 in the forward position (shown in FIG. 2 ), the rear section 52 and the front section 50 of the storage module 16 are concealed. To access the rear section 52 of the storage module 16 , both the upper module 12 and the lower module (hidden under the upper module) are moved to the forward position, as shown in FIG. 5 . Likewise, to access the front section 50 of the storage module 16 , both the upper module 12 and the lower module 14 are moved to the rearward position, as substantially shown in FIG. 6 .
As shown in FIGS. 4 and 7 through 10 , the console assembly 10 of the preferred embodiment of the invention also includes a latch module 76 . The latch module 76 functions to selectively hold the upper module 12 in a particular position along the guide track 18 . The latch module 76 preferably includes a latch member 80 , and a release member 82 . Alternatively, the left track 70 may be integrally formed with the right track. The guide track 18 is preferably made from a strong material, such as a metallic material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods.
The guide track 18 preferably includes a rearward notch 84 and a forward notch 86 , but may alternatively include one or more notches in other suitable locations. The particular location of the rearward notch 84 and the forward notch 86 allow the upper module 12 to be selectively held in the rearward position and the forward position. The latch member 80 of the latch module 76 functions to engage the rearward notch 84 and the forward notch 86 of the guide track 18 . The latch member 80 preferably includes a mounting arm 88 , an engaging arm 90 , a biasing spring 92 , and a large opening 94 . The mounting arm 88 is preferably mounted to the substrate member 26 of the upper module 12 for rotational movement about a peg 89 defining a first pivot axis 96 . The engaging arm 90 preferably extends downward through the upper module 12 towards the guide track 18 . The latch member 80 is rotated about the first pivot axis 96 in direction A, when the pegs 89 are located in the sockets 27 .
In a preferred embodiment, the biasing spring 92 of the latch module 76 is a torsional spring and is located on the peg 89 adjacent the mounting arm 88 to bias the latch member 80 in direction A. In an alternative embodiment, the biasing spring 92 may be a leaf spring or any other suitable device located adjacent the engaging arm 90 or any other suitable portion of the latch member 80 . The latch member 80 is preferably made from a strong material, such as a plastic material, and with conventional methods, but may alternatively be made from other suitable materials and with other suitable methods.
The release member 82 of the latch module 76 , which functions to disengage the engaging arm 90 of the latch member 80 from the guide track 18 , preferably includes mounting pegs 98 , a first lever 100 , a second lever 102 , a forward contact 104 , and a rearward contact 106 . The mounting pegs 98 are preferably mounted to the stand-offs 29 of the substrate, member 26 of the upper module 12 for rotational movement about a second pivot axis 108 . The first lever 100 and the second lever 102 preferably extend outward from the release member 82 , one in a forward direction and one in a rearward direction. When the release member 82 and the latch member 80 are mounted to the substrate member 26 , the release member 82 preferably extends through the large opening 94 of the latch member 80 and the first lever 100 and the second lever 102 preferably extend under the latch member 80 . With this arrangement, if the release member 82 is rotated forward about the second pivot axis 108 in direction B, then the second lever 102 moves direction C and raises the latch member 80 and disengages engaging arm 90 from the rearward notch 84 of the guide track 18 . Likewise, if the release member 82 is rotated rearward about the second pivot axis 108 in direction D, then the first lever 100 moves in direction E and raises the latch member 80 and disengages the engaging arm 90 from the notch 86 in guide track 18 .
The forward contact 104 and the rearward contact 106 of the release member 82 function to provide ergonomic contact surfaces to rotate the release member 82 forward and rearward about the second pivot axis 108 and to slide the upper module 12 into a particular position along the guide track 18 . In this manner, when the upper module 12 is in the rearward position, a vehicle occupant may extend a thumb into the release member 82 and push on the forward contact 104 thereby disengaging the latch member 80 from the guide track 18 and sliding the upper module 12 towards the forward position. Likewise, when the upper module 12 is in the forward position, the vehicle occupant may extend several fingers into the release member 82 and pull on the rearward contact 106 thereby disengaging the latch member 80 from the guide track 18 and sliding the upper module 12 toward the rearward position. This feature allows one-handed operation to disengage the latch module 76 and slide the upper module 12 .
In the preferred embodiment of the invention, as shown in FIG. 1, both the exterior panel 48 of the storage module 16 and the exterior member 28 of the upper module 12 coordinate with a center protrusion 110 of an instrument panel 112 of the vehicle interior 24 . In this manner, the exterior panel 48 preferably extends to cover a portion of the center protrusion 110 of the instrument panel 112 , while the exterior member 28 provides a smooth transition with the center protrusion 110 of the instrument panel 112 . In other words, the console assembly 10 preferably mates with the instrument panel 112 of the vehicle and acts as an extension of the center protrusion 110 between the driver-side seat 20 and the passenger-side seat 22 . In an alternative embodiment, the console assembly 10 may mate with another suitable component of the vehicle interior 24 .
The foregoing discloses and describes preferred embodiments of the present invention. One skilled in the art will readily recognize from such description, and from the accompanying drawings and claims, that changes and modifications can be made to the invention without departing from the true spirit and scope of the invention as defined in the following claims. | A console assembly includes: a storage module ( 16 ) having an interior compartment for holding items, an upper module ( 12 ) for storing items and a lower module ( 14 ) having a recess for holding items. The lower module ( 14 ) is connected to the storage module ( 16 ) in a track and translates across the opening into the interior compartment of the storage module ( 16 ) to selectively allow access to a portion thereof. The upper module ( 12 ) includes a storage area having a beverage holder and an ashtray. The upper module ( 12 ) is also connected to the storage module ( 16 ) in a track and translates independently and over the lower module ( 14 ) such that the upper module ( 12 ) can be located above the lower module ( 14 ) to provide an access to the interior compartment of the storage module ( 16 ) or the upper module ( 12 ) can be located away from the lower module ( 14 ) such that the upper module ( 12 ) and lower module ( 14 ) close the access to the interior compartment of the storage module ( 16 ). A latch module disposed in the upper module ( 12 ) holds the upper module ( 12 ) in position with respect to the storage module ( 16 ). | 1 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This continuation-in-part patent application claims priority to the regular patent application having Ser. No. 11/348,639, having filing date Feb. 7, 2006.
FIELD OF THE INVENTION
[0002] This invention relates generally to containers for the planting of flowers or potted vegetation, and more specifically pertains to a series of such pots which are stackable one upon the other, or in a plurality of parallel and adjacent erected positions, with each container incorporating a space for holding a quantity of planting soil, and having a water reservoir therebelow, with a segment of the soil continuously being exposed within the water reservoir to provide for moisture absorption and transferring upwardly into the potting soil, to sustain the watering of the implanted plants, over a substantial period of time.
BACKGROUND OF THE INVENTION
[0003] Varieties of plant containers, and other types of containers for holding planted flowers, herbs, vegetation, and the like, have long been available in the art. Some of these pots are more than just for use for planting purposes, but also incorporate means for providing the absorption of moisture into the potting soil, in order to sustain a continuous moisture watering and growth of the supported plant, throughout its vegetative life cycle. In addition, certain of said plant pots have been of the stackable type, where the pots can be stacked one upon the other, in a staggered fashion, and thereby still allow for the plants to grow within the pots at each level of implantation, and at the same time, allow for water to cascade down between the stacked pots, to assure that moisture is provided at each pot level, to sustain such continuous growth.
[0004] Various types of stackable pots have been available in the art. For example, the International patent application No. PCT/AU98/00432, discloses a plant pot, which, in use, is adapted to be stacked with one or more similar plant pots. The shape, appearance, and ornamentation of the plant pot shown therein, and its stackability feature, have been commercially marketed in the United States and throughout the world since 1996. It shows a plant pot which includes an upper rim made of lobe sections and bridge sections, a base portion, and a surrounding wall, extending between the upper rim and the base portion, shaped as so to define a plurality of radially extending lobe sections. The base portion includes a recess, formed in the underside of each lobe section. The upper edge and recesses are configured in such a way that when two or more plant pots are stacked, the rim and the recesses of a plant pot, and its subjacent pot, inter-engage and can be positioned together to hold the pots firmly in place. Thus, that shaped pot, as shown therein, has been available for many years in the art.
[0005] Other types of stackable plant pots, in addition to plant pots that furnish self watering features, have also long been available in the art. Such can be seen in the published application WO1998/056233, to Keats, which shows stackable plant pots. In addition, the Johnson, U.S. Pat. No. 3,452,475, shows related structure. In addition, the United States published application to Klein, US2001/0052199; in addition to the patent to Morrow, U.S. Pat. No. 4,012,081, show related type of structures. Certain foreign applications likewise show similar type structures. Such can be seen in the German patent No. 2704414, to Albrecht. The French patent to Marque, No. 2715269, shows related structure. The British patent to Stone, No. 2369980, shows stackable plant pots. The German patent to Henke, No. 3618833, in addition to the European patent No. 0142471, to Gerber, shows similar structure.
[0006] Earlier U.S. patents shows variations upon plant pots, some which may be stackable, and others which may include self watering features. Such can be seen in the Baldwin U.S. Pat. No. 129,451, which shows an improvement in flower pots. This particular pot shows a false floor, in the configuration of a fan-shaped disc, with crown like projection, and which extends up into the potting soil, such that when water is introduced into its lower chamber, moisturization can take place to keep the potting soil moist.
[0007] The Kneller, U.S. Pat. No. 2,055,844 shows another self watering flower vessel. It also includes a false floor or bottom, for separating the water area in the bottom, from the soil arranged upwardly in the pot.
[0008] The Magid, U.S. Pat. No. 2,810,235, shows a flowerpot and jacket for the same. This also includes a pot, which sits upon a plate, where the water flows into the bottom of an outside container, and also uses a wick that extends upwardly into the soil to provide for wicking thereat.
[0009] The Gallo, U.S. Pat. No. 3,076,290, shows a series of stackable flower pots.
[0010] The Mills, U.S. Pat. No. 3,686,791, shows walls, screens, and the like, formed as stackable members, for use as multiple flower pots. This particular patent also shows father fluted like pots that can be stacked, staggered, one upon the other, so that it's various flutes are exposed for the growth of vegetation thereat.
[0011] The Anderson, U.S. Pat. No. Des. 243,031, shows a design for a stackable flower pot.
[0012] The Pearce, U.S. Pat. No. 4,117,632, shows another plant watering pot, wherein a lower dish or pan holds a quantity of water, and a series of wicks provide for absorbing moisture up into the potting soil.
[0013] The Smith, U.S. Pat. No. 4,236,351, shows another planter with tubular air hole members. This particular receptacle has a dividing wall between a lower compartment, which drains excess water, and the soil as provided thereabove. The various tubes shown therein are designed to evaporate excess water, through the tubes, and keep the soil moist.
[0014] The Peterson, U.S. Pat. No. 4,346,532, shows another style of planter.
[0015] The Farkas, U.S. No. 4,614,056, shows various stacking planters. This device is formed of dual planting pots, stacked one upon the other, with a bottom tray.
[0016] The Mason, U.S. Pat. No. 4,779,378, shows an integradable, modular stackable multi-plant holder. Once again, this is a stackable type of three plant receiving receptacles on each level, and which receptacles can be stacked, one upon the other, as can noted.
[0017] The Mason, Jr, U.S. Pat. No. Des. 306,985, shows a design for a plant container unit.
[0018] Another Mason, Jr., U.S. Pat. No. Des. 309,878, is a further design upon the shown plant container. This particular design has the appearance of various flutes, and apparently allows for growth of vegetation upwardly out of said flutes, during usage.
[0019] The Kang, U.S. Pat. No. 5,136,806, shows a flower pot and water supplying member for the flower pot. This device has a false bottom, with water collecting therebelow, and potting soil arranged thereabove, with a moisture absorbing material extending from the lower water reservoir up into the soil.
[0020] The plant container water water-keeping assembly of Lui, as shown in U.S. Pat. No. 5,644,868, shows a plant pot with a false bottom, and a series of water or ventilating tubes, as can be noted.
[0021] The Hulsebus, U.S. Pat. No. Des. 382,512, shows a design for another planter. It appears that it may include a false bottom, with perforations therethorugh, and a center well that apparently is for reception of soil.
[0022] The Hsu, U.S. Pat. No. 5,819,469, shows a support plate for flower pots that prevents overflow and inhibits mosquito propagation. This is apparently a support for flower pots, which does include wheels or rollers to provide for its motivation.
[0023] The Klonel, et al, U.S. Pat. No. 6,128,853, shows a ball wheeled planter and method.
[0024] The Buss, U.S. Pat. No. 6,357,179, shows another self watering planter, where apparently soil extends down into the lower portion of the planter, as can be seen.
[0025] The Bradley, U.S. Pat. No. 6,520,366, discloses a beverage container holder.
[0026] The Powell, et al, U.S. Pat. No. 6,612,073, shows an intensive plant growing stacking container system. This device also shows a fluted plant pot, where apparently plants can be grown in the radially extending flutes, and the pots apparently can be stacked one upon the other, and also nested, as can be noted.
[0027] The design Pat. No. Des. 493,384, to Jensen, shows another stackable planter, with three planters being stacked one upon the other, and a tray provided underneath of the composite.
[0028] The Bullock, U.S. Pat. No. 6,840,008, shows a vertical planting system.
[0029] The Merayo, U.S. Pat. No. Des. 505,881, shows the design for a rolling plant and tree container.
[0030] The Australian patent No. 634522, to Grow-Max Systems, Inc., shows another arrangement for growing plants. This arrangement shows a series of stacked pots, one upon the other, for growing a multiplicity of plants, from at least three containers, and which allows for drain means between the various stacked containers to allow excess fluids to drain into the container located immediately therebelow.
[0031] Other patents show plant containers, of the individual type, such as in U.S. Pat. No. 4,102,081, to Morrow, which shows a plate above the bottom of the container for allowing excess water to pass therethrough, to avoid over saturation of the soil, and which is available for moisturization purposes.
[0032] The U.S. Pat. No. 3,452,475, shows another self-irrigated planter.
[0033] These are examples of a variety of published applications, patents, and the like, throughout the world, which show related technology.
SUMMARY OF THE INVENTION
[0034] This invention relates principally to variations added to the structure of stacking plant containers, which can be stacked one upon the other, have self moisturizing features constructed into its base portions, so that the potting soil within each plant pot remains reasonably moist, over extended periods of time, even though watering may not occur for lengthy periods.
[0035] The contents of the components of this invention, and their assembly for usage, can generally be summarized as follows:
[0036] a) the moisture absorbing and transferring self watering structured plant containers of this invention include a series of vertically stackable planters, two or more in number, that may be stacked vertically, in usage;
[0037] b) the vertical stackable planters can be applied to a lower planter or tray planter, that may mount directly onto or be pressure fitted upon the rail of a deck railing, porch railing, or like, to provide an assembly of planters that may be used and displayed in that manner;
[0038] c) the structured plant pots and planters of this invention may likewise be used in conjunction with a lower tray, which may be either stationarly located for reception of the variety of the planters, and planters stacked thereon, or the tray may include a series of casters, to make it a wheeled structured, to facilitates its movement and shifting, rather easily, when desired to provide for its relocation; and
[0039] d) all of the above assembly of trays, lower planters, planting containers, stackable pots, and the like, will include a slotted or perforated elevated base, that fits respectively into any one of the variety of containers previously referred to, and each base including one or more downwardly depending integral wells, into which moisture absorbing and wicking potting soil may be contained, for use for the migration of moisture upwardly into each planter, through its potting soil, for the watering of the root systems of any of a variety of plants or vegetations provided therein. This invention contemplates the formation of stacking pots, of the type of containers that are used to plant flowers, and other vegetation, and where the pots may be used individually, or in combination, stacked one upon the other, in order to assure constant moisturization of the potting soil holding the variety of vegetation, at the various levels, during usage. Each pot has a multi-shaped configuration, from an opened upper lip that extend around its entire periphery, and each pot tapers downwardly, into a base portion, where it pressure grips onto the lip of the subjacent planter, in order to reasonably hold the stacked containers together, during usage. There is a bottom tray that is applied underneath all of the stacked pots, and the tray may either be for mounting thereabove an individual vertical column of stacked pots, or the tray may be elongated, and hold erected rows of stacking pots thereon, so that the stacked pots may be erected upwardly, in two or more vertical columns, during their usage.
[0040] The trays provided underneath of the stacked pots, and regardless whether they be stacked in a singular or double column, are designed for either having rollers or castors provided thereon, upon their underside, in order to facilitate the movement of the stacked containers around the floor, patio, and the like. Furthermore, select of the trays are designed to accommodate their mounting onto a railing of a porch, or deck, so that the planters may be utilized even at that location, to enhance the beauty of the residence or building, during their application and usage.
[0041] One of the primary features of this invention comprises the usage of a uniquely shaped elevated base, one that sits within the approximate bottom of a container, and which includes an aperture therethorugh, so that it may be positioned, centrally, within the pot, during usage. The elevated base has a series of opening provided therethrough, and which allows for water and other moisture, excessively, to pass therethrough, and into the bottom of each container, for retention therein, and which moisture is available for further wetting of the potting soil, arranged upwardly thereof, within the pot, to sustain the life of any plants, and to assure that adequate moisture is provided thereto, over an extended period of time. Each elevated base has a unique shape formed having one or more integral wells provided therein, and extending downwardly into the central water reservoir, so that the potting soil that is arranged above the elevated base, and which extends down into each well, that soil within the well will be continuously exposed to the water, to provide for the absorption and migration of moisture upwardly, to sustain the wetting of the potting soil, during usage. Each elevated base extends outwardly to the inner proximate surface of the flutes formed of each planter, and the purpose for this is to sustain the potting soil thereabove, but yet allow and provide sufficient clearance for excessive water to enter downwardly into each pot; preferably at the central location where the water reservoir collects the water for further moisturization of the potting soil, but that the water at the outer edge of the elevated base, when it bypasses that portion of the base, and enters downwardly into the bottom of the pot, such accumulated water is allowed to drain from the planting pot into one or more planters arranged and stacked therebelow, in order to provide for multiple planter watering, whenever moisture is added to the upper planters, during usage. Furthermore, the contiguousness of the elevated base in proximity with the inner surfaces of the lower planter, internally thereof, further prevents the creation of flow paths, which under certain circumstances could allow for insects, such as mosquitoes, from entering into the central water reservoir, and forming a breeding ground thereat. Hence, the technical design of the elevated base as structured into the formed planters of this invention have attributes far beyond just functioning as flower pots, and not only furnish means for maintaining the critical moisturization of the potting soil within each planter, to channel excess water into the central reservoir region, which extends soil wells into the water, so as to constantly moisturize and wick water upwardly into the potting soil, while at the same time, acting as a hindrance against providing a breeding ground for insects, during usage. Furthermore, the main supporting trays for the stacked pots can either be applied and held onto a railing, one of standard size, or the wheeled structure for the modified tray allows for the easy transfer of all of the stacked pots, which may collectively have significant weight, to other locations, as desired.
[0042] It may also be commented that wicks, such as made of fabric, cotton, paperboard, or any other wicking material, may be used for extension through the elevated base of each planter, for assisting in migration of water contained within a container's reservoir to migrate upwardly into the potting soil, to further aid in the retention of its moisturization, and preservation of any plant life that is planted therein.
[0043] It is, therefore, the principle object of this invention to provide a series of stacking planter containers, that may be stacked one upon the other, either in single, double, or more vertical columns, applied to a tray, with each planter having an elevated base provided therein that allows for continuous integral moisturization of the potting soil within each planter, during usage.
[0044] Another object of this invention is to provide an elevated base for use within a planter that controls the migration of water and moisture, channels it towards the reservoir, but does not contract the potting soil that allows insects, or the like, to descend therein to the water for breeding purposes.
[0045] Another object of this invention is to provide a series of stacking planters, that may be applied and rested upon a floor or deck, or which may embrace a railing, during their usage.
[0046] Another object of this invention is to provide a series of stackable planters, which are self watering.
[0047] A further object of this invention is to provide a series of planters that when water is applied to the top planter, there is natural watering of all the subjacent planters, during usage.
[0048] Still another object of this invention is to provide a planter pot that functions to bring moisture up to the plants, through the potting soil, from a water reservoir maintained therebelow.
[0049] Still another object of this invention is to provide planters that allow for excess water to drip down to the planters provided therebelow.
[0050] These and other objects may become more apparent to those skilled in the art upon review of the invention as summarized herein, and as explained in the description of the preferred embodiment, in view of the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0051] In referring to the drawings,
[0052] FIG. 1 provides an isometric view of a series of three vertically stacked planters stacked upon an underlying tray;
[0053] FIG. 2 is a top plan view of FIG. 1 ;
[0054] FIG. 3 shows a series of planters mounted onto a railing planter tray;
[0055] FIG. 4 shows the series of planters and planter base all resting upon an underlying tray;
[0056] FIG. 4 a is a sectional view of a tray, also showing casters to provide and facilitate for its movement;
[0057] FIG. 5 is a top plan view of the planters and planter base;
[0058] FIG. 6 is an underside perspective view of an elevated base, with integral soil wells, that locates within each planter containers;
[0059] FIG. 7 is a top plan view of the elevated base of FIG. 6 ;
[0060] FIG. 8 is a side view thereof;
[0061] FIG. 9 discloses how the elevated bases may nest one upon another;
[0062] FIG. 10 is a sectional view of three stacked planter containers each showing its elevated base provided therein;
[0063] FIG. 11 is an isometric view of the planter base tray as shown in FIGS. 3 and 4 ;
[0064] FIG.12 is an inverted view thereof;
[0065] FIG. 13 is a plan view of the sloped elevated base that locates within the planter tray of FIG. 11 ;
[0066] FIG. 14 is a front view of the elevated base of FIG. 13 ;
[0067] FIG. 15 is a sectional view of part of the outer bottom of a container flute, showing its locking slot for engagement of a planter to its tray;
[0068] FIG. 16 provides a fractional view of a segment of the bottom of a planter base tray, showing the locking mechanism for attachment of the tray to a deck or porch rail;
[0069] FIG. 17 shows a fractional view of the planter base tray with a spacer means to allow the tray to be locked onto a narrower rail;
[0070] FIG. 18 shows the locking mechanism in an isometric view;
[0071] FIG. 19 is a top plan view of the locking mechanism;
[0072] FIG. 20 shows the spacer means of FIG. 17 , that engages with the base tray to allow it to attach to a narrower rail; and
[0073] FIG. 21 is a top plan view of FIG. 20 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0074] In referring to the drawings, in particular FIG. 1 , the basic assembly of the stacking containers 1 of this invention is readily disclosed. In this instance, it shows three containers, 2 , 3 and 4 , stacked one upon another, in staggered fashion, with all the pots being assembled for resting upon the lower tray 5 , as can be seen. More or less than three containers may be used. The stacked containers are more aptly disclosed in a top plan view in FIG. 2 . As can be seen, each container 4 is arranged approximately forty-five degrees from the location of the container 3 , so that the fluted sections of a pot will be arranged in alignment with the inturned portion of each pot, as can be noted. For example, the fluted or extended portions of each container can be seen at 6 , while the inturned portions can be noted at 7 . Hence, as noted, the flutes of container 3 are aligned with the inturned portions 7 of the container arranged thereabove.
[0075] It should be noted that the shape and configuration for these containers has been available, publicly, since the mid-1990's, for use for stack potting purposes.
[0076] Each of the containers has its shown reinforced upper lip, as at 8 , and each container then tapers downwardly, along the walls 9 , to a narrowing dimension. At the bottom of each container is a downwardly extending segment, as at 10 , and inwardly, integrally formed therewith, is a depending extension 11 . Thus, the space intermediate the downward extension 10 , and the dependent portion 11 , as can be noted at 12 , provides a clearance slot for use for embracing the upper rim 8 of the container arranged therebelow, to provide for a snug fit therein, and even some frictional connecting, to assure the stacked containers are held together, when assembled in the manner as showing in FIG. 1 . In addition, the downward extension 10 forms a well internally of the flute 6 for each planter, and each includes a series of slots, one for providing drainage downwardly from each well, but likewise, to furnish means for locking with the upward extensions 13 , provided upon each tray, for assuring that the bottom planter 2 is locked in place with its lower tray 5 , when assembled: In addition, the depending portion 11 , of each planter, and there being one associated with each of the flutes 6 of each container, and centrally inwardly thereof, forms a water reservoir at the bottom of each planter, so that any water that enters therein, remains centrally of the planter, and functions as a source for moisturization of the soil contained within each planter, in a manner to be subsequently described.
[0077] As can be seen in FIG. 2 , there is an elevated base, as at 14 , that rest within each planter. The base mounts on to a central cone shaped upward projection 15 , and each base has radially extending segments 16 , that flare outwardly, as can be seen at 17 , for embracing the inwardly grooved areas 18 of each planter, as can be noted. Thus, the elevated base is contiguously arranged internally of each container, and is located in close proximity with the encountered walls of each of the containers, as can be noted. Thus, soil that is placed upon the elevated base, and which fills up the open interior of the container arranged thereabove, cannot shift past the elevated base, and get into the lower water reservoir, thus preventing soil from clogging up the lower water reservoir, and to prevent the stacked planters from performing in a manner of their design. Each of the elevated bases includes a series of slots, as at 19 , and such can also be seen in FIGS. 6 and 7 . Thus, any excess water that is added into a planter, for irrigating its soil, and which drains to the bottom of the contained soil, will encounter the elevated base 14 , and pass therethrough, for collection within the lower water reservoir, as defined.
[0078] As can further be seen in FIG. 2 , the radially extending segments 16 , at their outer extremes, are of a flattened surface, as noted at 16 A, so that when moisture migrating down from the planter above encounters this area, it has a tendency to flow inwardly, towards the slots 16 B, so that the water that accumulates at that location will be deposited into the water reservoir centrally of the bottom of the planter, and be retained therein for moisturization purposes. It can be seen, as previously explained, that the outward radially extending flared portions of the elevated base, as noted at 17 , are in very close proximity with the interior of the planter in which they set, so that water will migrate onto the flat surface 16 A, and not just simply drain to the bottom of the planter, within its outer water wells 22 , and simply drain into the planter below. Hence, because moisture remains accumulated at these regions of the planter, above the elevated base, it keeps the soil moist, does not let it dry out or shrink away from the interior walls of the planter, which would otherwise allow water to simply drain right down into the planter therebelow.
[0079] It should also be noted that the elevated bases includes a series of downwardly extending wells, as at 20 , and these wells each include a series of slots, as at 21 , so that when soil is added into the planter, for filling its container, it will also fill up each of the wells 20 . Hence, since these wells extend downwardly, and down into the water reservoir, any soil contained therein will be exposed to the water within the lower reservoir, which migrates through the slots 21 , and thereby sustains wetness of the potting soil at that location. Since potting soil usually has a high moisture retention contend, since it frequently may contain other ingredients in its mixture, such as zeolite, or other moisture absorbing ingredients, such that the moisture absorbed into the potting soil within each well also migrates upwardly into the potting soil contained within the planter, so as to provide further irrigation for the root system of any plant that is planted within the container, during its usage. The bottom of each well 20 , extends downwardly into the water reservoir, as is arranged approximate the bottom of the containers, either 2 , 3 , or 4 , in which it is installed.
[0080] As can also be noted in FIG. 9 , these elevated bases 14 are capable of nesting, so as to facilitate their storage, transit, and even display as during sale, or usage, in combination with their planters, and their other components for each stacking pot. As can also be understood from reviewing FIG. 1 , when the stacking planters, or there containers, are aligned with each other, and are not arranged at a forty-five or sixty degree angle from each other, they likewise are capable of nesting one within the other, so as to facilitate there stacking, nesting, storage, shipment, packaging, and display for sale.
[0081] FIG. 10 displays how each of the containers 2 , 3 , and 4 mount and stack one upon the other. When doing so, it can be seen that the outer water well, as previously described, can be noted at 22 . As previously explained, this is formed within the lower extension 10 , for each of container. Likewise, the downwardly extension 11 provided for each container, and which forms the outer boundary of the water reservoir 23 , forms a lower opening into which a downwardly extending well 20 locates, when the container is properly aligned, and the planters are stacked vertically one upon the other, in their staggered fashion as previously reviewed. The lower and centered cone 15 , integrally formed of the bottom of each container, can be noted, and it provides a stable member upon which the elevated base 14 , for each container, locates, when it is inserted within its respective container, in preparation for filling of the planter with potting soil, for the eventual planting of plants, or other vegetation. A weir, 55 , of FIG. 10 , separates the water reservoir 23 , from the outer water well, as at 22 , as noted.
[0082] These are examples of how the various molded components for the containers, and their elevated bases, all cooperate together to provide for a convenient locating of each planter, one upon another, when they are staggered, and assembled, in preparation for their reception of plants.
[0083] A variation upon the planter of this invention can be seen in FIG. 3 . The containers 24 are the same configuration and design as the containers 2 , 3 , and 4 , as previously described. But, in this instance, a bottom planter 25 has a unique shape of furnishing a central planting area 26 , and a pair of integral side planters 27 and 28 . As such, and as can be noted, the contours for the upper rim of the lower planter 25 are such that the outer portions are contoured to accept and mount in a mating fashion thereon the planters 24 , as noted. Thus, flowers may not only be planted within the upper planters 24 , but they may likewise be planted within the outer planter fluted portions 27 and 28 , and in addition, vegetation may be planted within the central planter area 26 , as can be understood.
[0084] The bottom planter 25 , for the embodiment as shown in FIG. 3 , is also disclosed in FIGS. 11 and 12 . As can be seen, it includes a uniquely configured bottom contoured area, which includes spaced apart lower extensions, which may hold moisture, these extensions noted at 29 . The spacing, as at 30 , provided between these lower extensions is molded precisely to the dimensions that allows for the lower planter, when arranged in its up right position, to mount snuggly upon an upper rails R for a deck railing, as can be understood (see FIG. 3 ). Thus, the combination of lower planter 25 , and one or more containers 24 , may be elevated vertically, even stacked one on top of the other in a manner as shown in FIG. 1 , and be utilized in that manner, as a complete stacked multiple planter system, but yet be secured upon and snuggly held onto the rail or, in their installation. As noted in FIGS. 13 and 14 , an elevated base 31 is uniquely contoured in order to fit snuggly within the interior of the lower planter 25 , and this base also includes a series of slots, as at 32 , so that excessive moisture may drain into the bottom, as at 33 , of said lower planter or tray. In addition, there are a series of integrally formed and downwardly slotted wells 34 , as can be noted in FIG. 14 , and these wells are designed for holding a quantity of the potting soil, and said wells extend downwardly into the water reservoir 33 provided within the bottom of the lower planter tray 25 , so as to absorb moisture therein, and wick the water upwardly, within the potting soil to provide continuous moisturization to the root system of any plants that may be planted within this lower planter 25 . In addition, any excess moisture that is generated because of over watering within the containers 24 , of FIG. 3 , will likewise drain downwardly, into the water reservoir 33 of this lower planter 25 , during usage and function to add any moisturization to any plants planted therein.
[0085] FIG. 4 shows how the lower planter 25 , instead of mounting onto the rail R, may have its own lower tray, as at 34 , to hold the lower planter 25 therein, and to allow for stacking of additional containers, as at 24 , thereon, during assembly and usage.
[0086] FIG. 4 a shows the configuration of the lower tray 34 , and how it may contain a series of caster, as at 35 , to allow for the tray and the assembly of its lower planter 25 , and additional planters 24 , to be moved around a floor, deck, patio, and the like to facilitate it usage and application.
[0087] FIG. 15 shows the enlarged bottom of the downward extension 10 at the bottom of a flute for one of the containers. It shows the lateral slot 36 into which the locking means 13 engages, for locking a planter in place, within its tray. In addition, there are a series of further slots 37 provided across the bottom of the lower extension 10 , so that any water that accumulates therein may drain downwardly, into the next planter therebelow, or into the tray 5 , during usage.
[0088] It can also be seen in FIG. 10 that various wicks, as previously described, as noted at 38 , can be provided through the elevated bases, to aid in the migration of water contained within the containers reservoir upwardly into the potting soil, to add further moisturization therein.
[0089] FIG. 16 shows a partial view of the bottom of the planter base tray, such as previously disclosed in FIGS. 11 and 12 , and in this particular instance, this particular tray is designed for attachment to a rail of wider dimension, such as one formed of a two inch by six inch or related structure. This is the type of rail that may be provided upon the top of a railing, such as upon a porch, deck, patio, or other structure. Essentially, the tray, which is actually the lower planter 25 , has the lower spacing 30 provided therethrough, as previously reviewed, and a deck rail, such as the type as just previously described, can snuggly fit therein, when the tray is in the position as shown in FIG. 11 , and inserted onto the rail, during its application and usage. At that stage, since the planter may have a center of gravity that may be substantially above the rail, particularly when additional planters may be stacked thereon, it is desirable to provide means for engagement of the lower tray, onto the rail, so as to prevent any tipping or falling therefrom. Hence, a locking mechanism, as at 39 , is provided, on both sides of the bottom of the tray, and once fastened in place, can engage the rail, upon its underside, and thereby lock the planter in place, so as to prevent its untimely loosening, such as when a person may brush against it, inadvertently, while participating in some activity upon the deck, or the like. The locking mechanism is more aptly disclosed in FIG. 18 , and FIG. 19 . As disclosed, it includes a length of sleeve, as at 40 , which incorporates a lower base, as at 41 , and which is stepped interiorly, simply to provide for its enhanced seating within the slot, as at 42 , provided on either side of the tray. A fastening means, such as the screw 43 , locates down into the opening 44 of the sleeve, and locates through the opening 45 provided through the bottom of the mechanism, and can be firmly screwed and tightened in place, threading into the base of the slot 42 , so as to lock the locking mechanism in place. When in use, the locking mechanism has a lateral tab, as at 46 , which is integrally formed with the sleeve 40 , and that segment locks under the rail, so as to engage the tray into place.
[0090] As can also be noted, there is a clearance slot 47 provided to the side of the slot 42 , and it has sufficient dimensions and length so as to allow the tab 46 , as when not in use, to be pivoted to the side, when the screw 43 is loosened, and be tightened therein, when the locking mechanism may not be needed.
[0091] As an alternative, when the planter base tray 25 is to be mounted onto a railing of smaller dimensions, such as a two inch by four inch board, then it is required that spacer means be provided for accommodating a smaller rail, during the application of the planter assembly to the railing structure. In this instance, a spacer means, as can be seen at 47 , in FIG. 20 , is applied into the slot 30 that accommodates the insertion of the rail therein, and provides for a narrowing of the space that provides for snug locating of the railing therein, generally in the manner as can be seen in FIG. 17 . In this particular instance, the spacer means has various angular shapes, in order to fit accommodatingly within the area of the slot 30 just adjacent to the wall 48 of an extension, as at 29 , as previously described with respect to FIG. 12 . The spacer means is an amorphous shape, but yet is very accommodatingly located within that space 30 , and contiguous with the wall 48 , to allow for the extension 29 to provide a narrower dimension between it and the spacer means attaching to the opposite side of the slot 30 . Thus, a two by four type of rail will be snuggly located between the surface 49 of the spacer member 47 , as shown and a corresponding surface upon the spacer provided at the opposite side of the slot, as can be understood. In this particular instance, each spacer member has an integrally formed sleeve like member 50 , similar to the sleeve 40 as previously described, with an opening 51 provided therein, and into which a fastening means, such as one of the screws 43 , can locate, and threadedly engage down into the tray 25 , in the manner as previously described for the locking mechanism 39 . Once the spacer member 47 is engaged, then the planter may be located upon a two inch by four inch rail, or even a rail to any other dimension, as may be required under the circumstances, and a further locking member, equivalent to what has been described in FIG. 18 , can locate down into the slot 52 integrally formed therein, and that locking mechanism may be threadedly engaged into the threaded opening 53 provided in the bottom of the slot 52 , as can be noted, and as understood. FIG. 21 shows a top plan view of the spacer means 47 , with its various sleeve 50 , and slot 52 , formed therein, which provides for securement of the spacer means to the wall of the extension 25 , as previously reviewed.
[0092] Hence, with the use of a spacer member of the type as reviewed herein, the tray 25 can be accommodated on the upper rail of any deck railing, and be secured thereto, with the tray having sufficient versatility to accommodate the attachment of a type of spacer means as described herein, to allow the rail to have the tray locked in position thereon, as during usage, and prevent any untimely dislodgement of the entire stackable plant containers and their lower tray, from the same, during usage.
[0093] Thus, upon review of the structure of this invention, as described herein, you can be seen that the versatility of its assembly, application, and usage, even though the entire unit may be of significant weight, can hold a variety of planted vegetation, which sustains consistent moisturization of the root systems, and to provide a rather pleasing and attractive display of a floral pattern, for the home, business, and the like. The various adaptable usages of the stacking containers, as described, are intended to provide an illustration as to how its various components can be employed to furnish an overall planting system, that is convenient of assembly, usage, and planting of a multitude of flowers and other plants, after assembly.
[0094] Other variations or modifications to the subject matter of this invention may occur to those skilled in the art upon review of the invention as described herein. Such variations, and modifications, if within the spirit of this development, are intended to be encompassed within the scope of any claims to patent protection defined herein. The summary of the invention, its description in the preferred embodiment, and its depiction in the drawings, are set forth for illustrative purpose only. | A moisture absorbing and water transferring self watering structured planters, including a plurality of a tapering plant pots, capable of mounting one upon another in a staggered fashion, to provide a series of stacked planters, a bottom planter shaped to provide for its accommodations upon a deck rail, or the bottom planter may locate within a tray, even one that contains casters, to provide freedom for movement upon a patio, deck, or other floor. Contained within each of the stackable containers, and also within the bottom planter, is an elevated base, containing perforations, and a series of downwardly depending slotted wells, the latter into which potting soil may locate, for submerging into any water contained within water reservoirs provided within the bottom of each container, or bottom planter, to achieve migration of water upwardly into the potting soil, for irrigation and moisturization of the root system of any planted vegetation. | 0 |
This application is a continuation of Ser. No. 268,508 filed July 3, 1972 now abandoned.
BACKGROUND OF THE INVENTION
The field of the present invention is papermaking and more particularly the making of straw paper having high energy absorbing qualities and high resistance to tear.
Straw paper has been known for centuries and has been used in a wide variety of commercial applications. Straw paper is ordinarily grouped into two major categories. One category is paper made with grass straws. The other is paper made with cereal straws such as wheat, rice and rye. In this text the discussion will be confined to cereal straws although many of the methods described may be applicable to other types of straw utilized in paper making.
Papers made from cereal straw such as wheat and rice are employed in making corrugated medium, egg case stock, decorative wrappings and, when bleached, are used for high grade white papers such as bond, ledger paper and printing papers. However, paper made from straw is not considered to be suitable for sack or bag paper as straw fiber papers are unsuitable for applications where a high tear resistance is a requirement. Therefore, although some low strength decorative wrapping paper is made from straw fibers, high grade packaging and sack papers having a substantial constituent of straw fibers has not heretofore been made. It is well appreciated that a straw fiber paper which exhibits toughness and tear resistance is a desirable product. The instant invention describes such a product and discloses the method used to make it.
In addition, the instant invention allows for making a high basis weight straw paper whereas heretofore due to the slow draining characteristics of straw fiber it has been difficult to produce heavy weight straw paper.
SUMMARY OF THE INVENTION
The instant invention provides for the production of a new straw fiber paper with high tear resistance and high energy absorbing capabilities. Thus this new paper is particularly well suited to commercial applications where heretofore straw paper could not be used. The paper of the instant invention may be utilized in packaging or wrapping especially where tear resistance and toughness are requirements.
The new product is made in a process which includes digesting the straw fibers, washing the cooked straw, adding a proportion of other pulp such as softwood pulp in a thoroughly mixed furnish having at least 40 percent straw fibers, mixing in a rosin sizing where desired, passing the furnish to the forming wire in a specified consistency, consolidating the web on the wire with the aid of suction, further consolidating and partially drying the web and then, while the web is at a specified moisture content, upsetting the fibers of the web all generally in the plane of the web to still further consolidate the web by causing the fibers to crowd together and the straw fibers and the other fibers to intertwine, and then continuing the drying of the web.
In the instant invention the upsetting of the web fibers may be carried out in one direction only or alternatively may be carried out simultaneously or sequentially under the influence of forces acting in mutually crossing directions.
The product of the instant invention is recognized empirically by the particular intertwining of the fibers, by the presence of straw fibers in constituent amount in excess of about 40 percent of the total product weight, by the other fibers such as softwood fibers present and, under test conditions, by its tear strength and energy absorbing characteristics which are better than those of a typical straw paper of similar make-up but not produced according to the teachings of the instant invention.
The upsetting step of the method described herein may be carried out in a variety of ways, nevertheless as will be described later in more detail, the upsetting is preferably carried out in a pressure nip to which the web is fed in a tight draw and while the web is less thar about 50 percent wet. It is an aim of the instant invention to provide an improved straw paper.
A further object is to provide a method for making straw paper which is suitable for wrapping and packaging applications.
Another object is to provide a heavy basis weight straw paper.
Another object is to provide a method for making high basis weight straw papers.
A further object is to provide a high basis weight straw paper which exhibits high tear resistance and toughness.
To accomplish these and other objects of the present invention, the invention comprises the features hereinafter described and particularly set out in the claims, the description setting forth in detail certain illustrative embodiments of the invention. These embodiments are set out to show some of the ways in which the principles of the invention may be employed.
For a more complete understanding of the invention, reference should be made to the drawing wherein is shown an apparatus suitable for carrying out the process of the invention and making the product of the invention. The drawing is to be understood to be more or less of a diagrammatic character for purposes of illustration.
DESCRIPTION OF THE INVENTION
The instant invention will be described with respect to particular apparatus which may be used to produce the product of the invention. It will be appreciated that the various principles hereinafter described are applicable to other apparatus configurations.
Where reference is made to treated paper, the reference will indicate paper which has been made according to the process as set out herein.
The following description will be in connection with the drawing which shows the various apparatus elements used to produce the new straw paper. To begin the process, the straw to be used in making the new product must first be cut into the proper lengths. It is desirable that the straw be cut so that the majority of the pieces are in the range of approximately 1 to 3 inches in length. Preferably the pieces should be cut so that their lengths are fairly uniform to facilitate processing.
The cut straw will typically have many small loose fibers and dust particles as well as seeds and dirt. These impurities must be removed. The initial cleaning may be carried out by passing the cut pieces through a cyclone separator which removes the dust and loose fibers. This operation is followed by mechanical rolling or pressing to break the straw and to partially separate the fibers. Rolling and pressing aids in penetration of the cooking liquor in later processing.
Referring to the drawing, the cut and cleaned straw is passed to a digester or "cooker" designated generally as 10 upon a conveyor 11. The straw is metered into the digester through a metering system 12. Excess straw is carried off on a second conveyor 13. The straw delivered to the digester should be approximately 17 percent by weight and be fairly uniformly at this moisture. Wet washing may be used to produce a uniform moisture content. The above description has expressed the cutting, cleaning and moisture control as separate steps. All three steps may be carried out simultaneously in a pulper according to known means.
The straw, now clean, uniformly moist and cut, is typically sprayed with a metered amount of cooking liquor in a mixer-impregnator 14. In the mixer-impregnator the cooking chemicals are thoroughly intermixed with the straw. Ordinarily the cooking liquor contains sodium hydroxide and sodium sulfide. Where the former is used the process is termed a soda process and where the latter is used the cooking is termed a sulfate process. The use of one or another of these is generally determined by the availability of the chemicals. Cooking liquor recipes are well known. The sulfate process is probably preferred unless the pulp is to be bleached. However in high strength applications, high brightness is not usually a requirement.
The chemicals become thoroughly mixed and the straw is forced into a compactor 15 and then by a screw feed into pressurized digesting tubes 16 and 17. In the digesting tubes, the mixture of straw and chemicals is cooked in a live steam environment. There are ordinarily a series of such tubes though only two are pictured for purposes of illustration. In the horizontal tubes of the digester, the consistency of the mixture is approximately 10 to 12 percent straw.
At the outlet of the last digester tube, the straw-liquor mixture is forced abruptly into a tank 20 which results in a "fiberizing" of the straw. This abrupt passage of the straw into the tank is called blowing and serves to break up the straw pieces into fibers. Preferably the fiber length is in the range of approximately 0.70 to 4.00 millimeters in length. Thus the blowing carried forward the work begun in the digester. The straw is now ready for refining and mixing except for the presence of the digesting chemicals which must be thoroughly removed. Removal of the chemicals may be carried out in a washer by adding a substantial amount of clean water to the mixture of straw and chemicals to produce a consistency of about 3.5 percent. At this consistency the chemicals are washed from the straw pulp, typically by multi-stage vacuum filter and centrifugal cleaners. Once the cleaning has been accomplished, the water is squeezed out to return the pulp to about 12 percent consistency.
The pulp is then refined and mixed with pulp such as softwood pulp in a mixer 21. Additives such as rosin sizing may also be included where the end product application for the paper requires. After mixing, the various constituents are thoroughly interspersed in a furnish principally composed of cellulosic fibers which have been liberated to form a natural cellulose pulp. The consistency of the furnish is in the range of approximately 0.2 to 1.4 percent and it is at this consistency that the furnish is passed to the headbox 23 and thence onto the moving papermaking wire 24.
The drawing illustrates the suction box 25, the table rolls 26, couch roll 27, take-up roll 28 and four idler rolls all designated as 29. These elements along with the headbox and the Fourdrinier wire form the wet end or web-forming portion of the apparatus.
The furnish on the wire forms a wet mat as the water is removed. The mat is subjected to suction through means 25 which draws off the water from the mat as it moves along on the wire. Surface tension of the water being drawn from the mat, the natural bonding of the fibers and bonding caused by additives all combine at this point in the manufacture to begin the true formation of the paper web by consolidation of the fiberous structure.
A further consolidation of the web is carried out in the press section designated generally as 30 of the papermaking machine. The press section is made of a plurality of drying drums 31 over which the web W is passed. Associated with the drying drums is an upper felt 32 and a lower felt 33 along with various tensioning and guiding rolls for each felt or fabric. The felts serve to hold the web against the drums. The drums are ordinarily heated to assist in the drying of the wet. Due to the rather excessive fines and fiber debris in straw webs, the felts should be an open type with a high porosity. Also some means should be provided for continuous cleaning in order to keep the felts from clogging and thus inhibiting drainage of water from the web. There may also be used press rolls which serve to squeeze the water from the web and assist in consolidation of the web in the press section of the papermaking machine.
The water to fiber ratio of the web as it leaves the wire is approximately 4:1. This moisture must be reduced before the next major step in the web consolidation takes place. This next step is upsetting of the web fibers and should take place with the web moisture content in the range of approximately 30 to 50 percent wet by weight. An optimum wetness is considered to be about 37 percent.
The consolidating by upsetting of the fibers is carried out under forces which are applied generally parallel to the web faces while forces are simultaneously applied normal to the web surface. The result is that the individual fibers are crowded together and crimped and flexed upon themselves in a direction parallel to the web faces and entirely between the faces of the web.
This step can be best understood by reference to an apparatus which can be used to effect the individual web fiber upset. In general the preferred apparatus includes a soft surfaced roller or blanket which is urged against a hard, slippery surface. The soft surface is caused to recoil while against the hard surface. When the straw fiber web is placed in the nip formed by the two surfaces, this recoil causes the various web fibers to be moved generally randomly in the space between the web faces. More particularly the apparatus includes a thick elastomeric belt 40 which is carried by three idler rollers 41, 42 and 43. The idler rollers hold the belt or blanket against a large drum 44 about a part of the periphery of the drum. Bar 45 serves to press the blanket against the drum surface to form a localized pressure nip axially across the drum surface. The amount the blanket is wrapped around the drum is adjustable as is the nip bar pressure. The various adjusting means are not shown but are known in the art. As the belt 40 undergoes a reversal of its curvature in passing across the nip bar 45, the surface of the thick belt toward the drum is shortened and so moves slower than the drum surface. This difference in surface speeds causes a compression of the web fibers while at the same time the nip bar exerts sufficient pressure to prevent buckling of the web as a whole.
The belt or blanket is not driven independently by its own support rollers but rather by the engagement with the drum which is driven by means not shown in the drawing. The arc of contact of the belt must therefore be sufficient to provide the blanket drive. Since the amount of fiber upset is dependent upon the blanket contact or wrap as one of important parameters, the arc must be sufficient to provide the desired results.
An alternative means may include mating rollers, one elastomeric surfaced and one hard surfaced. The hard surfaced roll is driven while the elastomeric surfaced roll is braked. This arrangement creates the required elastomer recoil across the hard surface and the pressure which urges the two rolls into mating engagement serves to prevent web buckling. In either this or the previously described apparatus, it is preferable that the web be passed from the press section into the pressure nip under a tight draw.
It should be remembered that the straw fiber pulp and the other type or types of pulp must be well intermixed in order that the fibers of softwood etc. can assist in the inter-fiber bonding which is being enhanced by the upsetting or mechanical compacting of the web.
When it is desired to produce heavy weight (ream measure of 90 pounds per 3000 square feet and above), the treatment of the instant invention allows for the making of a heavier paper than could be produced on a similar capacity papermaking machine. This is true because consolidation of the web in the upsetting nip increases by approximately 10 percent the weight of the paper at the dry end of the machine. This allows a lower solids weight of the wet furnish to be run on the wire for the same weight of paper at the dry end of the machine. For example, to produce a 110 pound per 3000 square feet paper it is necessary only to run 100 pounds per 3000 square feet on the wire. The net effect is that the instant invention serves to increase the capacity of the papermaking machine by counteracting the slow draining characteristics of straw fibers.
From the compacting nip the paper is finally passed to a drying stack where the drying and smoothing of the web is carried out. It may be desirable in some instances to utilize a smooth surfaced drying roller or calender roller if a hard or glossy surface is desired.
As an illustrative example, sheets were produced according to the instant invention and then compared. Unbleached straw pulp was used along with long-fiber unbleached sulphate woodpulp. The straw pulp had a freeness of 74 seconds (Williams) and the woodpulp had a freeness of 29 seconds (Williams). The wire speed was 25 feet per minute and the wet end utilized a 10 inches of mercury vacuum. The headbox consistency was 0.64 percent and the basis weight at the wire was approximately 55 pounds per 3000 square feet. The sheets were introduced to the mechanical compactor at a 37 percent wetness and upset such that the sheet length was reduced about 12 percent.
Sheets were run with varying proportions of straw pulp to woodpulp and such things as T.E.A. (tensile energy absorption), elongation, edge tear and tensile strength were measured. These treated papers were compared with a standard untreated high grade multi-wall sack paper of 100 percent sulphate pine. The test results showed that a treated web with as much as 80 percent straw exhibited higher edge tear, higher T.E.A. and percent elongation. However the ultimate tensile of the straw paper was somewhat reduced. A paper made of 100 percent straw exhibited a higher T.E.A. after treatment than did the standard multiwall sheet and compared favorably in tear and percent elongation. These test comparisons are set out in table I. All figures have been adjusted to a 100 grams per square meter basis weight for the purpose of the comparison.
TABLE 1______________________________________ Edge Tensile % T.E.A. Tear% straw (kg/15mm) Elongation (cm kg/100cm.sup.2) (grms)______________________________________30 2.25 9.6 10.4 685540 4.20 14.5 26.3 408650 3.64 11.9 20.5 340560 3.42 10.1 16.5 358770 2.95 7.9 11.7 322380 3.18 8.8 13.8 367790 4.80 11.3 24.8 2225100 4.04 9.8 19.6 1725Control 5.23 2.4 6.5 3360______________________________________
The present invention has been described with reference to specific apparatus and specific method steps; however, it will be appreciated that a wide variety of changes may be made in both. For example, features of the invention may be utilized independently of others and equivalents may be substituted for the various method steps, all within the scope of the invention as defined in the claims. | Modified paper which exhibits high tear resistance and toughness and which contains a high percentage of straw fibers and which has fibers consolidated in a three step process including drawing water off by vacuum, press drying and fiber upsetting. | 3 |
BACKGROUND OF INVENTION
The present invention relates generally to pinion-to-gear alignment and, more particularly to, a method and apparatus for determining a pinion bearing move to achieve proper pinion-to-gear alignment based on temperature differentials of a pinion and a visual representation of a pinion-gear assembly.
Pinion-gear assemblies are widely used in a number of industrial and commercial systems, such as grinding mills. Conventional grinding mills are typically driven by a ring gear attached to the body of the mill. An electric motor or, in some circumstances, a gasoline powered engine, drives a pinion which powers the ring gear. To minimize wear and tear on the gear and pinion as well as to prevent costly down time due to broken or damaged teeth on the gear or pinion, it is imperative that the pinion be properly aligned to the ring gear. A number of techniques have been developed to properly align the pinion to the ring gear.
In one known method, an initial alignment of the pinion to the gear is achieved by collecting mechanical readings with feeler gauges and then making the best alignment possible based on those readings. Typically, this initial alignment is made with the pinion in a static condition and having no loads. As is well known, the pinion will take a slightly different position when running and under load conditions. Additionally, the alignment (or load distribution) of the pinion to the gear teeth will generate temperatures that are proportional to the load distribution. Simply, the side of the pinion with the heaviest load distribution will have higher temperatures than the side of the pinion with the lightest load distribution. These temperature differentials of the pinion when running with a load may be used to perform an alignment of the pinion-to-gear to achieve an even load distribution across the pinion teeth.
Complicating matters however, is that grinding mills are often driven by more than one pinion. Further, in grinding mills it is not uncommon for each pinion to be running in two directions. For example, autogenuous and semi-autogenuous mills are typically run in alternating directions in order to achieve longer liner life. Under these conditions, temperature data must be recorded on both pinions and in both directions. Additionally, a gear pressure angle, an angle of each pinion down from the mill center line, and a rotation of the mill while taking the temperature readings must be known in order to calculate a proper pinion move for realignment thereof. A number of computer programs have been developed to calculate pinion realignments based on temperature data. These specific programs are particularly well suited when the proper data is input directly into the program. However, it is relatively easy to make a mistake in the input of data into the computer program which ultimately could result in a damaged or broken gear or pinion due to an ill-advised alignment move. Additionally, manual calculations may be used to calculate a pinion realignment move, but manual calculations require considerable time and an extensive working knowledge of geometry as well as trigonometry.
It would therefore be desirable to design an apparatus and method for determining a pinion bearing move to align a pinion-to-gear assembly quickly and less prone to error without requiring a computer program or a number of complex manual calculations.
BRIEF DESCRIPTION OF INVENTION
A method and apparatus for determining a pinion bearing move to align a pinion-to-gear assembly overcoming the aforementioned drawbacks are provided. Using a realistic visual representation of a gear to pinion mesh showing pressure angles of the gear and pinion as well as the angle of the pinion down from the mill center line allows for a quick and accurate determination of a pinion bearing move to align the pinion-to-gear. Using temperature differential data of the pinion under load conditions, the present invention allows for an easy and efficient means of determining a pinion bearing move to align the pinion-to-gear without requiring complicated manual calculations or data input to a computer program. Furthermore, the present invention is lightweight and portable thereby avoiding the drawbacks often associated with handheld electrical devices and laptop computers.
Therefore, in accordance with an aspect of the present invention, a method for determining a pinion bearing move for a pinion-to-gear alignment assembly comprises positioning a gear tooth to a first angle and positioning a pinion tooth to a starting position. The method further includes determining a pinion temperature differential, Δt, and repositioning the pinion tooth to a corrected position based on the pinion temperature differential. The method further includes determining a distance from the starting position to the corrected position.
In accordance with another aspect of the present invention, a nomograph includes a gear tooth having a number of temperature gradient reference marks. The nomograph further includes a pinion tooth having a pair of aligned reference lines. The nomograph further includes a gradient grid having a plurality of reference points for determining a pinion bearing adjustment move.
In accordance with yet another aspect of the present invention, a tool for realigning a pinion to gear assembly is provided. The tool includes a visual representation of a gear to pinion mesh illustrating pressure angles of a gear and pinion assembly. The tool further includes an instructional manual having a set of instructions for determining one or more pinion bearing moves based on one or more pinion temperatures.
Various other features, objects, and advantages of the present invention will be made apparent from the following detailed description and the drawings.
BRIEF DESCRIPTION OF DRAWINGS
The drawings illustrate one preferred embodiment presently contemplated for carrying out the invention.
In the drawings:
FIG. 1 is a top view of a nomograph in accordance with the present invention.
FIG. 2 is an exploded view of the nomograph of FIG. 1 .
FIG. 3 is a cross-sectional view of the nomograph of FIG. 1 .
FIG. 4 is a top view of a portion of the nomograph of FIG. 1 showing a pinion tooth at a starting position.
FIG. 5 is an enlarged view of a portion of the nomograph shown in FIG. 4 .
FIG. 6 is a top view of a portion of the nomograph of FIG. 1 showing movement of a pinion tooth to a corrected position in accordance with the present invention.
FIG. 7 is an enlarged view of a portion of the nomograph shown in FIG. 6 illustrating movement of the pinion tooth from a starting position to a corrected position in accordance with the present invention.
FIG. 8 is a top view of a portion of the nomograph shown in FIG. 1 illustrating annular movement of a gear tooth and a pinion tooth in accordance with the present invention.
DETAILED DESCRIPTION
Referring to FIGS. 1-2, a nomograph 10 for determining a pinion bearing move to align a pinion-to-gear assembly based on temperature differentials of a pinion-gear assembly is shown. Nomograph 10 includes a gear tooth 12 and a pinion tooth 14 . In a preferred embodiment, pinion tooth 14 has a polygonal shape and a reference eyelet 15 , and is configured to be slidably positioned in pocket 16 of gear tooth 12 . Gear tooth 12 has a top surface 18 and an extending bottom surface 20 that cooperatively form pocket 16 . Movement of the pinion tooth 14 into pocket 16 is limited by a pair of convergent interfaces 22 joining the outer surface 18 to bottom surface 20 . That is, movement of pinion tooth 14 is prevented by the abutment of pinion tooth sidewalls 24 against interfaces 22 . Gear tooth 12 further includes a number of gradient reference lines 26 as well as a number of root change reference lines 28 . Two sets gradient reference lines 26 converge to an intersection (not shown) resulting in a mirrored alignment of the two sets. Additionally, each set of gradient reference lines includes a starting reference line 30 that is centrally disposed between the remaining reference lines 26 . Furthermore, reference line 30 , in a preferred embodiment, is conspicuously identified using a bold type.
Gear tooth 12 further includes a linearly extending positioning line 32 that extends along a bottom surface 20 . Line 32 extends from an eyelet 34 laterally through the intersection of the sets of reference lines 26 and is hiddenly positioned underneath the number of vertically oriented linearly arranged root reference lines 28 . Reference line 32 then extends from underneath the number of root reference lines 28 laterally along surface 20 . After a momentary break, line 32 begins again along surface 20 and extends to an outer edge 36 of gear tooth 12 . Gear tooth 12 further includes an alignment point 38 centrally disposed along one of the root reference lines 28 .
Nomograph 10 further includes an opaque base portion 40 having along the surface thereof a plurality of reference angle marks 42 angularly positioned from one another at, in a preferred embodiment, 5° intervals. A curvilinear grid 44 is also positioned along a top surface of base portion 40 and includes a plurality of angularly aligned reference points 46 . Reference points 46 are linearly aligned with angle reference marks 42 . Base portion 40 further includes a plurality of angular reference lines 48 extending angularly towards and in corresponding alignment with reference marks 42 from eyelet 50 . Base portion 40 may alternatively include a company name and logo section 52 .
Nomograph 10 further includes a transparent sheath portion 54 having a plurality of curvilinearly aligned access windows 56 . As will be discussed shortly, reference windows 56 enable a user to slidably position pinion tooth 14 within pocket 16 of the gear tooth 12 . Sheath 54 further includes an eyelet 56 that is aligned with eyelet 34 of gear tooth 12 and the eyelet 50 of the base portion 40 . Sheath 54 , gear tooth 12 , and base portion 40 are fasteningly connected to one another by a peg 58 , FIG. 2, disposed through eyelets 56 , 34 , and 50 . An angular ring or clamp 60 , FIG. 2, is used to secure components 12 , 40 , and 54 of nomograph 10 to one another.
Referring to FIG. 3, a cross-sectional view of nomograph 10 is shown illustrating the layered construction of sheath 54 , gear tooth top surface 18 , pinion tooth 14 , gear tooth bottom surface 20 , and base portion 40 . As shown, surface 20 of gear tooth 12 rests above base portion 40 but below pinion tooth 14 . Further, as is readily shown, sheath 54 is positioned atop the gear tooth surface 18 and pinion tooth 14 .
Referring to FIG. 4, the gear tooth 12 and the pinion tooth 14 are shown positioned in one of a number of starting positions. That is, the gear tooth 12 is positioned such that reference line 32 is linearly aligned with the angle reference mark 42 corresponding to 15° . Further, pinion tooth 14 is positioned within pocket 16 such that gear tooth sidewalls 24 align with bolded gradient reference lines 30 . Further, pinion tooth leading edge 24 ( a ) is positioned to align with root reference line 28 ( a ). As a result of aligning the pinion tooth sides 24 and edge 24 ( a ) with reference lines 30 , 28 ( a ), the pinion tooth eyelet 15 is aligned over a grid reference point 46 and, in the position illustrated in FIG. 4 , the pinion tooth eyelet 15 would be positioned over grid reference point 46 ( a ) which corresponds to angle reference mark 15°.
Angle reference lines 42 correspond to an angle below mill center line. Therefore, positioning the gear tooth reference line 32 as shown in FIG. 4 corresponds to a 15° angle below mill center line. That is, the present invention is designed such that gear tooth 12 may pivot angularly from eyelet 56 such that a number of mill center line angles may be selected. While FIG. 4 sets forth angles ranging from 0 to 30° at 2½° intervals, this is shown for illustrative purposes only and is not meant to limit the scope nor the breadth of the instant invention. Further, the present invention is designed such that gear tooth 12 may be repositioned along any angular line while the pinion tooth 14 is slightably engaged within pocket 16 . Angular movement of the gear tooth-pinion tooth assembly 12 , 14 may be achieved by simply moving gear tooth 12 and pinion tooth 14 through access windows 56 of sheath 54 , FIG. 2 .
FIG. 5 shows an enlarged view of the starting position achieved by placement of pinion tooth 14 within pocket 16 of gear tooth 12 . As may be readily seen, pinion tooth eyelet 15 is positioned such that grid point 46 ( a ) of gradient grid 44 is centrally positioned within the eyelet 15 . As indicated previously, this positioning of the gear tooth and pinion tooth is achieved when the gear tooth 12 is positioned to reflect a 15 below mill center line location of the pinion bearing assembly.
Now referring to FIG. 6, the gear tooth-pinion tooth assembly 12 , 14 is shown such that the position of the pinion tooth 14 within the pocket 16 and the gear tooth 12 have been moved to a corrected position 46 ( b ). Determining the proper pinion move to achieve corrected position 46 ( b ) is based upon pinion temperatures recorded of the pinion gear assembly. In one preferred embodiment, the pinion temperatures are recorded using an infrared heat gun whereupon temperatures are determined over a number of time intervals. These temperature readings are used to determine a temperature differential, Δt. For a dual direction mill, temperatures are recorded for both into mesh and out of mesh directions. The determined temperature differential of the pinion is then used to determine a scale for the pinion temperature change per gradient. For example, if the pinion temperature differential is greater than 30° F. and less than or equal to 60° F., then each gradient line 26 of the gear tooth 14 represents a 10° F. interval. If the pinion temperature differential is greater than 15° F. and less than or equal to 30° F., then each gradient reference line 26 represents a 5° F. interval. If the pinion temperature differential is less than 15° F., each gradient reference line 26 represents a 2½° F. interval. Furthermore, if the pinion tooth is moved laterally toward the gradient grid 44 , an “out of mesh” pinion move is being represented. However, if the pinion tooth is moved laterally away from the gradient grid 44 , an “into mesh” pinion move is being represented. If the pinion teeth on the top half of the pinion diverge with the gear teeth, this is considered to be “out of mesh” rotation. Conversely, if the pinion teeth on the top half of the pinion converge with the gear teeth, this is considered to be “into mesh” rotation.
Now referring to FIG. 7, an enlarged view of the corrected position 46 ( b ) illustrated in FIG. 6 is shown. As readily shown in FIG. 7, the pinion tooth 14 has been moved “out of mesh” by two gradient lines as indicative by pinion tooth sidewalls 24 being moved inward of gradient reference line 30 by two gradient lines 26 . This “out of mesh” movement of the pinion tooth 14 results in pinion tooth opening highlighting a new gradient grid point or corrected position 46 ( b ).
Once the pinion tooth 14 has been repositioned according to the proper temperature differential scale, it is possible to determine an appropriate pinion bearing move to correct for the measured temperature differential. That is, referring to the individual gradients of gradient grid 44 and by determining a position of the corrected position 46 ( b ) compared to the starting position 46 ( a ) and by measuring and determining the number of gradients along an x and y axis from the starting reference position 46 ( a ) to the corrected position 46 ( b ), it is possible to determine the appropriate pinion bearing move to correct the pinion alignment to the gear of a grinding mill. For example, the corrected position 46 ( b ) corresponds to approximately 3½ gradients along an x axis and one gradient downward along a y axis to the corrected position 46 ( b ). Therefore, to correct for the recorded temperature differentials, it is necessary to move the pinion out of the mesh 3½ gradients and downward one gradient.
Determining the value of each gradient depends upon which temperature differential scale was used to determine pinion tooth repositioning. That is, in one embodiment, each gradient represents 0.5 thousandths of an inch if the pinion tooth was repositioned according to a 2½° F. gradient scale. Additionally and as best shown in FIG. 6, repositioning of the pinion tooth 14 causes a repositioning of pinion tooth leading edge 24 ( a ). The number of root gradient lines between initial position 38 and the position following movement of the pinion tooth is indicative of the relative root change of the pinion gear assembly that will result once the pinion gear assembly is recalibrated to correct the temperature differentials. Like each gradient of grid 44 , each root change line 28 has a different value depending upon which temperature differential scale was used in moving the pinion tooth. For example, if each gradient reference line 36 represents a 2½° F. per gradient change, then each root line 28 represents 0.25 thousandths of an inch of change. The table below sets forth the additional root change and pinion bearing per gradient values for each temperature differential scale.
PINION TEMPERATURE CHANGE/GRADIENT
CHANGE IN
PINION TEMP
PINION BEARING
RELATIVE
SCALE
PER GRADIENT
MOVE
ROOT CHANGE
NO.
(*)
(*)
(*)
1
2.5° F./GRAD.
.0005″/GRAD.
.00025/GRAD.
2
5.0° F./GRAD.
.001″/GRAD.
.0005″/GRAD.
3
10.0° F./GRAD.
.002″/GRAD.
.001″/GRAD.
(*) These values assume the pinion face width is half the distance between the pinion bearing centerlines, the mill is drawing full power, and the gear and pinion tooth pressure angles are 25°.
By determining the appropriate values, it is possible for a service technician, engineer, etc. to determine the appropriate pinion move.
As indicated previously and referring to FIG. 8, the present invention is designed such that gear tooth 12 and pinion tooth 14 may be aligned at any number of angles depending upon the angle of the pinion bearing below mill center line. The gear tooth 12 and the pinion tooth 14 are positioned at a starting reference point 46 ( a ) and at a 30° angle below mill center line. As indicated previously, the range of angles shown in FIG. 8 represent only one embodiment of the present invention and is not intended to limit the scope thereof.
Therefore, the present invention includes a method for determining a pinion bearing move to align a pinion-to-gear assembly. To determine the proper realignment move, the gear tooth is set to a proper angle below mill center line. The pinion tooth is then inserted or positioned into a pocket of the gear tooth such that the eyelet of the pinion tooth is positioned over a starting reference point. Temperature differentials recorded from the pinion gear assembly are then analyzed to determine the appropriate scale for a pinion temperature change per gradient. Simply, the highest temperature differential recorded over a series of time intervals determines which pinion temperature change per gradient scale is to be used. Once the appropriate scale has been determined, the pinion tooth is accordingly moved to correct for the differential in temperature. For example, if the pinion temperature differential for the “out of mesh” rotation is 10° F., then each gradient line of the gear tooth corresponds to 2½° F. Therefore, to increase the pinion temperature by 10° F., the pinion tooth must be moved closer to mesh four gradient lines for the “out of mesh” rotation. Conversely, if the pinion temperature for the “out of mesh” rotation is to be decreased by 10° F., the pinion tooth is moved away from the mesh four gradient lines for the “out of mesh” rotation. Moving the pinion tooth the requisite number of gradient lines to account for the temperature differentials will result in the eyelet of the pinion tooth to be repositioned. The distance of the new position of the eyelet in relation to the starting position may then be used to determine the appropriate pinion bearing move. Simply, the pinion bearing move of the pinion gear assembly required to reduce the pinion temperature differential to zero is the difference between the pinion bearing starting reference point and the end point of the pinion tooth target after correction. After determining the distance in an x and in a y direction between the final position and the initial reference position, it is necessary to determine the appropriate scale to use in determining the pinion bearing realignment move. As discussed previously, the appropriate pinion bearing move as well as relative root change may be determined based upon which temperature gradient scale that was selected for moving the pinion tooth to the final corrected position.
Determining appropriate pinion bearing moves to correct pinion-to-gear alignment in accordance with the present invention are easy, quick and accurate. Furthermore, the present invention may also be used not only as an in-field product to recalibrate grinding mills and other pinion bearing assemblies, but may also be used as a teaching tool for those learning pinion gear alignments. The visual representation of the actual gear-pinion pressure angles and the pinion positions down from mill central line enables students to ascertain gear pressure angles, angles of the pinions below mill central line, and why and how pinion alignment corrections may be made. Further, those learning pinion alignment correction techniques may implement the present invention without having to input a significant amount of data into a computer program or solving a number of highly complex and often geometrical and trigometrical mathematical calculations. Further, the present invention also contemplates including a series of instructions on a reverse side of base portion 40 , FIG. 2, for instructing users on determining pinion bearing moves to correct pinion-to-gear alignments in accordance with the teachings of the present invention.
Therefore, in accordance with an embodiment of the present invention, a method for determining a pinion bearing move to correct pinion-to-gear alignments for a pinion-gear assembly comprises positioning a gear tooth to a first angle and positioning a pinion tooth to a starting position. The method further includes determining a pinion temperature differential, Δt, and repositioning the pinion tooth to a corrected position based on the pinion temperature differential. The method further includes determining a distance from the starting position to the corrected position.
In accordance with another embodiment of the present invention, a nomograph includes a gear tooth having at least one set of a number of temperature gradient reference lines. The nomograph further includes a pinion tooth having a pair of aligned reference points. The nomograph further includes a gradient grid having a plurality of reference points for determining a pinion adjustment move.
In accordance with yet another embodiment of the present invention, a tool for realigning a pinion gear assembly is provided. The tool includes a visual representation of a gear to pinion mesh illustrating pressure angles of a gear and pinion assembly. The tool further includes an instructional manual having a set of instructions for determining one or more pinion bearing moves based on one or more pinion temperatures.
The present invention has been described in terms of the preferred embodiment, and it is recognized that equivalents, alternatives, and modifications, aside from those expressly stated, are possible and within the scope of the appending claims. | A method and apparatus for determining a pinion bearing move to correct pinion-to-gear alignment based on pinion Δ t overcoming the aforementioned drawbacks are provided. Using a realistic visual representation of a gear to pinion mesh showing pressure angles of the gear and pinion as well as the angle of the pinion down from the mill center line allows for a quick and accurate determination of a pinion bearing to align a pinion-to-gear assembly move. Using temperature differential data of the pinion under load conditions, the present invention allows for an easy and efficient means of determining a pinion bearing move to align a pinion-to-gear assembly without requiring complicated manual calculations or data input to a computer program. Furthermore, the present invention is lightweight and portable thereby avoiding the drawbacks often associated with handheld electrical devices and laptop computers. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the invention
The invention concerns a device for simulating a golfcourse comprising a series of holes into which a player must direct a ball in corresponding successive stages, the ball being played from a start area to the hole forming the stage objective in a series of strokes.
2. Description of the prior art
On a real golfcourse where the distances between the start area and the objective hole are frequently as much as several hundred meters the strokes played by the players are of two kinds:
Firstly, long-distance strokes called "swings" or "long drives" where the player attempts to get the ball close to the hole, covering the greatest possible distance, possibly tens or even hundreds of meters.
Secondly, precision strokes or "putts" where the player attempts to reach the objective hole directly and the length of which rarely exceeds a few meters.
Players use specific clubs for each kind of stroke.
Evidently there is no clear-cut boundary between "swings" and "putts", the distinction depending partly on the skill of the player and partly on the configuration of the terrain around the hole.
As far as the applicant is aware, virtually all simulation devices previously proposed simulate only one of the two kinds of stroke, in the majority of cases putts.
However, some devices designed to simulate swings incorporate holes catering for simplified putting, with no obstacles. In these devices there is no interelationship between the swings and the putts.
The document U.S. Pat. No. 1,904,034 describes a putting simulator device with a track situated between a start area and a hole with a surface covering that simulates a lawn (green). The track can be tilted by means of a lever to return the ball to the player. A counter device registers entry of the ball into the hole and displays a successful stroke, while impact of the ball on a target behind the hole registers and displays a missed stroke.
The document U.S. Pat. No. 3,184,239 proposes a similar device except that there is a gully beyond the hole to recover balls which have gone past the objective hole and a scraper bar for returning balls that have stopped on the track as the result of a stroke that is too short.
U.S. Pat. Nos. 3,601,407 and 2,465,418 describe flexible material tracks that can be deformed to create bumps or hollows and increase the difficulty of the strokes. The first document discloses a single hole while the second discloses a plurality of holes.
U.S. Pat. No. 3,114,554 describes a track for training in putting with a plurality of holes which are opened one at a time in sequence. Control devices are provided to react to entry of a ball into an open hole, to open the next hole in the sequence and to display the results.
U.S. Pat. No. 4,133,534 describes a device similar to the previous one. The track comprises various obstacles; the holes are opened one at a time in sequence; when a ball enters the open hole the result is registered and then the hole is closed, ejecting the ball onto the track.
U.S. Pat. No. 3,633,917 describes a starting base for golf training but does not give any information as to the location or structure of the holes.
In this document the start configuration is variable; firstly three different types of starting terrain are available, disposed on a triangular prism-shaped rotor which rotates about a horizontal axis, one simulating a green, the second simulating a rough and the third simulating a bunker. This starting base is situated at the center of a platform that can be tilted about two orthogonal horizontal axes. Flexible aprons connect the platform to the surrounding surface.
Other documents are directed to training in swings.
U.S. Pat. No. 3,684,293 describes a tunnel-like cage. The walls of the cage, and in particular the back wall, comprise coatings selected to damp impact in a particular way. In this way it should be possible to evaluate the length of the swing and the effects imparted to the ball. As an accessory there is provision for training in putting by placing a hole in the cage.
U.S. Pat. No. 4,045,023 describes a device for training in swings which essentially comprises at a distance from a starting base a target provided with impact sensors and divided widthwise and heightwise in sectors. The division into widthwise sectors corresponds to the accuracy of the stroke in terms of direction while the heightwise division is used to evaluate the theoretical range of the stroke.
The description in this patent is full of ancillary and redundant descriptive material, such as the arrangement of the playing area in the form of an individual cabin; there is some doubt as to the feasibility of the real object of this patent.
Be this as it may, the prior art devices either offer sporting games similar to golf or can be used for training in this sport under severely restricted conditions. These devices fall a long way short of simulating the variety and the sequencing of strokes on a real golfcourse and of making it possible to evaluate the qualities of a player. In particular, none of these devices makes the conditions for any stroke dependent on the results of a preceding stroke and thus they do not simulate a course with a sequence of strokes in each stage (hole) in which the position of the ball as the result of one stroke determines the origin of the next stroke.
SUMMARY OF THE INVENTION
The present invention consists in a golfcourse simulator device comprising a series of holes into which a player must direct a ball in corresponding successive stages in each of which one hole constitutes a stage objective to which the ball advances from a start area, the player playing all his strokes from the same point and the progress of the ball along the course being simulated by displacement of the objective hole according to parameters of the preceding stroke, said device comprising a driving area, a first ball sensor in said driving area, an elongate track extending from said driving area, a plurality of selectively openable and closable holes on said track, a plurality of second ball sensors each associated with a respective hole, a plurality of third ball sensors disposed along the length of said track to determine the farthest position reached by a ball on said track after a stroke, a target closing said track at the end opposite said driving area and adapted to define a real space between it and said driving area and a virtual space on the side of said target opposite said driving area, a plurality of impact sensors on said target and control means including a computer programmed:
to define the series of stages each corresponding to a field extending from a start area to an objective hole and subdivided into an ordered plurality of contiguous cells memorized in said computer in the form of a file comprising plurality of blocks of information each associated with a respective one of said cells of said field and each containing data for identifying the associated cell relative to the start area and the objective hole for the stage in question;
to determine stroke parameters either from conditions of impact on said target or from the position of the ball on said track after the stroke according to whether the objective hole for the cell in which the origin of the stroke is simulated is in said virtual space or in said real space, respectively;
to determine the cell of said field in which the ball is located after a stroke from the stroke parameters and the cell reached after the preceding stroke;
to fetch from said file objective parameters associated with the cell reached after the preceding stroke, which parameters condition the opening of a particular hole on said track if said cell is in said real space; and
to register the end of a stage in response to activation of one of said second ball sensors corresponding to entry of the ball into the opened hole.
It should be understood that if the objective hole is in the virtual space the player must attempt to get closer to the hole by playing swings with in each case the resulting virtual location of the ball being determined from the ball departure parameters: initial speed and orientation at the start of the trajectory, measured by the time interval between the departure of the ball and its impact on the target at a known distance on the one hand and from the position of the impact sensor on the target struck by the ball on the other hand; the virtual ball location after each swing becomes the basis for the next stroke, supplying information on the relative position of the objective hole of the next stroke relative to the starting point; subsequently, if the parameters of a swing place the final ball location in the real space the objective hole is materialized by opening the appropriate one of the multiplicity of holes; the player then starts putting and unsuccessful putts are measured by means of the third ball sensors to determine the position of the objective hole for the next putt, materialized by opening the appropriate hole.
An image synthesizer preferably produces a synthesized image on the target based on digital data stored in an information block associated with the cell of the stage field corresponding to the origin of the stroke, the image representing a panorama centered on the objective hole as seen from the stage field cell from which the stroke is played.
The driving area preferably comprises a plurality of stroke start areas adapted to be exposed individually and configured to simulate a kind of terrain, the information block associated with the stage field cell comprising specific data as to the nature of the terrain.
The first ball sensor is preferably a photoelectric device below an orifice on which the ball is placed so that the departure of the ball enables external light to impinge on the photoelectric device.
In a preferred embodiment the target comprises in longitudinal succession from a vertical rigid stop panel towards the driving area a first layer of rectilinear, parallel and regularly spaced conductors, a second layer of rectilinear, parallel and regularly spaced elastic conductors disposed parallel to the first layer with a gap between them, the conductors of one layer being horizontal and those of the other layer being vertical, and a flexible mat parallel to the stop panel and spaced from the second layer, the distances from the mat and the second layer to the stop panel being such that the impact of a ball on the mat pushes at least one conductor of the second layer into contact with at least one conductor of the first layer in line with the point of impact.
It will be understood that the contact between a specific wire of the first layer and a specific wire of the second layer as the result of an impact locates this impact in a way that is well suited to digitization of the impact point abscissa and ordinate. Each conductor of each layer is connected to one input of a matrix encoder. The layer of vertical wires gives information as to the direction of the stroke and the layer of horizontal wires gives information as to the lift which, in combination with the initial speed information obtained from the time for the ball to travel from the start area to the target, in combination with the distance separating the start area from the target, determines a range indication. If this distance is constant, at least for golf swings, the length of the swing can be determined by looking up a memorized stroke table with one input for the duration and another input for the lift.
Secondary characteristics and the advantages of the invention will emerge from the following description which is given by way of example only with reference to the appended diagrammatic drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a general perspective view of a device in accordance with the invention.
FIG. 2A is a plan view of the driving area.
FIG. 2B is a cross-section on the line IIB--IIB in FIG. 2A.
FIG. 2C is a cross-section on the line IIC--IIC in FIG. 2A.
FIG. 3 is a plan view of the track.
FIG. 4A is a view in elevation of the track in a longitudinally horizontal position.
FIG. 4B is a view in elevation of the track with a longitudinal tilt.
FIGS. 5A, 5B, 5C and 5D are transverse cross-sections through the track when respectively horizontal in the transverse direction, tilted towards the left, tilted towards the right, and strongly tilted towards the right to recover balls.
FIG. 6A is a plan view of a retractable hole.
FIG. 6B is a cross-section on the line VIB--VIB in FIG. 6A.
FIG. 7A is a view in elevation of the target with the protective mat partially cut away.
FIG. 7B shows in cross-section a detail of the target during the impact of the ball.
FIG. 8 is a schematic of a circuit for determining stroke parameters.
FIG. 9 is a memorized schematic of the virtual space between a stroke start area and an objective hole on which is located the arrival point of a stroke.
FIG. 10 is a schematic of the virtual space between the stroke start area and the objective hole, for determining the objective parameters for an intermediate stroke.
FIG. 11 shows a typical synthesized image displayed on the target when the objective hole is in the virtual space.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In the selected embodiment shown in FIG. 1 the golfcourse simulator device essentially comprises a playing area 1 at one end of a track 5. The playing area 1 has a roof 2 provided with means (not shown) for illuminating the playing area 1 and the track 5 which is articulated relative to the playing area 1 to which it is joined by a flexible carpet 4. The playing area 1 includes a driving area 3 and the track 5 comprises a plurality of "retractable" holes 6 distributed along it at various distances from the driving area 3. A mobile target 8 is mounted to slide along the track 5 by means of a carriage sliding in rails.
The upper surface of the track 5 has a covering which simulates a green. The track 5 comprises, supported by articulated frames 15, a protective net (not shown to avoid overcomplicating the diagram) which forms the lateral walls and roof of a rectangular cross-section corridor open at one end to the playing area 1 and closed at the other end by the target 8. The net is held by appropriate means to the edge of the target 8, for example by magnets cooperating with the steel wires of the protective net. Balls played from the driving area 3 therefore remain within the corridor.
The driving area 3 shown in FIGS. 2A and 2B comprises in a centered longitudinal arrangement four stroke start areas 32, 33, 34 and 35; these are respectively a putting start area 35, a "tee" start area 34 shown in more detail in FIG. 2E, a "rough" start area 33 and a "bunker" start area 32. All of these start areas have a common feature, to be described with reference to the "tee" start area 34 (FIG. 2C), in that they are mounted on a plate 41 which occupies either of two positions at 180°, controlled by a motor 44. In a first position of every plate 41 one side of the plate with a coating simulating a green is flush with the ground of the driving area 3. In the second position the plate has a specific character: this means for the area 35 a simulated green, for the area 34 a tee 42 on which the ball B is placed, for the area 33 a simulated rough, and for the area 32 a depression simulating a bunker. All the areas have a rest position with the ball centered and comprise a vertical channel directed downwards and a photoelectric cell 43 on the axis of the channel. A light source fixed to the roof 2 vertically above the vertical channel directs a light beam towards the cell 43. As the ball B in the starting position closes off the entry to the channel the cell 43 is masked. It is therefore able to send a signal when the ball leaves its starting position when hit by a club. The use of this starting signal will be explained later.
It will have been understood that only one start area is uncovered for each stroke, this start area being chosen to correspond to the nature of the terrain from which the stroke is to be played. This will also be explained in the section of the description concerning operation of the device.
The driving area 3 comprises to either side of the aligned start areas 32 through 35 two symmetrical panels 30 and 31 the dimensions of which are such that a player can stand on one or other of the panels 30 and 31 to play the ball. The panel 30 to the left of the aligned areas is intended for a righthanded player and the panel 31 to their right is intended for a lefthanded player.
As seen more clearly in FIG. 2B the panels 30 and 31 can be inclined by a jack 36 the piston rod 37 of which operates two links 38 and 39 to achieve one extreme position with a downward slope towards the start area (shown in full outline) and another extreme position with an upward slope towards the start area. It will be understood that the purpose of this is to simulate uneven terrain on the golfcourse requiring an adjustment to the position of the player to play the ball.
Reference will now be made to FIGS. 3, 4A, 4B, 5A, 5B, 5C and 5D in order to describe the track 5. It will be noted that the specific features to be described relate for the most part to putting, where the results of previous strokes have simulated the ball approaching the hole to within a distance less than the length of the track.
The track 5 is joined to the driving area 3 by a flexible apron 4 to enable the track to be inclined relative to the driving area. As already mentioned, the track 5 has a covering simulating a green or fairway. Retractable holes 6 are distributed along the track and in this instance one hole 7 is open to constitute the objective.
The track (FIGS. 4A and 4B) rests on a frame in the form of a truss with a ball-joint articulation at its posterior end linked to the platform of the driving area 3. To the anterior end 16 are attached cables which can be wound onto a drum 14 of a winch to raise the anterior end 16 so that the track 5 slopes upwardly towards the anterior end. Also, as shown in FIGS. 5A through 5D, a jack 21 is coupled to a lateral edge of the track 5 and can be extended (FIGS. 5C and 5D) or retracted (FIG. 5B) to impart a lateral slope to the track 5. The inclinations represented in FIGS. 5B and 5C correspond to difficult strokes as compared with the FIG. 5A position. Also, the strong inclination to the right shown in FIG. 5D corresponds to a ball return maneuver: by virtue of this inclination balls will first be directed into a gully 9 between the track 5 and the edge member 20, to be then impelled towards the posterior end of the track 5 to enter a ball reservoir/dispenser 12 the outlet from which onto the playing area 1 can be seen in FIG. 1.
Note that the recovery gully 9 has photoelectric cells 10 along its length; a signal appears at the cells 10 when the ball masks them in returning to the posterior part of the track 5. This provides information as to the distance travelled by the ball.
As shown in FIGS. 6A and 6B the retractable hole comprises a fixing plate 60 in which is a circular orifice the diameter of which corresponds to conventional golfcourse holes. In this circular orifice is accommodated a circular closure member 61 with the same surface coating as the track 5. The closure member 61 is fitted with a central depending rod 63 which is fixed to a blade member 61a parallel to the closure member 61 with a hinge 61b at one end and a return spring 66 at the other end.
The circular orifice that the closure member 61 closes off is extended downwardly by a skirt 62 which is a sector of a torus the axis of which is coincident with the axis of the hinge 61b and in which are slots for the blade member 61a to pass through. Coupled to the base of the central stem 63 is a cord 64 coupled at the other end to the piston rod of a jack 65. It will be understood that retraction of the jack 65 will lower the closure member 61 which pivots about the hinge 61b substantially as far as the lower end of the skirt 62.
Towards the exterior of the skirt 62 are two peep-holes 67 and 68 one containing a light source and the other containing a photoelectric cell. When the hole 6 is opened by lowering the closure member 61 the entry of a ball into the hole interrupts the optical path between the peep-holes 67 and 68. Expansion of the jack 65 releases the closure member 61 and the blade member 61a which is attached to it through the intermediary of the central stem 63. The spring 66 then returns the combination of the pivoting blade member 61a and the closure member 61 until the latter is level with the track 5, expelling the ball which had entered the hole 6.
The target 8 shown in FIGS. 7A and 7B is a rectangular frame closed by a stop panel 85. It comprises a first layer of equidistant vertical wires 81(1-16) resting against the stop panel 85 and a second layer parallel to the first layer made up of equidistant horizontal wires 82(1-16). The wires 82(1-16) are tensioned elastically so that they are near the first layer 81 but not in contact with it. In front of the two layers 81 and 82 is a flexible mat 80 which is capable of absorbing the impact of balls B. As shown in FIG. 7B the impact of a ball B from the playing area drives the mat 80 towards the stop panel 85. As a consequence of this wires 82(n) and 82(m+1) of the layer 82 are deformed by the mat 80 and the wire 82(n) comes into contact with wire 81(m) of the layer 81.
The arrays of wires 81(1-16) and 82(1-16) terminate at a matrix coder 83 which sends from an output 83a an impact address signal m, n corresponding to the point of impact on the target 8.
Note that it is possible to double the resolution of the target by assigning address components of the form m+1/2 or n+1/2 if two wires of index m and m+1 or n and n+1 are in contact simultaneously at the time of impact.
Note also that the stop panel 85 may constitute an image synthesizer screen, as will be explained later.
As already mentioned, the use of the golfcourse simulator device entails two playing phases for each course stage (hole) from a start area to an objective hole, the first phase corresponding to swings and the second phase to putting. It was also pointed out that FIGS. 3, 4A, 4B, 5A-5D, 6A, 6B were essentially concerned with putting executed over a distance less than the length of the track 5.
Swings must be simulated and the location of the ball after the stroke reconstituted in a virtual space which, neglecting for the time being the possibility of longitudinal displacement of the target 8, begins beyond the target 8.
To locate the end of the trajectory of the ball the first step is to establish stroke parameters which will essentially be an initial speed of the ball, a lift angle (angle in a vertical plane with which the ball leaves the horizontal plane passing through the origin of the trajectory), and a drift angle (angle in a horizontal plane by which the trajectory at the origin departs from the aiming line).
For simulating swings the target is placed at a known distance from the area from which the ball is played; the initial speed will be the quotient on dividing the duration separating a start signal emitted by the photocell 43 as described with reference to FIG. 2C and contact between the wires 81m and 82n as described with reference to FIG. 7B. Also, the index n of the wire of the layer 82 in contact with the wire 81m will be representative of the angle of lift while the number m-8 where m is the index of the wire of the layer 81 in contact with a wire of the layer 82 will be representative of the drift, the sign of this drift indicating whether it is to the right or to the left.
FIG. 8 is a schematic representation of a circuit for determining stroke parameters and stringing to the next stroke.
The figure shows a start area 3 at which a ball B intercepts the light emitted by the source 40 towards the photocell 43 and the matrix coder 83 connected to the target 8. A calculator circuit 121 provided with a clock 120 receives on a first input 121a the signal sent by the photocell 43 and on a second input the signals sent by the matrix coder 83. The signal sent by the photocell 43 triggers the counting of pulses from the clock 120 which is stopped by the signal indicating contact between two wires of the target 8 transmitted by the matrix code 83. The calculator 121 then determines the initial speed given the actual distance from the start area to the target and places the initial speed value on the output 121c. It also indicates the tangent of the angle of lift deduced from the index n (on the output 121d) and the angle of drift deduced from the index m (on the output 121e).
The initial speed signal on the output 121c and the lift angle tangent signal on the output 121d are applied conjointly to a read-only memory 122 organised as a stroke table in which are recorded ranges defined by a pair of initial speed and lift angle tangent values taken from a double multiplicity of discrete values.
The stroke table 122 is constructed from a number of experimental values by appropriate interpolation.
The range appears at the output 122a and is applied conjointly with the drift angle appearing at the output 121e to a calculator 123 for determining the trajectory which, as will be explained in more detail later, converts polar coordinates defined relative to a pole at the origin of the stroke, the polar coordinates consisting of the range and the drift angle, into polar coordinates defined relative to a pole at the objective hole. This latter pair of signals (distance and bearing of the end of the trajectory relative to the objective hole) is memorized at 124 to initialize the calculator 123 for the next stroke and is directed via an output 125 to other control circuits.
This is because the circuit shown in FIG. 8 is naturally integrated into a controlling microcomputer programmed to define a series of course stages (holes), to determine the progress of the ball in, the virtual space by the process previously described, to determine the moment at which a stroke corresponds to entry of the objective hole into the real space, to open a hole 7 at the distance from the driving area corresponding to the distance between the end of the previous stroke and the objective hole, then to determine (from the length of the stroke measured by means of the cells 10 along the length of the track 5 when the tilting shown in FIG. 5E causes the balls to be returned to the reservoir/ dispenser 12) the hole 6 to be opened for the next stroke, and so on in this way until the ball is played into the objective hole, to start the next course stage. Of course, the microcomputer records and displays (at 11 in FIG. 1) the player's performance, in particular the number of strokes needed to complete the stage and also a total for the stages already completed.
FIG. 9 is a schematic representation of the configuration of a field corresponding to a course stage from a pole 100 corresponding to the stage start area (the "tee" start area 34) to an objective 103 corresponding to the objective hole. This field comprises a plurality of cells such as the cell 104 delimited laterally by two rays of a beam 101(1-16) the rays in which are angularly equidistant. It is delimited longitudinally by two circular arcs of a plurality 102(1-27) of arcs with their radius increasing in regular increments. It will be readily understood that the address of a cell 101p, 102q is defined by the angle of drift and the range of a stroke assumed to be executed from the pole 100.
The microcomputer includes a memory in which data specific to each cell is stored in a respective memory location with address p, q, this data comprising the distance to the objective hole, the orientation of the polar ray (103, 104) the nature of the terrain (fairway 105 or bunker 106 or water 107 or rough if no contrary indication) and the transverse slope of the terrain, all this numerically encoded data being used to control the driving area 3 (choice of one start area 32 through 35, inclination of the panels 30 and 31 on which the player stands).
Each memory location contains information for recalling from floppy disk type memory assigned to the current field elements for forming an image to be addressed to the image synthesizer disposed conjointly with the target 8, this image reconstituting the appearance of the field centered on the objective hole as seen from the cell 104 at which the previous stroke ended. FIG. 11 shows an image of this kind with at the centre the hole 113 and its flag, a fairway 114 and a bunker 116. Above the target screen 8 is an area for displaying alphanumeric information of interest to the player, in particular the distance to the hole 103 and the stroke start cell 104.
The foregoing comments with reference to FIG. 9 have so far considered only the first stroke, from the "tee" start area 34. As shown in FIG. 10 there may be superimposed on the field shown in FIG. 9 a plurality of circular arcs 110 with radii increasing with equal increments (the same increment as for the arcs 102(1-27)), the position of the terminal point 104 of the preceding stroke lying between two consecutive circular arcs 110 to define the distance to be taken into account for the next stroke.
To bring the point 104 to the point 100 for the next stroke the scale is changed by a factor which is the quotient of dividing the distance 100-103 by the distance 103-104, after which the field is rotated through the angle 104-103-100. The range and the drift angle for the next stroke will therefore be corrected to allow for the change of scale and the pivoting of the field to determine the cell at which the next stroke terminates.
In this way it is possible to string the strokes until the objective hole is situated in the real space, where the course is continued by opening successive holes 6.
It will be noted that the computations performed by the microcomputer have been mentioned here only to illustrate the operation of the various hardware devices by the programmed control means in an ordered process whereby the hardware devices cooperate to simulate effectively a golfcourse from the start area of the first stage (hole) to the last hole. In themselves these computations are outside the scope of the invention and their execution could be modified provided that they determine the simulation of the progress of the ball by successive actual strokes on the stage field between the start area and the stage objective hole.
Moreover, the invention is not limited to the examples described but encompasses all variant executions thereof within the scope of the claims. | A golf course simulator comprises a track running between a driving area and a target. The track incorporates a plurality of selectively openable and closable holes. The target marks the boundary between the virtual space in which an objective hole is situated in a first phase of the game, when the strokes played are swings, and a real space in which the objective hole is materialized by opening one hole, once the player has come close enough to the objective hole. The simulator is controlled by an appropriately programmed computer. For swings the driving area incorporates a ball sensor and the target incorporates an impact detector matrix. Measuring the time between the departure of the ball and the impact on the target, at a known distance, and location of the point of impact on the target supply initial speed, lift and drift information to determine the point of arrival of the ball in the virtual space and to deduce therefrom objective parameters. If the objective hole is in the real space one hole is opened and the length of the putt as determined by sensors arranged along the track results in the opening of another hole corresponding to the distance for the remaining putt or putts. | 0 |
BACKGROUND OF THE INVENTION
1 Field of the Invention
This invention relates generally to offshore drilling systems and more particularly to a pressurized slip joint for use with a marine intervention riser system for workover applications after a well has been drilled. The slip joint enables expeditious operations in the moon pool of a vessel in heavy seas.
2 Background of the Art
Risers for drilling operations typically consist of large diameter pipes extending from the wellhead through an opening in the bottom (“moon pool”) of the vessel. Drilling operations are carried out by means of a drill string within the riser. Drilling mud required for drilling is circulated through the drillstring to the drillbit at the bottom of the drillstring, back up the wellbore and through the annulus between the drillstring and the riser. The riser serves to separate the drilling fluid from the surrounding seawater. When drilling operations are carried out in deep water, the danger of buckling of the riser increases. The reason for this is that the riser has the same buckling characteristics as a vertical column and structural failure under compressive loading may occur. To avoid this structural failure, riser tensioning systems are installed on the vessel for applying a tensile force to the upper end of the riser. A variety of such tensioning systems have been used in prior art, including cables, sheaves and pneumatic cylinder mechanisms connected between the vessel and the upper portions of the riser.
Because the riser is fixed at the bottom to the wellhead assembly, wind, wave and tidal action will cause movement of the vessel relative to the top end of the riser. Motion compensating equipment must be incorporated into the tensioning system to maintain the top of the riser within the moon pool. This may include a telescopic coupling arrangement to compensate for heaving motion and a flex joint within the riser to compensate for lateral movement of the vessel. During drilling, pressure inside the riser pipe is comparatively low. However, the pressure may increase if a shallow pocket if gas is encountered and the sliding joint is typically designed to withstand a pressure of 2000 psi or less.
In the case of producing wells, however, the pressure inside the riser can easily approach 10000 psi. Fixed production platforms do not require telescopic risers. In deeper waters, tension leg platforms have been used. Such platforms are subject to more motion than fixed platforms and the risers have to be designed accordingly. On marginal fields where the cost of a production platform would be prohibitive, drilling vessels have been used for production. Production riser pipes for mobile production platforms have been constructed as an integrated unit suspended in tension systems and guides, capable of absorbing the necessary telescopic, lateral and angular movements. U.S. Pat. No. 5,069,488 discloses a telescopic device that is volume and pressure balanced for mobile production platforms. Because of the requirement of no relative vertical motion between the riser and the production vessel, the telescopic system has to be designed to withstand the maximum motion expected in heavy seas.
Marine intervention riser systems are functionally similar to risers used with mobile production platforms in terms of the pressures that are encountered. However, there is one major difference: workover operations typically require a variety of devices to be inserted into the well. Use of these devices requires a considerable amount of human involvement in the vessel. Any system in which the riser pipes in the moon pool have a large vertical movement with respect to the vessel presents a serious safety hazard when humans are preforming workover operations in the vessel. At these times, it is desirable to have no movement between the top of the riser assembly within the moon pool and the vessel. At other times, when humans are not involved, vertical movement of the riser within the moon pool is acceptable: at such times, a system that allows relative motion between the top of the riser assembly within the moon pool and the vessel is acceptable. The present invention is capable of meeting these requirements.
SUMMARY OF THE INVENTION
The present invention provides a slip joint assembly for use in a marine intervention riser system. When devices for workover operations are being installed by humans, the invention is configured to act like a low pressure slip joint with the upper end of the assembly fixed relative to the vessel, allowing for safe installation of the devices. Once the workover devices have been installed, the upper end of the assembly is fixed to the riser and is capable of sealing at high pressures.
Examples of the more important features of the invention have been summarized rather broadly in order that the detailed description thereof that follows may be better understood, and in order that the contributions to the art may be appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject of the claims appended hereto.
BRIEF DESCRIPTION OF THE DRAWINGS
For detailed understanding of the present invention, reference should be made to the following detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings, in which like elements have been given like numerals:
FIG. 1 is an overall elevational view of a riser assembly incorporating the present invention in operation.
FIG. 2 is a view of an embodiment of the flexible slip joint
FIG. 3 is a sectional view of a flexible slip joint.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a vessel 10 floating at the surface 12 of a body of water 20 . The vessel includes a vertical opening or “moon pool” 14 through its hull. The moon pool is typically located at the center of the vessel in order to avoid destabilizing the vessel due to operations being carried out. The vessel is provided with a support, such as a wireline rig or coiled tubing inserter 16 , that is used for lowering equipment into the well. A riser string 118 carries the wireline or coiled tubing through the wellhead assembly 102 into the borehole (well) 104 . Details of the wellhead assembly and other devices associated with connecting the riser string 118 to the wellhead are not shown.
Ocean currents, ocean waves and the like will cause movement of the vessel 10 at the surface 12 relative to the fixed wellhead assembly 102 at the bottom of the body of water. The motion may be vertical (surge or heave), horizontal (drift) or rotational (yaw, pitch and roll). Drillships are usually provided with thrusters to compensate for the drift of the vessel. Additional mechanisms have to be provided for compensate for the other types of motion to avoid damage to the riser that is fixed to the ocean bottom and vessel. At the top of the riser string is a flowhead assembly 32 in the moon pool 14 . A motion compensating system (not shown) compensates for relative motion of the riser string 118 and the vessel 10 . Such motion compensating systems will still result in a relative motion between the flowhead assembly 32 and the vessel. The present invention is part of a decoupling assembly 30 that is adapted to decouple the motion of the flowhead assembly 32 from that of the riser string 118 , so that equipment changes required for workover operations may be safely carried out on the flowhead assembly.
Turning now to FIGS. 2 and 3, the main components of the decoupling assembly are shown. Conceptually, it can be considered to have two main components: one component that is fixed to the riser string 118 and a second component that is fixed to the flowhead assembly 32 . The first and second components are designed to move in unison when locked together by a locking mechanism and to be decoupled when unlocked by the locking mechanism.
The lower part includes a pressurized slip joint assembly 100 connected at its lower end to the top of the riser string 118 . The top of the slip joint assembly 100 is connected by means of a collet connector and guide funnel 116 to a flexible joint assembly 110 . In a preferred embodiment of the invention, a hydraulic quick connect device is used for coupling the flexible joint assembly to the top end 108 of the slip joint assembly. Such quick connect devices would be known to those versed in the art and are not discussed further. For illustrative purposes, the slip joint assembly 100 and the flexible joint assembly 110 have been shown in a disconnected position. The purpose of the flexible joint assembly is to compensate for the yaw, roll and pitch of the vessel relative to the riser string 118 . The top of the flexible joint assembly 110 is connected to a flowhead assembly (not shown in FIGS. 2 and 3) in the moon pool of the vessel. The flexible joint assembly includes a flex joint and may also include a swivel joint. Flex joints and swivel joints would be known to those versed in the art and are not discussed further.
Shown near the top end 108 of slip joint assembly 100 and enclosing it is part of the tension assembly for keeping the riser 18 under tension. A rotational tension ring 112 surrounds the slip joint assembly. The tension ring 112 is provided with lugs 114 through which cables (not shown) are passed. Such tension assemblies for keeping risers under tension would be known to those versed in the art and are not discussed here.
FIG. 3 shows a partial sectional view of the slip joint assembly. For clarity, it is shown disengaged from the flexible joint assembly 110 . The rotational tension ring 112 is shown along with the lugs 114 . The rotational tension ring 112 and a downwardly extending cylindrical portion 122 may be considered to define a substantially cylindrical outer housing. Supported inside the rotational tension ring 112 by bearings 119 is an inner housing 120 . This allows rotational movement between the inner housing 120 and the tension ring 112 . The inner housing is of substantially cylindrical shape with a lip 124 at its lower end. Extending circumferentially around the inside wall of the inner housing is a groove 126 . Near the bottom of the cylindrical portion 122 and on its inside is a shoulder 141 . A quick connect device 142 at the bottom of the outer housing is used to connect the slip joint assembly to the riser 118 (not shown in FIG. 3 ).
The sliding member 128 of the slip joint assembly has a head 132 and a downwardly extending cylindrical body 134 . The head is sized to fit on the inside of the inner housing 120 while the body (a liner) 134 is sized to fit inside the outer housing. The head is provided with a lockdown ring (or segments of a lockdown ring) 130 that is designed to engage the cylindrical groove 126 of the inner housing in a locked position and to allow slidable movement (in a vertical direction) of the sliding member in an unlocked position. The sliding member is provided with a number of hydraulic leads to control its operation. These are labeled 148 , 150 , 152 , and 154 and are discussed below.
When the sliding member 128 is in the locked position, the bottom end 135 of the body 134 forms a metal-to-metal seal 146 against the shoulder 141 on the outer housing. This seal 146 forms the primary high pressure seal when sliding member 128 is in the locked position. Secondary 140 and tertiary 138 high pressure seals are also provided between the body 134 of the sliding member and the outer housing 122 as a backup to the primary high pressure seal 146 . The secondary and tertiary seals are preferably made of elastomeric material. In addition, a dynamic low pressure seal 136 is also provided for the annulus between the body 134 of the sliding member and the outer housing 122 .
A plurality of hydraulic leads that perform various functions lead into the head 132 of the sliding member. Leads 148 a, 148 b and 150 a, 150 b activate the latch/unlatch and the lock/unlock mechanism of the lockdown ring 130 . Lead 152 activates the dynamic low pressure seal 136 . Lead 154 is provided to monitor the pressure in the space 144 between the primary 146 and secondary 140 seals. A pressure monitor 149 is used for the purpose. This may also be used to monitor the position of the sliding member 128 relative to the outer housing and hence the integrity of the primary metal-to-metal seal.
The operation of the slip joint is now discussed. Under normal conditions, wellhead assembly is in the open position and the inside of the riser 118 would be at high pressure. The riser string 118 , the rotational tension ring 112 , the flexible joint assembly 110 ( and the flowhead assembly in the moon pool of the vessel, not shown) move in unison, so that there may be relative motion between the flowhead assembly and the vessel. The dynamic low pressure seal 136 may be inoperative at this time. When it is desired to perform workover operations, e.g., run a wireline, the wellhead assembly is closed so that there is no direct communication between the inside of riser string 118 and the well 104 . The pressure inside the riser assembly is bled down and the locking ring 130 is disengaged. This allows relative motion between the body 134 of the sliding member and the outer housing 122 . The low pressure dynamic seal is activated. In this configuration, the flowhead assembly (not shown) above the sliding member 128 and the flexible joint assembly 110 is decoupled from the riser string 118 . Tool changeover may safely be performed by humans in the moon pool. Once the new tools have been inserted into the flowhead assembly and lowered to the well head, the lockdown ring 130 is engaged, and the wellhead opened up. In this manner, the invention makes it possible to decouple relative motion of the upper end of the riser assembly from the lower end of the riser assembly.
To connect the slip joint, the slip joint is closed by stroking the inner liner 134 fully into the outer housing item 122 . Pressure is applied down a hydraulic line 148 a to activate the lockdown ring or collet mechanism 130 . The lockdown ring 130 engages the groove 126 to lock the inner liner 134 and outer housing together and providing the force to seal the metal—metal seal 146 . Pressure is then applied down line 150 a to lock the lockdown ring 130 in place preventing accidental unlatching of lockdown ring 130 from the groove 126 . To monitor the status of the primary seal during well operations line 154 is used as a monitor line from the pressure monitor 149 .
To disconnect the slip joint, pressure is applied down line 150 b to unlock the lockdown ring. Pressure is applied down line 148 b to unlatch ring 130 from groove 126 . The slip joint is then free to move with vessel motion. Line 152 provides a positive LP dynamic seal (air or hydraulic fluid) to prevent loss of wellbore fluids to the environment and may also provide lubrication for the slip joint during movement of the inner to the outer barrel (although lubrication may come from an alternative source). The sliding members (inner barrel and outer housing) are not controlled by hydraulic lines. The lifting and lowering of inner barrel to outer housing is provided by means of a external lifting device on the vessel. Motion between these items 122 and 134 is the motion of the vessel relative to the seabed during the unlatched state of the lockdown ring.
While the foregoing disclosure is directed to the preferred embodiments of the invention, various modifications will be apparent to those skilled in the art. It is intended that all variations within the scope and spirit of the appended claims be embraced by the foregoing disclosure. | A pressurized slip joint for a marine intervention riser decouples the flowhead assembly in the moon pool of a vessel from the riser string, enabling safe changeover of equipment during workover operations. One part of the slip joint assembly is coupled to the flowhead assembly through a flexible joint assembly. A second part of the slip joint assembly supports the riser string and is coupled to the tensioning mechanism. The first part may be inserted into the second part and locked in place during workover operations except when equipment changeover is taking place. When changeover is being carried out, the first and second parts are unlocked, so that the flowhead assembly does not move relative to the vessel. In the locked position, a metal-to-metal high pressure seal, with a secondary and tertiary seal controls the pressure in the riser. In the unlocked position, a hydraulically operated dynamic low pressure seal is used. | 4 |
The invention described herein may be manufactured, used, and licensed by or for the United States Government for governmental purposes without the payment to us of any royalty thereon.
BACKGROUND OF THE INVENTION
This invention is in the field of semiconductor solar cells, and more particularly is a semiconductor solar cell with an inversion layer having a relatively high concentration of charge carriers and a method of preparation thereof.
Semiconductor solar cells are well-known in the art. They are known to have p-n junctions near the surface of the device which are exposed to solar light radiation. The photoelectric energy is created by light waves which generates hole-electron pairs. Solar cells, such as Si or CdS cells are sensitive to wave lengths from about 1 μ down to 0.45 μ.
It is well-known that a silicon dioxide layer formed on the surface of p-type silicon or other p-type semiconductors will produce an n-type inversion layer in the semiconductor. Thus, a p-n junction will exist at a shallow depth. However, it is widely accepted that the ordinary oxidation of p-type silicon surface results in an inversion layer having a charge concentration of only 10 11 charge carriers/cm 2 as contrasted with a diffused type junction with a diffused layer having a charge concentration of 10 15 carriers/cm.sup. 2. It may be noted that an inversion layer is induced and when the inducing material, e.g., silicon dioxide, is removed the inversion layer disappears and a substrate reverts back to the p-type semiconductor.
The reason why the silicon dioxide produces an inversion layer in the semiconductor material is attributed partially to interface states and also to the fact that silicon dioxide has a tendency to become positively charged when in contact with another material.
Oxidized silicon surfaces have been studied in connection with transistors, micro circuits and MOS transistors. All these studies indicate that the oxide induces in silicon a negative charge having a charge concentration of approximately 10 11 charge carriers/cm. The oxide may also be contaminated with foreign ions such as hydrogen or sodium, etc. These ions are usually positive so that they can add to the produced charge and raise it to 10 12 charges/cm 2 . Generally, the presence of foreign ions is undesirable because their density cannot be controlled and they are mobile in the oxide.
U.S. Pat. No. 3,769,558 of Lindmayer discloses a semiconductor device of a p-type substrate having oxide covering layers of silicon and chromium of thicknesses between 800 and 1,000 angstroms thick. The oxide covering gives rise to inversion layer of the n-type conductivity on the bulk substrate. The collection of the charge to the external circuit would be accomplished by a Schottky type metal-semiconductor contact wherein the metal is in direct contact with the semiconductor.
One of the concepts proposed for obtaining electrical energy is the electrical power from space concept. This concept involves satellites in space equipped with solar cells which would convert the solar energy to DC power. The DC power generated in space by the satellites would be beamed by means of microwaves to the ground and reconverted to high voltage DC or AC power. The essential characteristics of the solar cells for use in this application are that the solar cells be capable of covering as much of the solar spectrum as possible to obtain the highest practical conversion efficiency and that the fabrication of the solar cells be free of critical processing steps so as to reduce the cost of producing them and to make them feasible for large-scale use.
SUMMARY OF THE INVENTION
The present invention relates to an improved solar cell having a thin oxide layer wherein the current flow is by means of tunneling across or through the thin oxide layer. More particularly, the present invention relates to solar cells containing the combination of features of:
1. Having a thin oxide layer of silicon of between 20 to 50 angstroms so as to permit the direct tunneling of one of the carriers between a silicon substrate and a metal substrate. The utilization of such a thin layer of oxide would also tend to minimize the absorption of the incident light of short wave lengths in the oxide layer and permit greater absorption in the silicon itself.
2. The utilization of p-type conductive silicon so that an inversion layer can be created at the surface and the electron which has a higher mobility than the hole in the silicon can be used as the minority carrier. The electron may also be the tunneling element in the charged transport or conduction process used to make the device function.
3. Supplying a lateral conductivity at the interface through the generation of an inversion layer. The inversion layer being located close to the incident absorption of light, preferably for short wave lengths, and serving as a conduction path for electrons that may be tunneled between the silicon and a metal contact. Additionally, the inversion layer is such that it may permit a decrease in the amount of metal present on the oxide surface which in turn would reduce the amount of incident light absorbed on the outside surface.
The metal contact utilized is preferably aluminum or other metals with a high metal-semiconductor work function difference.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the appearance of an inversion layer of the solar cell device according to the present invention.
FIG. 2 schematically illustrates the solar cell in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As seen in FIG. 1, a method for providing a solar device containing an inversion layer together with the inherent unique characteristics is to utilize a cobalt 60 source for generating the inversion layer and a 30 angstrom oxide layer with a p-type conductivity silicon substrate together with an aluminum metal contact. The presence of an inversion layer can be seen from the frequency dependent, capacity-voltage measurements as shown in FIG. 1. In accordance with the present invention, the characteristics noted in the inversion layer are at the lower frequency, such as the 100 HZ shown in the drawing. This effect only appears on p-type substrates and not n-type substrates. The amount of radiation constitutes approximately 10 minutes of exposure to the radiation source. Further, it may be noted that the increase in capacity symbolic of the inversion, occurs without any applied bias, a condition which is especially of interest for solar cells wherein no external bias is applied.
Other methods of generating the inversion layer with a zero applied bias using the non-stoichiometric growth of silicon is described in Reference 1.* Another technique of generating the inversion is to utilize a hydroxy radical as introduced through water vapor in the growth of the oxide. However, in both of these cases an applied bias may be necessary for optimum utilization of the inversion layer.
The type of metal which may be used to contact the oxide layer should be one which would give rise to a sizable work function difference with p-type silicon. For example, aluminum metal and a p-type silicon of about 10 16 carriers/cm 2 having a work function difference of about 1 volt may be expected.
FIG. 2 schematically illustrates a thin oxide MOS solar cell 10 with a silicon substrate 16 having a silicon oxide layer 12 of about 20 to 50 angstroms. Metal contacts 14, 14' are placed over the oxide layer. The cell 10 utilizes the radiation in the processing of the inversion layer only when all of the combined features of the present invention are present. The cell permits an increase of response to the shorter wave lengths of the solar spectrum and results in higher quantum yield. The device utilizes tunneling as part of the conduction process rather than mainly relying on diffusion as in n-p junction. In operation of the device, the electrons are able to travel along the inversion layer until they tunnel through the oxide to the metal located in a region on the oxide surface as shown in FIG. 2. By this means, there is an extension of the effective area available to the incident solar spectrum.
By fabricating the solar cell according to the structure of FIG. 2, there is eliminated the necessity of controlling the impurity profile of a junction.
The thin oxide MOS solar cell of the present invention preferably utilizes an oxide of silicon such as SiO and SiO 2 . The oxides of silicon may be either in the mono or polycrystalline form, epitaxial, ribbon type, or bulk form.
One method of forming the solar cell of the present invention is to immerse a silicon body in hydrofluoric acid, nitric acid and water, so as to produce a silicon monoxide coating on the p-type regions of the silicon body so as to form the specific thickness of the oxide layer contemplated by the present invention. In utilizing this method, it is necessary that the concentration of nitric acid in the solution be maintained within a narrow critical range and that the silicon solar cell remain in the solution for a controlled time so as to ensure that a coating having a thickness of 20-50 angstroms will result. One means of preparing the solar cell is disclosed in U.S. Pat. No. 3,091,555 of Smythe; however, a control of the oxide thickness is required.
The metal contact in the solar cell is placed over the oxide layer in a small region for contact. This feature is also a critical requirement in the present invention. The current flow occurs by electrons conducted in the inversion layer and tunneling to the metal contact while holes flow into the bulk p-type silicon to the bottom metal contact.
Additionally, the silicon dioxide layer may be formed on the silicon surface by vapor deposition by conventional means such as disclosed in U.S. Pat. No. 3,706,918 of Barone et al.
It is understood that the invention is not limited to the exact details of construction as shown and described, for obvious modifications may be made by persons skilled in the art. | A semiconductor device comprising a first layer of semiconductor material ving a bulk region of p-type conductivity and an inversion surface of n-type conductivity which forms a p-n junction with said bulk region, a covering layer on said inversion surface of oxides of silicon in a thickness of about 20-50 angstroms, and metallic contacts placed over said oxide layer. | 8 |
The invention relates to a tensioning machine for the heat treatment of a continuously transported length of textile material which is guided widthwise in its movement.
BACKGROUND OF THE INVENTION
In the heat treatment of lengths of textile material in a tensioning machine, in addition to maintaining the material at a suitable temperature and for a sufficient period of dwell time, it is important that optimum tensioning of the lengths of textile material across their width (that is to say in a direction at right angles to the transport direction) is always ensured. In this connection, it should be borne in mind amongst other things that varying alterations in width and thur alterations in the transverse tension can occur over the length of the heat treatment section in the tensioning machine as a result of the selected temperature and transit time and as a function of the type of textile material undergoing treatment. In order to be able to control the widthwise material tension within the length of textile material according to a desired overall tension, various machine constructions have already been developed in which the spacing of the two continuously moving tensioning chains which hold a length of material on its longitudinal edges is set with the aid of at least one transverse width-adjusting spindle.
This type of construction is described in German Offenlegungsschrift No. 2,335,124. Here the width-adjusting spindle consists of two half spindles with threaded sections, the threaded section of one half spindle being threaded in the opposite direction to that of the other half spindle so that when the width-adjusting spindle rotates in one direction or the other the guide rails for the tension chains, which are held on the half spindles by means of threaded nuts, can be moved towards or away from each other. While one half spindle is axially fixed and provided with a spindle drive, the second half spindle is axially movable but connected to the first half spindle so as to be rotationally fixed. The outer end of this second half spindle is extended towards the outside by a rod and is there articulated on a forked one-arm control lever, the lower free end of which is articulated on the piston rod of a pneumatic or hydraulic cylinder and which in its central region cooperates with one or two control switches in such a way that the spindle drive motor arranged at the opposite end of the width-adjusting spindle can be actuated to create a greater or smaller distance between the chain guide rails or tensioning chains so that a maximum permissible or minimum necessary widthways tension can be maintained. The working pressure of the pnuematic or hydraulic operating cylinder should be a criterion for the textile material tension provided.
In a practical construction of the known tensioning machine described above, the control provided there for the heat treatment of carpet lengths and the like may be sufficiently accurate; however, in tensioning machines for other textile finishing processes, particularly for lengths of more delicate textile materials, e.g. tulle, curtains, material for outer clothing, or industrial fabrics, the control provided in order to maintain a desired widthwise tension must be capable of being effected with considerably greater precision than is described above. In addition this known construction involves comparatively high construction costs and requires a correspondingly large amount of space.
The object of the invention, therefore, is to provide a tensioning machine which has a simple, space-saving construction and is distinguished by an extremely sensitive control for the widthwise tensioning of the length of material.
SUMMARY OF THE INVENTION
In a tensioning machine according to the invention, the control element connected to the second spindle section consists of a force sensitive or measuring cell and it is therefore possible on the one hand to use an extremely sensitive control element for adjusting the widthwise tension and on the other hand to be able to fall back on an extremely simple structural and space-saving component which is commercially available. The way in which such force measuring cells operate is based upon the use of strain gauges, piezoelectrics and similar sensitive measuring arrangements. In addition a force measuring cell can be arranged most advantageously on an outer wall of the tensioning machine or the tensioning machine frame so that it is easily accessible from the outside and is protected against the high operating temperatures which frequently occur in the interior of the tensioning machine. Utilizing the measurement signals from the force measuring cell and associated electrical controls, a desired width adjustment of the rotating tensioning chains can be made in a suitable manner with the aid of the spindle drive by means of the width-adjusting spindle, the threaded nuts and the chain guide rails.
THE DRAWINGS
Further details and advantages of the invention are set out in the following description of an embodiment illustrated in the accompanying drawings, in which:
FIG. 1 is is a greatly simplified plan view of a tensioning machine with the top removed;
FIG. 2 is a simplified cross-sectional view through the tensioning machine approximately along the line II--II in FIG. 1;
FIG. 3 is a cross sectional detail on an enlarged scale of section III in FIG. 2 and illustrates the assembly of the force measuring cell and the associated outer end of the second spindle section, including the relevant bearings; and
FIGS. 4 and 5 are cross sectional views on an enlarged scale corresponding to the sections IV and V, respectively, in FIG. 2 and illustrating further bearing arrangements for the width-adjusting spindle.
DETAILED DESCRIPTION
First of all the general construction of the tensioning machine 1, in so far as it is of interest in the present case, will be explained with the aid of FIGS. 1 and 2. In the illustrated example, the tensioning machine 1 has an inlet zone E, three heat treatment zones F 1 , F 2 , F 3 and an outlet zone A. In this tensioning machine 1, a length of textile material 3 which is continuously transported in the direction of the arrow 2 can be tensioned widthwise and subjected to heat treatment, for example, dried, fixed or treated in a similar manner. Two continuously moving tenter or tensioning chains 4, 4a (cf. FIG. 2) serve in the usual way for continuous transport and tensioning of the length of textile material 3 by holding the two longitudinal edges 3a, 3b of the material with known retaining means, such as clip plates or pin plates (indicated at 5). The two tensioning chains 4, 4a are guided in conventional chain guide rails 6, 6a which hold the tensioning chains 4, 4a in the individual treatment zones at a distance from one another which corresponds to the necessary width of the length of textile material in each case.
As can be seen clearly in FIG. 1, the two tensioning chains 4, 4a can be adjusted so that in the relevant zones E, F 1 , F 2 , F 3 and A they tension the length of textile material 3 and cause it to be increasingly stretched (divergent guiding of the tensioning chains), kept at the same width (parallel guiding of the tensioning chains), or allowed it to become increasingly narrow in width (convergent guiding of the tensioning chains). In this way, the tensioning layout shown in FIG. 1 is produced for the length of textile material 3.
For a tensioning layout running symmetrically to the longitudinal axis 1a of the tensioning machine, accurate measuring control and adjusting facilities must be provided for the relative spacing of the two continuously moving tensioning chains 4, 4a in order to ensure the optimum widthwise tension for the length of material 3 for any special type of treatment and material to be treated in any zone of the tensioning machine.
As has already been mentioned above, the distance between the tensioning chains is adjusted by means of the chain guide rails 6, 6a which are divided into a plurality of longitudinal sections which are articulated to one another, as is sufficiently known and indicated in FIG. 1. The distance between the two tensioning chains 4, 4a and thus the relevant material width is adjusted with the aid of width-adjusting spindles 7 which extend in the transverse direction of the machine and at least one of which is associated with a treatment zone. Each width-adjusting spindle 7 is preferably located in the region of the junction of two adjacent zones or the transition from one zone to another (cf. also FIG. 1).
FIG. 2 indicates in a simplified manner that the chain guide rails 6, 6a have threaded nuts 8, 8a each of which is screwed onto an appropriate threaded part 9, 9a of the width-adjusting spindle, these threaded parts having opposite threads so that when the width-adjusting spindle 7 turns in one or the other direction the chain guide rails 6, 6a are correspondingly moved towards one another or away from one another, uniformly in each case with respect to the longitudinal central plane 1a (cf. FIG. 2). With regard to the chain guide rails 6, 6a, it should be added that in the illustrated example these rails are intended for tensioning chains 4, 4a which move around continuously in a vertical plane and thus also extend into the region below the width-adjusting spindles 7.
Each width-adjusting spindle 7 is divided approximately in half into first and second spindle sections, the first spindle section 7a having the threaded part 9 and the second spindle section 7b having the opposing threaded part 9a. The inner ends 7a' and 7b', respectively of the two spindle section 7a, 7b are splined or otherwise suitably connected to each other--as is illustrated in greater detail in FIG. 5--so that they are fixed against relative rotation but can be moved towards or away from each other. The outer end 7a" of the first spindle section 7a and thus one end of the whole width-adjusting spindle 7 is connected to a controllable and reversible spindle drive 10, while the opposite end, i.e., the outer end 7b" of the second spindle section 7b, is connected to a force sensitive control element formed by a force measuring cell 11.
With the aid of FIG. 3 it will now be explained how the force measuring cell 11 is on the one hand connected to the axially outer end 7b" of the second spindle section 7b and on the other hand is supported in a fixed position.
A type of bearing block 13 is fixed on or in an outer wall 12--which is merely indicated in FIG. 3--of the tensioning machine frame. This bearing block 13 contains a spherical segment bearing 14, which is constructed as a sliding bearing and is arranged directly on the outer end 7b" of the second spindle section 7b, and a radial sliding bearing 15 which is arranged adjacent to the spherical segment bearing 14 in the direction of the inner end 7b' of the second spindle section 7b. While the stationary radial sliding bearing 15 supports the outer end 7b" of the spindle section 7b so that it is rotatable but axially movable, the spherical segment bearing 14 is fixed on the end 7b" of the spindle section 7b with the aid of a threaded clamping ring 16 so that it is not axially movable, i.e., this spherical segment bearing 14 participates in every movement of the second spindle section 7b in its axial direction (double arrow 17). This spherical segment bearing 14 is arranged inside the inner end 18a of a preferably cylindrical housing 18 which is directed towards the center of the tensioning machine and is supported towards the center of the tensioning machine by a flange 18b on the housing. However, the essential part of the force measuring cell 11 is also accommodated inside this housing 18, i.e., the force measuring cell 11 is arranged in axial extension of the outer end 7b" of the second spindle section 7b a short axial distance therefrom. The force measuring cell 11, which is of conventional construction, has a first measuring cell part 11a which is arranged approximately centrally and is immovably fixed on the outer wall 12 with the aid of a screw 19 on an outer plate 20 of the bearing block 13. This first measuring cell part 11a is enclosed by a housing of a second measuring cell part 11b which has an approximately cylindrical external shape and is also arranged inside the cylindrical housing 18, but at the end 18c thereof adjacent the exterior. This second measuring cell part 11b is operatively connected to the first measuring cell part 11a by an inner measuring element 11c (e.g. a strain gauge), as will be explained in greater detail below. Inside the common housing 18 the spherical segment bearing 14 and the force measuring cell 11 are connected to each other, and thus to the outer end 7b" of the second spindle section 7b, by the housing flange 18b, a spacer ring or spacer tube 21, a further spacer ring 22 and a clamping ring 23. The cell 11 and the outer end of the spindle section 7b are spaced apart, but are axially immovable relative to each other. However, the outer end 7b" of the spindle section 7b can rotate freely within the cylindrical housing 18 and relative to the cell 11 because of the spherical segment bearing 14. The housing 18 and the second measuring cell part 11b are not rotatable relative to each other because of a housing pin 24 which projects radially outwards and is accommodated in a slot 25 in a bracket 26 fixed to the outer plate 20. An electrical cable 27 which is connected to electrical control means (not shown) of conventional construction leads out from the force measuring cell 11.
The outer end 7a" of the first spindle section 7a (FIG. 4), that is, the end of the spindle which is connected to the spindle drive 10, is mounted in a spherical segment bearing 28 which in this case is fixed with its housing 29 on the other outer wall 12a of the frame of the tensioning machine. In contrast to the opposing end of the spindle, which is connected to the force measuring cell 11, this end of the spindle drive is fixed so as to be immovable in the axial direction. The spindle drive 10 (cf. FIG. 2) to be associated with this end of the spindle can be constructed in any suitable manner so that it can be controlled by means of the aforementioned control arrangement in order to drive the width-adjusting spindle in one direction of rotation or the other depending upon whether the tensioning chains 4, 4a are to be moved away from each other or towards each other.
The connection 30 between the inner ends 7a', 7b' of the two spindle sections 7a and 7b is shown in detail in FIG. 5 and comprises a sleeve part 31 on the inner end 7a ' of the first spindle section 7a which is open towards the second spindle section 7b. The end 7b' of the second spindle part 7b is received in the sleeve 31 and is so dimensioned as to be capable of sliding movement in the axial direction. However, the inner end 7b' of the second spindle section 7b is a sufficient distance from the sleeve base 31a that there is enough axial clearance available in the event of axial movements (double arrow 17) of the second spindle section 7b during operation. In order for the rotary movement imparted to the first spindle section 7a by the spindle drive 10 to be transmitted to the second spindle section 7b as well, the two inner spindle ends 7a', 7 b' are connected to each other so as to be fixed against relative rotation, for example by means of a keyway 32 and a key 33.
At the connection 30 between the two spindle sections 7a and 7b, these two sections are supported by means of the sleeve part 31 in a radial sliding bearing 34 so as to be rotatable, and this radial sliding bearing 34 is additionally supported, as indicated in FIG. 2, by means of a support 35 on the base. Thus the width-adjusting spindle 7 is reliably supported over its whole length (i.e., across the width of the machine), and the preferred use of spherical segment bearings on the outer spindle ends permits a sufficiently rotatability of the spindle 7.
In the preferred embodiment each of the width-adjusting spindles 7 of the tensioning machine 1 is equipped at one end with an individual spindle drive 10 and a force measuring cell at the opposing end so that by means of appropriate, known control means, each individual spindle can be adjusted extremely accurately and sensitively to the necessary tension independently of other spindles. Thus, if a length of textile material 3 is to undergo heat treatment during operation of the machine, the force measuring cell associated with each width-adjusting spindle can be set to a predetermined mean value. If during treatment of the length of material 3 the tension deviates from the predetermined widthwise tension, this can be determined extremely accurately by the force measuring cell 11 which generates and transmits a corresponding signal to the control means so that the control means sets the relevant spindle drive 10 in operation in the necessary manner so that the widthwise tension of the length of textile material is restored to the predetermined tension by means of the chain guide rails 6, 6a and the tensioning chains 4, 4a.
If one assumes that the widthwise tension in the length of textile material 3 has become too great, then a corresponding traction may be exerted in the direction of the arrow 17a (FIG. 3) on the second spindle section 7b by means of the tensioning chain 4a, the chain guide rail 6a and the threaded nut 8a (cf. also FIG. 2). Since the outer end 7b is connected to the housing 18 and the second measuring cell part 11b so as to be axially fixed to the spindle, these elements also move inside the bearing block 13 in the direction of the arrow 17a, whereas the first measuring cell part 11a remains immovable, i.e., stationary, so that a signal is generated by the inner measuring element 11c of the force measuring cell 11. This signal is passed via the electrical cable 27 to the control means which in turn, as already mentioned, supplies in known manner a corresponding control signal to the spindle drive 10 as regards the desired new setting for the widthwise tension. If the predetermined widthwise tension for the length of textile material 3 is relaxed, this is followed by the sensing of an alteration in the predetermined tension and the generation of a signal to operate the spindle drive 10 in the reverse manner. With this extremely compact and very simply designed construction and arrangement, particularly that of the force sensitive element (force measuring cell), an extremely sensitive adjustment of the widthwise tension can be achieved at any time, which is important particularly for delicate textile materials.
Finally, it should be borne in mind that the spindle construction described in detail on the basis of FIGS. 2 to 5 with its advantageous control possibilities does, of course, apply to all the spindles 7 of the tensioning machine. However, in addition to the control, as described in detail, of the width setting by appropriate adjustment of the working width at the point of measurement, a further control function is provided which is at least as important: the sensing of the force is also necessary in particlar in order to prevent the breaking loads of the chains from being exceeded by excessively high tensions and also to adjust the widthwise guiding, i.e., the overall tension, in order to keep the tensions within limits which are beneficial for example for thermofixing and are also suitable for achieving the correct product width. | A tensioning machine for use in the heat treatment of textile fabric for controlling the widthwise dimension of the fabric comprises a pair of continuously movable tenter chains for moving the fabric along a path and supported by guides which are coupled to one or more rotatable spindles operable to adjust the guides transversely of such path. One end of each spindle is both rotatable and axially movable and cooperates with a force sensitive device that is operable in response to an alteration in the force applied thereon to generate a signal. Each spindle is coupled to a rotary drive, the operation of which is controlled by the signal generated by the associated force sensitive device. | 3 |
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 60/731,797, filed on Oct. 31, 2005, the entire teachings of which are incorporated herein by reference.
BACKGROUND
[0002] Various approaches exist for providing RF power to dynamic loads. RF generators provide power to dynamic loads typically at frequencies between about 400 kHz and about 200 MHz. Frequencies used in some scientific, industrial and medical applications are approximately 2 MHz, 13.56 MHz and 27 MHz.
[0003] As shown in FIG. 1A , one system 100 for providing RF power to dynamic loads (i.e., a plasma load 140 ) involves a fixed frequency RF generator 110 and a two-axis tunable matching network 120 connected by a 50 Ω transmission line 130 . The tunable matching network 120 includes a series motorized vacuum variable capacitor 122 and inductor 124 and a shunt motorized vacuum variable capacitor 126 . The algorithm used to determine the series and shunt capacitance is based on impedance measurements typically made using a magnitude and phase detector 150 . Independent power control is based on power measurements at the RF generator 110 . The power control loop 160 and impedance control loop 162 are independent.
[0004] As shown in FIG. 1B , another system 100 ′ for providing RF power to dynamic loads involves a fixed element matching network 120 ′ fed by an RF generator 110 and connected by a 50 Ω transmission line 130 . The fixed element matching network 120 ′ includes a series capacitor 122 and inductor 124 and a shunt capacitor 126 . The frequency of the RF generator 110 can be tuned to a certain range (e.g., 13.56 MHz ±5%). The RF generator 110 frequency command is based on the value of voltage standing wave ratio (VSWR). The independent power loop and VSWR (impedance) control loop 160 ′ are based on measurements at the output of the RF generator 110 .
[0005] As shown in FIG. 1C , another system 100 ″ for providing RF power to dynamic loads involves an integrated RF generator-impedance matching network 120 ″. The RF generator-impedance matching network 120 ″ includes a series capacitor 122 and inductor 124 and a plurality of shunt capacitor 126 a . . . 126 n . The shunt capacitor 126 a . . . 126 n are coupled to a switching circuit 127 a . . . 127 n that couples and decouples the capacitors 126 to ground. The power control and frequency control 160 ″ of the system 100 ″ are not conducted simultaneously.
SUMMARY
[0006] These prior art techniques and methods have disadvantages. Higher cost is typically associated with prior art techniques and methods due to the need for at least two separate modules: 1) the RF generator/amplifier and 2) the impedance matching network, which are to be connected via a transmission line. Furthermore, each module requires a RF voltage/current sensor or a magnitude/phase detector.
[0007] Plasma impedance is a function of the power delivered to the plasma. Furthermore, the power delivered by the RF generator is a function of the impedance “seen” by the generator. As a result, a clear circular interdependence exists between delivered power and load impedance yielding a multi-input-multi-output (MIMO) system with cross-coupling. In prior art systems, the RF generator control loop and the impedance matching control loop are independent and thus cannot compensate for the cross-coupling between power control and impedance matching control loops. This leads to poor closed-loop performance.
[0008] The dynamic response of any controlled system is only as fast as the slowest functional module (sensor, actuator, or control system parameters). In prior art systems, the slowest functional module is typically the DC power supply. Specifically, the DC power supplied to the input of the RF power amplifier usually includes a large electrolytic capacitor that is used to filter higher frequencies. The downside of using such a filter network is that the dynamic response (e.g., response to a step change in power command) is slow regardless of the control update rate. The system is therefore unable to sufficiently compensate for plasma instabilities.
[0009] In systems that use a vacuum capacitor driven by motors, the response time is on the order of hundreds of milliseconds. Owing to the fact that plasma transients (sudden and rapid change of impedance) of interest occur within hundreds of microseconds, the vacuum capacitor cannot be used to match load changes attributed to plasma transients.
[0010] Control algorithms for matching networks used in the prior art have relied upon the real and imaginary components of the measured impedance. Impedance measurement-based matching control suffers from an inherent disadvantage. For example, a change in shunt capacitance to correct or modify the real component of the impedance results in an undesirable change in the imaginary component of the impedance. Similarly, a change in the series capacitance or frequency to correct or modify the imaginary component of the impedance results in an undesirable change in the real component of the impedance. The matrix that relates the controlled variable vector (formulated by the real and imaginary components of the impedance) and the controlling variable vector (formulated by the shunt and series capacitance or the shunt capacitance and frequency) is non-diagonal. Impedance measurement-based control algorithms are therefore not effective. Control algorithms based on the impedance formulated by using magnitude and phase measurements of the impedance are similarly ineffective.
[0011] Calibration methods for prior art systems calibrate the RF impedance analyzer or VI probe at the input of the electronic matching network. These calibration methods assume the power loss in the electronic matching network is fixed for all states of the electronic matching network and operating frequencies. However, the losses of the electronic matching network contribute significantly to the overall system operation.
[0012] Accordingly, a need therefore exists for improved methods and systems for controlling power supplied to a dynamic plasma load and the losses associated therewith.
[0013] There is provided a system for delivering power to a dynamic load. The system includes a power supply providing DC power having a substantially constant power open loop response, a power amplifier for converting the DC power to RF power, a sensor for measuring voltage, current and phase angle between voltage and current vectors associated with the RF power, an electrically controllable impedance matching system to modify the impedance of the power amplifier to at lease substantially match an impedance of a dynamic load, and a controller for controlling the electrically controllable impedance matching system. The system further includes a sensor calibration measuring module for determining power delivered by the power amplifier, an electronic matching system calibration module for determining power delivered to a dynamic load, and a power dissipation module for calculating power dissipated in the electrically controllable impedance matching system.
[0014] In one embodiment, the electrically controllable impedance matching system can include an inductor, a capacitor in series with the inductor, and a plurality of switched capacitors in parallel with the dynamic load. The inductor can be a multiple tap-type inductor or a variable-type inductor. Each of the plurality of switched capacitors can be in series with a switch and an additional capacitor. In another embodiment, the electrically controllable impedance matching system can include a capacitor, and a plurality of switched capacitors in parallel with the dynamic load, wherein each of the plurality of capacitors is in series with a switch and an additional capacitor. In yet another embodiment, the electrically controllable impedance matching system can control the frequency of the impedance matching between the power amplifier and the dynamic load.
[0015] In one embodiment, the controller can control the electrically controllable impedance matching system for simultaneous control of conductance and susceptance associated with the impedance between the power amplifier and the dynamic load. In another embodiment, the controller can simultaneously control RF power frequency, RF power magnitude and the impedance between the power amplifier and the dynamic load. In yet another embodiment, the controller can control the electrically controllable impedance matching system for regulating conductance and susceptance to setpoints that stabilize an unstable dynamic load.
[0016] The power dissipated in the electrically controllable impedance matching system is the difference between the power delivered by the power amplifier and the power delivered to the dynamic load. The power delivered to the dynamic load is a sum of the power delivered to a resistive load and the power dissipated inside the load simulator.
[0017] The sensor calibration measuring module calibrates the sensor into a resistive load, wherein the resistive load is 50 Ω. The electronic matching module calibrates an output of the electrically controllable impedance matching system into a load simulator. The load simulator can be an inverse electrically controllable impedance matching system. The electronic matching system calibration module can include a power meter calibration module for determining power delivered to a resistive load; and a load simulator calibration module for determining power dissipated inside the load simulator. The resistive load can be 50 Ω. The radio frequency power delivery system provides at least the following advantages over prior art systems. The system can enhance power setpoint regulation, impedance matching, and load disturbance mitigation using high-speed (e.g., in excess of 50 kHz in one embodiment) digital multi-input-multi-output (MIMO) control. The system can operate in the presence of transient changes in plasma load properties and under conditions involving fast plasma stabilization. The system can provide a RF power delivery system that is robust to transients during startup of the system. The system can provide a high power step-up ratio, wherein the high power step-up ratio is 100 (e.g., 15 W to 1500 W). The system can measure power delivered to the load connected to the output of the integrated generator system. The system can allow for regulation of power that is independent of the power loss variation associated with the state/value of various controlled variables. The system can eliminate the need for recipe-based calibration for plasma loads.
BRIEF DESCRIPTIONS OF THE DRAWINGS
[0018] The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
[0019] FIG. 1A is a diagram of an RF power delivery system having a two-axis tunable matching network according to the prior art;
[0020] FIG. 1B is a diagram of an RF power delivery system having a fixed matching network according to the prior art;
[0021] FIG. 1C is a diagram of an RF power delivery system having an integrated RF generator-impedance matching network according to the prior art;
[0022] FIG. 2 is a module-based diagram of the On-Chamber RF power delivery system;
[0023] FIG. 3 is a plasma stability graph;
[0024] FIG. 4 is one embodiment of a fast DC bus of FIG. 2 ;
[0025] FIG. 5 is one embodiment of an RF impedance analyzer or VI Probe of FIG. 2
[0026] FIG. 6 is one embodiment of an electronic matching network of FIG. 2 ;
[0027] FIG. 7 is one embodiment of a module-based diagram of a DSP compensator board of FIG. 2 ;
[0028] FIG. 8 is a block diagram for calibrating the On-Chamber RF power delivery system;
[0029] FIG. 9A is one embodiment for calibrating a power meter to a 50 Ω calorimeter power reference;
[0030] FIG. 9B is one embodiment for calibrating a load simulator to a DC power reference;
[0031] FIG. 9C is one embodiment for calibrating an RF impedance analyzer into a 50 Ω load; and
[0032] FIG. 9D is one embodiment for calibrating power delivered into the load simulator.
DETAILED DESCRIPTION
[0033] Generally, an integrated radio frequency (RF) power delivery system is provided for dynamic load applications (e.g., inductive and/or capacitive plasma load). FIG. 2 is an illustration of the integrated radio frequency (RF) power delivery system 200 . Representative functional modules of the integrated system 200 include a fast DC bus 210 , an RF power amplifier (“PA”) 220 , a digital signal processor (“DSP”) compensator board 230 , an RF impedance analyzer or VI probe 240 , and an electronic matching network 250 . The system 200 is coupled to a plasma load 260 . It should be understood by one skilled in the art that the integrated system 200 can be implemented for a wide range of resistive and reactive loads.
[0034] Generally, the fast DC bus 210 delivers DC power to the power amplifier 220 . The power amplifier 220 converts the DC power from the fast DC bus 210 to an RF power at a frequency. The electronic matching system 250 switches shunt capacitors (not shown) to match the impedance between the power amplifier 220 and the plasma load 260 to facilitate stable and maximum power transfer from the power amplifier 220 to the plasma load 260 . The DSP compensator board 230 controls the operation of the system 200 based on measurements received from the fast bus controller 212 and RF impedance analyzer 240 . The RF impedance analyzer 240 measures the RMS voltage, RMS current, and phase angle between the RF voltage and current vectors. Based on these measurements, relevant RF parameters are computed by the DSP compensator board 230 . These parameters include, but are not limited to impedance vector z , admittance vector y , delivered power P del , and voltage-standing wave ratio (“VSWR”). Typical operations of the DSP compensator board include power setpoints through the fast bus controller 212 , RF power frequency setpoints through the power amplifier driver 222 , and switching frequency through the electronic match controller 252 .
[0035] In one aspect, the system 200 achieves simultaneous power and impedance regulation. Independent susceptance regulation allows for the implementation of a frequency control algorithm based only on the deviation of the conductance from the conductance setpoint. As a result, both control loops can be operated simultaneously and at high-speed resulting in improved robustness. Further, well-known instabilities for electronegative plasmas at low-pressure (e.g., SF 6 at 5 mT at 300 W as illustrated in FIG. 3 ) can be stabilized by setting arbitrary conductance and susceptance setpoints in conjunction with operation of the Fast DC bus 210 .
[0036] FIG. 4 is a diagram of a partial resonant inverter power supply type fast DC bus 210 . The fast DC bus 210 provides process stability due to its associated constant power open loop response. The fast DC bus 210 improves FET utilization over the entire load space which results in more power being delivered to the load with the same PA 220 ( FIG. 2 ). The fast DC bus 210 has a fast response rate allowing it to deliver increased power to the plasma so it does not extinguish while also allowing the flexibility to reduce the bus voltage to ensure the FETs on the PA 220 operate in a safe mode. Other types of topologies can for the fast DC bus 210 can be used. See for example, co-pending continuation-in-part application it's parent U.S. application Ser. No. 10/947,397 filed Sep. 22, 2004, the entire teaching of each application are herein incorporated by reference.
[0037] In one embodiment, the fast DC bus can be a partial resonant inverter 210 that includes a pair of switches (MOSFETs) 302 a , 302 b , an inductor (L) 306 , a capacitor (C) 308 , and four diodes 310 a , 310 b , 310 c , and 310 d . In operation, the partial resonant inverter 300 converts the input voltage into a square wave or other known type DC wave form. The square wave is passed through the inductor 306 and capacitor 308 , the combination of which form an LC filter, clamped by the diodes 310 c , 310 d , coupled and rectified by a transformer rectifier 304 and filtered to obtain a desired DC voltage (power setpoint). The DC power setpoint is provided from the DSP compensator board 230 ( FIG. 2 ). The desired impedance setpoint can be specified in terms of its vector inverse (referred to as admittance) and which constitutes simultaneous regulation of conductance to an arbitrary conductance setpoint and regulation of susceptance to an arbitrary susceptance setpoint. The output of the partial resonant inverter 300 (DC-DC converter) is connected to DC input of the RF power generator/amplifier 220 .
[0038] In operation, the capacitor 308 is periodically charged to an input rail voltage (+Vin) and discharged while the capacitor current is passed via the plasma load 260 ( FIG. 2 ). Every charge or discharge cycle, the energy deposited in the resistive load is equal to CV 2 /2, independent of load resistance. Thus, the power is equal to F SW ×CV 2 /2, where F SW is the switching frequency and V is the input voltage. The inductor 306 ensures that the capacitor 308 is fully charged and discharged in finite time. One advantage of the partial resonant inverter 300 design is the ability to control the output voltage by varying either V or/and F SW .
[0039] FIG. 5 is a diagram of one embodiment of an RF impedance analyzer or VI Probe 240 . The VI Probe 240 includes a DC power supply 242 , an analysis board assembly 244 , and a probe head assembly 246 . The analysis board assembly 244 receives low-level RF signals from the probe head assembly 246 . The probe head assembly 246 provides two voltage outputs: 1) a voltage representation of the time varying electric field present in the probe head assembly 246 (voltage signal); and 2) a voltage representation of the time varying magnetic field present in the probe head assembly 246 (current signal). The analysis board assembly 244 receives and processes the two voltage outputs of the probe head assembly 246 and outputs the RF parameters to the DSP compensator board 230 ( FIG. 2 ). MKS Instruments, Inc. VI-Probe- 4100 and VI-Probe- 350 are exemplary analyzers that can be used for this purpose.
[0040] FIG. 6 is a diagram of one embodiment of an electronic matching network 250 . In one embodiment, the electronic matching 250 includes an inductance 254 in series with the load 260 (e.g., a compact inductor with multiple tap points), a fixed or variable series-padding capacitor 252 , and field effect transistors (“FET's”) 256 a . . . 256 n that switch one or more upper capacitors C tu (i) 258 a . . . 258 n to a corresponding lower capacitor C td (i) 258 a ′ . . . 258 n ′, which is terminated to ground. In some embodiments, the electronic matching 250 network does not include the inductance 254 in series with the load 260 . Other types of electronic matching networks can be used. See for example, U.S. Pat. No. 6,887,339, the entire teaching of which is herein incorporated by reference.
[0041] FIG. 7 shows a module-based diagram of a DSP compensator board 230 . The DSP compensator board 230 incorporates both a digital signal processor (“DSP”) and a field programmable gate array (“FPGA”), and together controls the entire integrated system 200 . The DSP compensator board includes an admittance compensation module 232 , a frequency control module 234 , an electronic match control module 236 , an RF power computation module 237 , and an RF power control module 238 . Generally, the DSP compensator board receives the output from the VP probe 240 . The admittance computation module 232 uses the VI probe outputs to calculate the admittance of the system 200 . The frequency control module 234 uses the admittance to vary the frequency of the power amplifier 220 . The electronic match control module 236 uses the admittance to switch the FETs 256 of the electronic matching network 250 on or off. The RF power computation module 237 uses the VI probe outputs to calculate the RF power of the system 200 . The RF power control module 234 uses the RF power computation to regulate the power supplied from the fast DC bus power 210 . A more detailed description of the operation of the system 200 is set forth below.
[0042] One embodiment of the power regulation objective and algorithm is set forth below: The objective is to regulate the delivered power P del to a user-defined setpoint P sp . To ensure smooth transitions, trajectory generators are used. In one embodiment, a first-order trajectory is generated as follows:
ⅆ P t ⅆ t = 1 τ t ( P t ( t ) - P sp ) EQN . 1
where τ t is the trajectory time constant and P t is the desired power trajectory. The delivered-power control algorithm, in terms of the change in power commanded to the Fast Bus, is given by the following relationship:
P cmd =k p ( P t −P del )+ k i ∫( P t −P del ) dt EQN. 2
where k P and k i are the proportional and integral gains, respectively.
[0043] Admittance regulation objective: A normalized admittance vector is defined as follows: y =g+jb where g is the normalized conductance and b is the normalized susceptance. The impedance matching control objective is formulated as follows: g→g sp and b→b sp where g sp and b sp are arbitrary setpoints selected to improve plasma stability. The above objective is reinterpreted in terms of impedance by noting that impedance is defined as the reciprocal of admittance, according to the following relationship:
z = 1 y = r + j x = R + j X Z 0 = R + j X R 0 + j 0 EQN . 3
where z is the normalized impedance, r and x are the resistance and reactance, respectively, Z 0 =R 0 +j 0 denotes a nominal RF amplifier characteristic impedance. It follows that when g→1 and b→0, we obtain R→R 0 and X→0.
[0044] Admittance regulation algorithm: The frequency control loop is designed by using conductance measurements, for example, as a PI control algorithm as follows:
f tcmd =−k pf ( g sp −g )− k if ∫( g sp −g ) dt EQN. 4
where k pf and k if are scalar proportional and integral control gains. The shunt capacitance control loop is designed by using conductance measurements, for example, as a PI control algorithm as follows:
C tcmd =−k pc ( b sp −b )− k ic ∫( b sp −b ) dt EQN. 5
where d pc and k ic are scalar proportional and integral control gains.
[0045] In operation, referring now to FIGS. 2, 3 and 6 , after the user provides a non-zero setpoint, the trajectory generator and the power and admittance control algorithms are simultaneously activated and executed. The VI probe 240 provides analog signals proportional to the RF voltage and RF current, which are synchronously sampled by the analog-to-digital converters, sent to a mixer and CIC filter (not shown) and ultimately sent through a calibration matrix to yield RF voltage and RF current measurements given by the following relationships:
V =V r +jV i
and
I =I r +jI i EQN. 6
where V , I denote vector representations of the instantaneous RF voltage and current, respectively, and subscripts r and i are used to denote the scalar values of the real and imaginary components.
[0046] The average delivered power is computed as follows:
P del = 1 2 Re { VI _ * } = V r I r + V i I i EQN . 7
where Re{} denotes the real component of the vector, and superscript * is used to denote the complex conjugate of the vector.
[0047] The admittance vector Y is then computed as follows:
Y _ = I _ V _ = ( I r V r + I i V i ) V r 2 + V i 2 + j ( I i V r - I r V i ) V r 2 + V i 2 ≡ G + j B EQN . 8
where the conductance G and the susceptance B are real and imaginary components of the admittance Y .
[0048] The normalized conductance g and nonnalized susceptance b are computed as follows:
g = Z 0 G = Z 0 ( I r V r + I i V i ) V r 2 + V i 2
and
b = Z 0 B = Z 0 ( I i V r - I r V i ) V r 2 + V i 2 EQN . 9
where Z 0 denotes the characteristic impedance of the RF amplifier. The measurements of P del , g, b are respectively sent to the control algorithms for P cmd , f cmd , C tcmd respectively.
[0049] The electronic match controller 252 switches the FETs 256 ( FIG. 6 ) thereby switching the shunt capacitors 258 to match the impedance between the power amplifier 20 and the dynamic load 260 . The absence of moving mechanical parts leads to higher reliability. In one embodiment, the step response of the system 200 is faster than about 1 ms because the speed of the response is governed by the electronics and not by the mechanical response.
[0050] A change in frequency results in a change in both the conductance and the susceptance. However, for an integrated system without transmission line cables, a change in shunt capacitance results only in a change in the susceptance and does not affect the conductance value. Thus, the matrix that relates the controlled variable vector (formulated by the real and imaginary components of the admittance) and the controlling variable vector (formulated by the shunt and series capacitance or the shunt and frequency) is triangular. As a result, independent susceptance regulation is achieved by varying the shunt capacitance.
[0051] Independent susceptance regulation allows for the implementation of a frequency control algorithm based only on the deviation of the conductance from the conductance setpoint. As a result, both the conductance-based frequency control loop and the susceptance-based shunt capacitance control loop can be operated simultaneously and at high-speed, resulting in improved robustness.
[0052] FIG. 8 is a block diagram 300 of a method for determining the power dissipated (loss) in the electronic matching network 250 ( FIG. 2 ) to improve the efficiency of the system 200 . Step one ( 310 ), a power meter 314 ( FIG. 9A ) is calibrated into a 50 Ω calorimeter power reference to determine the power delivered to the 50 Ω load. Step two ( 320 ), a load simulator calorimeter 332 ( FIG. 9B ) is calibrated to a DC power reference to determine the power dissipated inside a load simulator 342 ( FIG. 9D ). Step three ( 330 ), the VI probe 240 ( FIG. 2 ) is calibrated into a 50 Ω load to determine the power delivered by the power amplifier 220 ( FIG. 2 ). Step four ( 340 ), the output of the system 200 is calibrated into the load simulator 342 to determine the power delivered to Z L =R L +jX L . Step 5 ( 350 ), the power dissipated in the electronic matching system is calculated by difference between the he power delivered by the power amplifier 220 and the power delivered to. Z L =R L +jX L .
[0053] FIG. 9A is detailed implementation diagram of step 310 for calibrating the power meter 314 . A calorimeter 322 is coupled to the output of the VI Probe 240 , RF power is applied from the power amplifier 220 , and the power meter 314 is calibrated. Calorimetry is the measurement of thermal losses. It is implemented by thermally insulating the 50 Ω load in the calorimeter ( 322 ) to prevent ambient thermal losses and measuring the flow rate and the temperature rise of the cooling water. The power meter is calibrated to the power dissipation in the load computed by
Q = ⅆ m ⅆ t C ( T out - T i n ) , where ⅆ m ⅆ t
denotes the mass flow rate, C denotes the specific heat of water, and T in , T out denote the inlet and outlet temperatures, respectively. A computer 324 acquires flow rate and temperature measurements to compute the power dissipation in the load and the difference (error) with respect to readout of the power meter. The computer 324 then applies this error as a correction to the power meter to complete the calibration.
[0054] FIG. 9B is detailed implementation diagram of step 320 for calibrating the load simulator calorimeter 332 . A load simulator calorimeter 332 is coupled to a DC power supply 334 , DC power is applied, and the load simulator calorimeter 332 is calibrated. The DC power supply provides the DC power measurements. Using flow rate and temperature measurements at the inlet and outlet of the cooling system, a computer 324 computes the power dissipated in the load simulator. The computer 324 then applies the error between the power reported by the DC power supply and the power computed using calorimetry as a correction to the load simulator to complete the calibration.
[0055] FIG. 9C is detailed implementation diagram step 330 for calibrating an RF impedance analyzer or VI probe 240 . Generally, the VI Probe 240 calibration in each integrated RF generator system 200 includes the following steps that yield a matrix transfer function that relates the VI probe voltage and current measured by the DSP compensator board 230 to an actual RF line voltage and current.
[0056] First, a short circuit connector 312 is coupled to the RF line output terminal of the VI probe 240 , RF power is applied from the power amplifier 220 , and Z dsp sc is computed, wherein Z dsp sc is defined as the ratio of V dsp /I dsp as measured by the DSP compensator board 230 for short circuit. Second, an open circuit connector 314 is coupled to the RF line output terminal of the VI probe 240 , RF power is applied from the power amplifier 220 , and Z dsp ac is computed, wherein Z dsp ac is defined as the ratio of V dsp /I dsp as measured by the DSP compensator board 230 for open circuit. Third, a 50 Ω load (Z L ) 316 is coupled to the output of the VI Probe 240 , RF power is applied from the power amplifier 220 , V m and I m are recorded and the RF line voltage V L is computed, wherein V L =√{square root over (P L Z L )}·P L is the delivered power measured by a power meter 318 at the 50 Ω load 316 . Lastly, the VI probe calibration matrix transfer function is computed by the following equation:
[ V L ( t ) I L ( t ) ] = ( V L V m - Z sc dsp I m - Z sc dsp V L V m - Z sc dsp I m - V L Z L ( - Z sc dsp I m - V m ) Z sc dsp V L Z L ( - Z sc dsp I m - V m ) ) [ V dsp ( t ) I dsp ( t ) ] EQN . 10
[0057] The expression in equation 10 translates VI probe measurement signals into RF line voltage and RF line current at the output of the VI probe 240 .
[0058] FIG. 9D is detailed implementation diagram step 340 for calibrating the system 200 ( FIG. 2 ). The system level calibration is used to quantify the power loss in the electronic matching network 250 for a range of values matching network variables. A load simulator 342 is coupled to the output of the electronic matching network 250 . Typically, the load simulator is an electronic matching network inverse to the electronic matching network 250 . A 50 Ω load is coupled to the output of the load simulator 342 . The system-level calibration of the RF generator system 200 is performed as follows. First, a series inductance is adjusted in ll steps for L S ε[L s min , L s max ]. Second, a power setpoint value is changed in pp steps P sp ε[P sp min , P sp max ] W. Third, a shunt capacitance setpoint value is changed in cc steps C tcmd ε[C tcmd min , C tcmd max ]. Lastly, an RF frequency value is changed in ff steps fε[f min , f max ] Hz.
[0059] For each combination of the aforementioned steps, the load simulator 342 is set to present an impedance mismatch at the output of the electronic matching network 250 . Next, RF power is applied from the power amplifier 220 and the power meter 314 measures the terminating load 312 resistance. The terminating load resistance is denoted by P 50Ω and transformed to the input of the load simulator 342 . The simulated load is denoted by P sys as P sys =f 50-to-sim (P 50Ω , C 1 , C 2 ), where C 1 , and C 2 , represent the series and shunt capacitance of the load simulator and f 50-to-sim represents a tabular arrangement. The losses associated in electronic matching network 250 is computed by the difference between the P L and P 50Ω .
[0060] In some embodiments, a calibration table which has dimensions ll×pp×cc×ff can stored in non-volatile memory (e.g., flash memory) as P sys =f VI-to-sim (L s , P sp , C tcmd , f), where f VI-to-sin represents a tabular arrangement. High-speed real-time control loops necessitate fast searches through the calibration table during operation of the system 200 . Non-volatile memory (e.g., flash memory) tends to be slower than the volatile memory (e.g., Dynamic RAM). The high-speed volatile memory is effectively utilized, wherein the arrangement of the calibration table (dimensions ll×pp×cc×ff) can be based on how frequently L s , P sp , C tmcd , and f are changed. Specifically, the calibration table can be segmented into ll memory blocks; each block including pp memory pages; each memory page including a cc×ff dimensional table. A new memory block can be loaded into non-volatile memory when L s is changed, a new memory page can be loaded when power setpoint is changed, and calibration points for the appropriate memory page associated with C tcmd and f can be executed in real-time.
[0061] While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. | A system and method are provided for delivering power to a dynamic load. The system includes a power supply providing DC power having a substantially constant power open loop response, a power amplifier for converting the DC power to RF power, a sensor for measuring voltage, current and phase angle between voltage and current vectors associated with the RF power, an electrically controllable impedance matching system to modify the impedance of the power amplifier to at least a substantially matched impedance of a dynamic load, and a controller for controlling the electrically controllable impedance matching system. The system further includes a sensor calibration measuring module for determining power delivered by the power amplifier, an electronic matching system calibration module for determining power delivered to a dynamic load, and a power dissipation module for calculating power dissipated in the electrically controllable impedance matching system. | 7 |
CROSS REFERENCE
[0001] This application is a continuation-in-part of U.S. Non-provisional application Ser. No. 12/961,954 filed on Dec. 7, 2010, which patent application is incorporated by reference herein in its entirety.
BACKGROUND
[0002] In the downhole drilling and completion industry, there is often need to contain fluid within a formation during various operations. Conventionally, a mechanical barrier is put in the system that can be closed to contain the formation fluid when necessary. One example of a system known in the art will use a valve in operable communication with an Electric Submersible Pump (ESP) so that if/when the ESP is pulled from the downhole environment, formation fluids will be contained by the valve. While such systems are successfully used and have been for decades, in an age of increasing oversight and fail safe/failure tolerant requirements, additional systems will be well received by the art.
SUMMARY
[0003] A completion system, including a barrier valve transitionable between an open position and a closed position; and an upper completion operatively coupled with the barrier valve for mechanically transitioning the barrier valve to the closed position when the upper completion is withdrawn.
[0004] A method of operating a completion system, including withdrawing an upper completion, the upper completion operatively coupled to a barrier valve for controlling operation of the barrier valve; and closing the barrier valve mechanically due to the withdrawing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
[0006] FIG. 1 is a schematic view of a stackable multi-barrier system;
[0007] FIG. 2 is a schematic view of the system of FIG. 1 in partial withdrawal from the borehole;
[0008] FIG. 3 is a schematic view of a new stackable multi-barrier system engaged with the remains of the system illustrated in FIG. 1 ;
[0009] FIG. 4 depicts a quarter cross sectional view of a portion of a hydraulically actuated valve employed in the stackable multi-barrier system of FIGS. 1-3 ;
[0010] FIG. 5 is a partial cross-sectional view of a completion system in which an intermediate assembly is being engaged with a lower completion;
[0011] FIG. 5A is an enlarged view of the area circled in FIG. 5 ;
[0012] FIG. 6 is a partial cross-sectional view of the completion system of FIG. 1 in which the intermediate assembly is engaged with the lower completion;
[0013] FIG. 7 is a partial cross-sectional view of the completion system of FIG. 1 in which a barrier valve of the intermediate assembly is closed for testing a packer of the intermediate assembly;
[0014] FIG. 7A is an enlarged view of the area circled in FIG. 7 ;
[0015] FIG. 8 is a partial cross-sectional view of the completion system of FIG. 1 in which a fluid isolation valve for the lower completion is opened;
[0016] FIG. 9 is a partial cross-sectional view of the completion system of FIG. 1 in which a work string on which the intermediate assembly was run-in is pulled out, thereby closing the barrier valve of the intermediate assembly;
[0017] FIG. 10 is a partial cross-sectional view of the completion system of FIG. 1 in which a production string is being run-in for engagement with the intermediate assembly;
[0018] FIG. 11 is a partial cross-sectional view of the completion system of FIG. 1 in which the production string is engaged with the intermediate assembly for opening the barrier valve and enabling production from the lower completion;
[0019] FIG. 12 is a partial cross-sectional view of the completion system of FIG. 1 in which the production string has been pulled out, thereby closing the barrier valve of the intermediate assembly and a subsequent intermediate assembly is being run-in for engagement with the original intermediate assembly; and
[0020] FIG. 13 is a partial cross-sectional view of the completion system of FIG. 1 in which the subsequent intermediate assembly is stacked on the original intermediate assembly;
[0021] FIG. 14 is a partial cross-sectional view of a completion system according to another embodiment disclosed herein; and
[0022] FIG. 15 is a partially cross-sectional view of a completion system according to another embodiment disclosed herein.
DETAILED DESCRIPTION
[0023] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
[0024] Referring to FIG. 1 , a stackable multi-barrier system 10 is illustrated. Illustrated is a portion of a lower completion 12 , a packer 14 and a portion of an upper completion 16 . One of ordinary skill in the art will be familiar with the lower completion 12 and the packer 14 and the concept of an upper completion 16 in operable communication therewith. In the illustrated embodiment an electric submersible pump (ESP) 18 is included in the upper completion 16 , which is a device well known to the art. Between the illustrated ESP 18 and the lower completion 12 however, one of ordinary skill in the art will be surprised to see a number of mechanical barriers 20 , 22 (sometimes referred to herein as “valves”) that is greater than one. As illustrated in the figures hereof there are two but nothing in this disclosure should be construed as limiting the number of mechanical barriers to two. Rather more could also be added, if desired.
[0025] In one embodiment the more downhole valve 20 is a hydraulically actuated valve such as an ORBIT™ valve available commercially from Baker Hughes Incorporated, Houston Tex. and the more uphole valve 22 is a mechanically actuated valve such as a HALO™ valve available from the same source. It will be appreciated that these particular valves are merely exemplary and may be substituted for by other valves without departing from the invention.
[0026] Control lines 24 are provided to the valve 20 for hydraulic operation thereof. In the illustrated embodiment the lines also have a releasable control line device 28 in line therewith to allow for retrieval of the upper completion 16 apart from the lower completion 12 . Also included in this embodiment of the system 10 is a stroker 30 that may be a hydraulic stroker in some iterations.
[0027] The components described function together to manage flow between the lower completion 12 and the upper completion 16 . This is accomplished in that the valve 20 is settable to an open or closed position (and may be variable in some iterations) based upon hydraulic fluid pressure in the control line 24 . The valve 22 is opened or closed based upon mechanical input generated by movement of the upper completion 16 , or in the case of the illustration in FIG. 1 , based upon mechanical movement caused by the stroker 30 that is itself powered by hydraulic fluid pressure. Of course, the stroker 30 could be electrically driven or otherwise in other embodiments. In any condition, the valve 22 is configured to close upon withdrawal of the upper completion 16 . In normal production, both of the valves 20 and 22 will remain open unless there is a reason to close them. Such a reason occurs, for example, when it is required to retrieve the upper completion 16 for some reason. One such reason is to replace the ESP 18 . Regardless of the reason for closure, employment of the system 10 in a completion string provides more than one mechanical barrier 20 , 22 at an uphole extent of the lower completion 12 . The barriers when closed prevent fluid flow after the upper completion is retrieved.
[0028] Attention is directed to releasable control line devices 28 and FIG. 2 . During a withdrawal of the upper completion 16 , the control lines 24 are subjected to a tensile load. The releasable control line devices will release at a threshold tensile load and seal the portion of the control lines 24 that will remain in the downhole environment as a part of the lower completion string 12 . The valve 20 , if not already closed, is configured to close in response to this release of the control lines 24 . This will complete the separation of the upper completion 16 from the lower completion 12 and allow retrieval of the upper completion 16 to the surface. With more than one mechanical barrier 20 , 22 in place at the uphole extent of the lower completion 12 , there is improved confidence that fluids will not escape from the lower completion 12 . Important to note here briefly is that the system 10 also includes provision 44 for allowing the reopening of the valve 20 using tubing pressure after the upper completion 16 is reinstalled. This will be addressed further hereunder.
[0029] In order to restore production, another system 110 is attached at a downhole end of upper completion 16 and run in the hole. This is illustrated in FIG. 3 . The original system 10 has components such as packer 14 , valves 20 and 22 and control lines 24 are seen at the bottom of the drawing and a new system 110 stackable on the last is shown. The new system 110 includes a packer 114 valve 120 , valve 122 , lines 124 , stroker 13 , ESP 118 and releasable hydraulic line device 128 . In essence each of the components of system 10 is duplicated in system 110 . Moreover, it should be understood that the process of pulling out and stabbing in with new systems can go on ad infinitum (or at least until practicality dictates otherwise).
[0030] Since the valves 20 and 22 will be in the closed position, having been intentionally closed upon preparing to retrieve the upper completion 16 , they will need to be opened upon installation of the new system 110 . This is accomplished by stabbing a mechanical shiftdown 142 into valve 22 and setting packer 114 . The mechanical shiftdown 142 mechanically shifts the valve 22 to the open position. It should be pointed out that, in this embodiment, the mechanical shiftdown 142 does not seal to the valve 22 and as such the inside of the upper completion 16 is in fluidic communication with annular space 146 defined between the packers 14 and 114 . Applying pressure to the tubing at this point will result in a pressure buildup that will act on the valve 20 through the string uphole thereof since all valves thereabove, 22 , 120 and 122 are in the open position. Referring to FIG. 4 , a view of valve 20 illustrates the provision 44 that includes a port 52 in operable communication with an optional shifter 50 . The shifter 50 is configured to open the port 52 in response to retrieval of the upper completion 16 . As illustrated the shifter 50 in this embodiment is a sleeve that is automatically actuated upon retrieval of the upper completion 16 . More specifically, when upper completion 16 begins to move uphole, the provision 44 is shifted to the open position. When the provision 44 is in the open position tubular fluid pressure is in communication with the port 52 . The port 52 includes an openable member 54 such as a burst disk or similar that when opened provides fluid access to an atmospheric chamber 56 . The member 54 opens upon increased tubing pressure and allows fluid to fill the atmospheric chamber 56 . Fluid in the atmospheric chamber causes one or more pistons 58 to urge the valve 20 to the open position. In one embodiment, ratcheting devices (not shown) may be provided in operable communication with the one or more pistons 58 to prevent the pistons from moving in a direction to allow the valve to close by serendipity at some later time. It may also be that the valve 20 itself is configured to be locked permanently open by other means if the atmospheric chamber floods.
[0031] The foregoing apparatus and method for its use allows for the retrieval and replacement of an upper completion without the need for a wet connection. It will be further appreciated in view of the below that certain components, aspects, features, elements, etc. of the above described embodiments can be utilized in other completion systems. For example, as disclosed above, features of the system 10 can be used to enable barrier valves of other systems to “automatically” close when the upper completion is pulled out, i.e., transition to a closed position based upon mechanical movement of the upper completion as taught above.
[0032] Referring now to FIG. 5 , a completion system 210 is shown installed in a borehole 1 && (cased, lined, open hole, etc.). The system 210 includes a lower completion 214 including a gravel or frac pack assembly 216 (or multiples thereof for multiple producing zones) that is isolated from an upper completion 218 of the system 210 by a fluid loss or fluid isolation valve 220 . The gravel or frac pack assembly 216 and the valve 220 generally resemble those known and used in the art. That is, the gravel or frac pack assembly 216 enables the fracturing of various zones while controlling sand or other downhole solids, while the valve 220 takes the form of a ball valve that is transitionable between a closed configuration (shown in FIG. 5 ) and an open configuration (discussed later) due to cycling the pressure experienced by the valve 220 or other mechanical means, e.g., through an intervention with wireline or tubing. Of course, known types of fluid loss valves other than ball valves could be used in place of the valve 220 . Additionally, it is to be appreciated that the lower completion 214 could include components and assemblies other than, or in addition to, the frac pack and/or gravel pack assembly 216 , such as for enabling stimulation, hydraulic fracturing, etc.
[0033] The system 210 also includes a work string 222 that enables an intermediate completion assembly 224 to be run in. Essentially, the assembly 224 is arranged for functionally replacing the valve 220 . That is, while the valve 220 remains physically downhole, the assembly 224 assumes or otherwise takes off at least some functionality of the valve 220 , i.e., the assembly 224 provides isolation of the lower completion 214 and the formation and/or portion of the borehole 212 in which the lower completion 214 is positioned. Specifically, in the illustrated embodiment, the assembly 224 in the illustrated embodiment is a fluid loss and isolation assembly and includes a barrier valve 226 and a production packer or packer device 228 . By packer device, it is generally meant any assembly arranged to seal an annulus, isolation a formation or portion of a borehole, anchor a string attached thereto, etc. The barrier valve 226 is shown in more detail in FIG. 5A . Initially, as shown in FIGS. 5 and 5A , a shifting tool 230 holds a sleeve 232 of the barrier valve 226 in an open position by an extension 234 of the shifting tool 230 that extends through the packer 228 . The term “shifting tool” is used broadly and encompasses seal assemblies and devices that allow relative movement or shifting of the sleeve 232 other than the tool 230 as illustrated. When the sleeve 232 is in its open position, a set of ports 236 in the sleeve 232 are axially aligned with a set of ports 238 in a housing or body 240 of the barrier valve 226 , thereby enabling fluid communication through the barrier valve 226 . Of course, movement of the sleeve 232 for enabling fluid communication is not limited to axial, although this direction of movement conveniently corresponds with the direction of movement of the work string 222 . In the illustrated embodiment, a shroud 244 is radially disposed with the barrier valve 226 for further controlling and/or regulating the flow rate, pressure, etc. of fluid, i.e., by redirecting fluid flow from the lower completion 214 out into the chamber formed by the shroud 244 , and back into the barrier valve 226 via the ports 236 and 238 when the valve 226 is open. In the illustrated embodiment, the extension 234 of the shifting tool 230 (and/or the sleeve 232 ) includes a releasable connection 246 for enabling releasable or selective engagement between the tool 230 and the sleeve 232 . For example, the connection 246 could be formed by a collet, spring-loaded or biased fingers or dogs, etc.
[0034] A method of assembling and using the completion 210 according to one embodiment is generally described with respect to FIGS. 5-13 . As illustrated in FIG. 5 , the work string 222 with the assembly 224 is initially run in for connection to the lower completion 214 , thereby providing a fluid pathway to surface and enabling production. For example, while circulating fluids in the borehole 212 , the assembly 224 can be properly positioned by lowering the work string 222 until circulation stops. After noting the location and slacking off on the work string, the assembly 224 is landed at the lower completion 214 , as shown in FIG. 6 . Once landed at the lower completion 214 , the production packer 228 is set, e.g., via hydraulic pressure in the work string 222 , thereby isolating and anchoring the assembly 224 . At this point, the barrier valve 226 is open and an equalizing port 248 between the interior of the work string 222 and an annulus 250 is closed by the extension 234 of the shifting tool 230 .
[0035] As illustrated in FIG. 7 , the work string 222 can then be pulled out in order to axially misalign the ports 236 and 238 , which closes the barrier valve 226 . That is, as shown in more detail in FIG. 7A , communication through the port 238 and into the barrier valve 226 is prevented by a pair of seal elements 252 sealed against the sleeve 232 . As also shown in more detail in FIG. 7A , pulling out the work string 222 slightly also opens the equalizing port 248 , enabling the packer 228 to be tested on the annulus 250 and/or down the work string 222 .
[0036] As depicted in FIG. 8 , by again slacking off on the work string 222 , the barrier valve 226 re-opens (e.g., taking the configuration shown in FIG. 5A ) and pressure can be cycled in the work string 222 for opening the fluid loss valve 220 . Next, as shown in FIG. 9 , the work string 222 is pulled out of the borehole 212 . Pulling out the work string 222 first shifts the sleeve 232 into its closed position (e.g., as shown in FIG. 7A ) for the barrier valve 226 . Then due to the packer 228 anchoring the assembly 214 , continuing to pull out the work string 222 disconnects the tool 230 from the sleeve 232 at the releasable connection 246 .
[0037] In order to start production, a production string 254 is run and engaged with the assembly 224 as shown in FIGS. 10 and 11 . The production string 254 includes a shifting tool 256 similar to the tool 230 , i.e., arranged with a releasable connection to selectively open and close the barrier valve 226 by manipulating the sleeve 232 . In this way, the production string 254 is first landed at the assembly 224 and the tool 230 extended through the packer 228 for shifting the sleeve 232 to open the barrier valve 226 . Once the barrier valve 226 is opened, a tubing hanger supporting the production string 254 is landed and fluid from the downhole zones, i.e., proximate to the frac or gravel pack assembly 216 , can be produced. In the illustrated embodiment the production string 254 takes the form of an artificial lift system, particularly an ESP system for a deepwater well, which are generally known in the art. However, it is to be appreciated that the current invention as disclosed herein could be used in non-deepwater wells, without artificial lift systems, with other types of artificial lift systems, etc.
[0038] Workovers are a necessary part of the lifecycle of many wells. ESP systems, for example, are typically replaced about every 8-10 years, or some other amount of time. Other systems, strings, or components in the upper completion 218 may need to be similarly removed or replaced periodically, e.g., in the event of a fault, damage, corrosion, etc. In order to perform the workover, reverse circulation may be performed by closing a circulation valve 258 and shifting open a hydraulic sliding sleeve 260 of the production string 254 . Advantageously, if the production string 254 or other portions in the upper completion 218 (i.e., up-hole of the assembly 224 ) needs to be removed, removal of that portion will “automatically” revert the barrier valve 226 to its closed position, thereby preventing fluid loss. That is, the same act of pulling out the upper completion string, e.g., the production string 254 , the work string 222 , etc., will also shift the sleeve 232 into its closed position and isolate the fluids in the lower completion. This eliminates the need for expensive and additional wireline intervention, hydraulic pressure cycling, running and/or manipulating a designated shifting tool, etc. The packer 228 also remains in place to maintain isolation. This avoids the need for expensive and time consuming processes, such as wireline intervention, which may otherwise be necessary to close a fluid loss valve, e.g., the valve 220 .
[0039] A replacement string, e.g., a new production string resembling the string 254 , can be run back down into the same intermediate completion assembly, e.g., the assembly 224 . Alternatively, if a long period of time has elapsed, e.g., 8-10 years as indicated above with respect to ESP systems, it may instead be desirable to run in a new intermediate completion assembly, as equipment wears out over time, particularly in the relatively harsh downhole environment. For example, as shown in FIGS. 12 and 13 an additional or subsequent intermediate completion assembly 224 ′ is run in on a work string 222 ′ for engagement with the original assembly 224 . As noted above with respect to the valve 220 , the subsequent assembly 224 ′ essentially functionally replaces the original assembly 224 . That is, the subsequent assembly 224 ′ substantially resembles the original assembly 224 , including a barrier valve 226 ′ for preventing fluid loss, a production packer 228 ′ for reestablishing isolation, and a sleeve 232 ′ that is manipulated by a shifting tool 230 ′ on the work string 222 ′. It should be appreciated that the aforementioned components associated with the assembly 224 ′ include prime symbols, but otherwise utilize the same base reference numerals as corresponding components described above with respect to the assembly 224 , and the above descriptions generally apply to the corresponding components having prime symbols and of the assembly 224 ′ (even if unlabeled), unless otherwise noted.
[0040] Unlike the assembly 224 , the assembly 224 ′ has a shifting tool 262 for shifting the sleeve 232 of the original assembly 224 in order to open the barrier valve 226 , which was closed by the shifting tool 256 when the production string 254 was pulled out. As long as the assembly 224 ′ remains engaged with the assembly 224 , the tool 262 will mechanically hold the barrier valve 226 in its open position. In this way, the assembly 224 ′ can be stacked on the assembly 224 and the barrier valve 226 ′ will essentially take over the fluid loss functionality of the barrier valve 226 of the assembly 224 by holding the barrier valve 226 open with the tool 262 . It is to be appreciated that any number of these subsequent assemblies 224 ′ could continue to be stacked on each other as needed. For example, a new one of the assemblies 224 ′ could be stacked onto a previous assembly between the acts of pulling out an old upper completion or production string and running in a new one. In this way, the newly run upper completion or production string will interact with the uppermost of the assemblies 224 ′ (as previously described with respect to the assembly 224 and the production string 254 ), while all the other intermediate assemblies are held open by the shifting tools of the subsequent assemblies (as previously described with respect to the assembly 224 and the shifting tool 262 ).
[0041] The shifting tool 230 ′ also differs from the shifting tool 230 to which it corresponds. Specifically, the shifting tool 230 ′ includes a seat 264 for receiving a ball or plug 266 that is dropped and/or pumped downhole. By blocking flow through the seat 264 with the plug 266 , fluid pressure can be built up in the work string 222 ′ suitable for setting and anchoring the production packer 228 ′. That is, pressure was able to be established for setting the original packer 228 because the fluid loss valve 220 was closed, but with respect to FIGS. 12 and 13 the valve 220 has since been opened and fluid communication established with the lower completion 214 as described previously.
[0042] After setting the packer 228 ′, the string 222 ′ can be pulled out, thereby automatically closing the sleeve 232 ′ of the barrier valve 226 ′ as previously described with respect to the assembly 224 and the work string 222 (e.g., by use of a releasable connection). As previously noted, the original barrier valve 226 remains opened by the shifting tool 262 of the subsequent assembly 224 ′. As the assembly 224 ′ has essentially taken over the functionality of the original assembly 224 (i.e., by holding the barrier valve 226 constantly open with the tool 262 ), a new production string, e.g., resembling the production string 254 , can be run in essentially exactly as previously described with respect to the production string 254 and the assembly 224 , but instead engaged with the assembly 224 ′. That is, instead of manipulating the barrier valve 226 , the shifting tool (e.g., resembling the tool 256 ) of the new production string (e.g., resembling the string 254 ) will shift the sleeve 232 ′ of the barrier valve 226 ′ open for enabling production of the fluids from the downhole zones or reservoir.
[0043] It is again to be appreciated that any number of the assemblies 224 ′ can continue to be run in and stacked atop one another. For example, this stacking of the assemblies 224 ′ can occur between the acts of pulling out an old production string and running a new production string, with the pulling out of each production string “automatically” closing the uppermost one of the assemblies 224 ′ and isolating the fluid in the lower completion 214 . In this way, any number of production strings, e.g., ESP systems, can be replaced over time without the need for expensive and time consuming wireline intervention, hydraulic pressure cycling, running and/or manipulation of a designated shifting tool, etc. Additionally, the stackable nature of the assemblies 224 , 224 ′, etc., enables the isolation and fluid loss hardware to be refreshed or renewed over time in order to minimize the likelihood of a part failure due to wear, corrosion, aging, etc.
[0044] It is noted that the fluid loss valve 220 can be substituted, for example, by the assembly 224 being run in on a work string resembling the work string 222 ′ as opposed to the work string 222 . For example, as shown in FIG. 12 , a modified system 210 a includes the assembly 224 being run in on the work string 222 ′. In this way, fluid pressure suitable for setting the original packer 228 can be established by use of the ball seat 264 and the plug 266 instead of the valve 220 . Accordingly, as illustrated in FIG. 14 , the fluid loss valve 220 is rendered unnecessary or redundant by use of the system 210 a , as the plug 266 and the seat 264 of the work string 222 ′ enable suitable pressurization for setting the packer 228 , and the tool 230 ′ of the work string 222 ′ enables control of the barrier valve 226 such that the assembly 224 can completely isolate the lower completion 214 . After isolating the lower completion 214 , a production string, e.g., the string 254 , subsequent intermediate assemblies, etc., can be run in and interact with the assembly 224 as described above.
[0045] As another example, a modified system 210 b is illustrated in FIG. 15 . The system 210 b is similar to the system 210 a in that a separate fluid isolation valve for the lower completion 214 , e.g., the valve 220 , is not necessary and instead the system 210 b can be run in for initially isolating the lower completion 214 . Unlike the system 210 a , the system 210 b is capable of being run-in immediately on the production string 254 without the need for the work string 222 ′ of the system 210 a . Specifically, the system 210 b is run-in with a plug 266 ′ already located in a shifting tool 256 ′ of the production string 254 . The tool 256 ′ resembles the tool 256 with the exception of being arranged to hold the plug 266 ′ therein for blocking fluid flow therethrough. By running the plug 266 ′ in with the system 210 b , the plug 266 ′ does not need to be dropped and/or pumped from surface, as this would be impossible for various configurations of the production string 254 , e.g., if the string 254 includes ESPs or other components or assemblies that would obstruct the pathway of a dropped plug down through the string. The plug 266 ′ is arranged to be degradable, consumable, disintegrable, corrodible, dissolvable, chemically reactable, or otherwise removable so that once it has been used for providing the hydraulic pressure necessary to set the packer 228 , the plug 266 ′ can be removed and enable production through the string 254 . In one embodiment the plug 266 ′ is made from a dissolvable or reactive material, such as magnesium or aluminum that can be removed in response to a fluid deliverable or available downhole, e.g., acid, brine, etc. In another embodiment, the plug 266 ′ is made from a controlled electrolytic material, such as made commercially available by Baker Hughes, Inc. under the tradename IN-TALLIC®. Once the plug 266 ′ is removed, the system 210 b would function as described above with respect to the system 210 .
[0046] It is thus noted that the current invention as illustrated in FIGS. 5-13 is suitable as a retrofit for systems that are in need of a workover, i.e., need to have the upper completion replaced or removed, but already includes a valve resembling the fluid loss valve 220 (e.g., a ball valve or some other type of valve used in the art that requires wireline intervention, hydraulic pressure cycling, the running and/or manipulation of designated shifting tools, etc., in order to transition between open and closed configurations). Alternatively stated, the system 210 enables downhole isolation of a lower completion for performing a workover, i.e., removal or replacement of an upper completion, without the need for time consuming wireline or other intervention.
[0047] In view of the foregoing it is to be appreciated that new completions can be installed with a valve, e.g., the fluid loss valve 220 , that requires some separate intervention and/or operation to close the valve during workovers, or, alternatively, according to the systems 210 a or 210 b , which not only initially isolate a lower completion, e.g., the lower completion 214 , but additionally include a barrier valve, e.g., the barrier valve 226 , that automatically closes upon pulling out the upper completion, as described above.
[0048] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. | A completion system, including a barrier valve transitionable between an open position and a closed position. An upper completion is operatively coupled with the barrier valve for mechanically transitioning the barrier valve to the closed position when the upper completion is withdrawn. A method of operating a completion system is also included. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Ser. No. 61/053,061, filed May 14, 2008. That application is hereby fully incorporated by reference herein.
BACKGROUND
[0002] The present disclosure relates generally to an inflatable, substantially oval or oblong sportsball, such as a football, for competitive play. In particular, the football is configured so that it has improved spiral rotation when thrown, kicked, etc.
[0003] A football is an inflated oval ball made of a bladder encased usually in leather, rubber, or plastic. It is used for throwing and kicking in the games of rugby and football, such as American style or Canadian football.
[0004] A football has a generally prolate spheroid shape defined by a major axis and a minor axis, with lacing on one side of the ball. To obtain maximum distance and/or precision, a football is preferably thrown to rotate about its major axis. Such spiral rotation increases the stability of the football's flight path and the distance traveled for a given amount of energy. However, throwing a spiral is a somewhat difficult skill to learn and/or reproduce repetitively. A poorly thrown ball is evident in its wobbly flight, travels a shorter distance than could otherwise be obtained, is less accurate, and is more difficult to catch.
[0005] A sportsball that can enhance the distance thrown, kicked, etc. and improve the desired flight path, even when thrown, kicked etc. by one of lesser skill, is desirable.
BRIEF DESCRIPTION
[0006] Disclosed, in various embodiments, are non-uniformly configured sportsballs, such as perimeter weighted footballs. The sportsballs can spiral better when launched, thereby increasing their potential travel distance and/or accuracy. Methods of making and/or using such sportsballs are also disclosed.
[0007] In embodiments, a sportsball is disclosed having a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the sportsball into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) is at least 2, including 2.1.
[0008] In further embodiments, the ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) for the sportsball may be at least 2.2, at least 2.5, or from 2 to about 2.5.
[0009] In still other embodiments, a sportsball is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the sportsball into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to the end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least 1.5 times greater than the weight of one end portion.
[0010] In further embodiments, the weight of the middle portion may be at least two times greater, at least four times greater, about five times greater, or from two times greater to about five time greater, than the weight of one end portion.
[0011] In still more embodiments, a football is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the football into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to the end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least 45% of the total weight of the football.
[0012] In further embodiments, the weight of the middle portion may be at least 50%, at least 65%, or at least 70% of the total weight of the football.
[0013] In additional embodiments, a bladder for a sportsball is disclosed having a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the sportsball bladder into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) is at least 3.
[0014] In other embodiments, the ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) for the bladder may be at least 5 or at least 5.5.
[0015] In still other embodiments, a bladder is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the bladder into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to the end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least four times greater than the weight of one end portion.
[0016] In further embodiments, the weight of the middle portion may be about five times greater than the weight of one end portion.
[0017] In yet other embodiments, a bladder is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the bladder into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to the end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least 65% of the total weight of the bladder.
[0018] In further embodiments, the weight of the middle portion may be at least 70% of the total weight of the bladder.
[0019] In alternative embodiments, a casing for a sportsball is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the casing into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) is at least 3.
[0020] In further embodiments, the ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) for the casing may be at least 5 or at least 5.5.
[0021] In still other embodiments, a casing is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the casing into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to the end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least four times greater than the weight of one end portion.
[0022] In further embodiments, the weight of the middle portion may be about five times greater than the weight of one end portion.
[0023] In yet further embodiments, a casing is disclosed which has a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the casing into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to the end portion length) is from about 0.5 to about 0.95; and the weight of the middle portion is at least 65% of the total weight of the casing.
[0024] In further embodiments, the weight of the middle portion may be at least 70% of the total weight of the casing.
[0025] Sportsballs, such as footballs comprising the above-mentioned bladder and/or casing are also disclosed.
[0026] Some methods of forming the disclosed bladder comprise adding a high-density filler to the middle portion of the bladder. Other methods of forming the disclosed bladder comprise adding an extra layer to the middle portion of the bladder, wherein the extra layer is made of a material having a higher density than the material from which the bladder is made.
[0027] Yet other methods of forming the disclosed bladder comprise: providing a first bladder layer and a second bladder layer, the second bladder layer being dimensioned so as to fit inside the first bladder layer; joining the first bladder layer and second bladder layer using one or more seams so as to form at least one pocket; and filling the pocket with a high-density material.
[0028] Some methods of forming the disclosed casing comprise adding an extra layer to the middle portion of the casing, wherein the extra layer is made of a high-density material that increases the weight of the middle portion of the casing compared to one end portion of the casing. Yet other methods of forming the disclosed casing comprise tapering the casing so the middle portion of the casing has a thickness which is greater than the thickness of one end portion of the casing. The tapering may be at a constant rate, or include a sharp transition.
[0029] Disclosed in other embodiments is a sportsball having a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the sportsball into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) is at least 2, including at least 2.1, or at least 2.5.
[0030] The middle portion length may be from about 2.5 inches to about 3.5 inches. The ratio of the middle portion length to one end portion length may be from about 0.5 to about 0.95.
[0031] To increase the weight of the middle portion, the middle portion may comprise a plurality of weighted strips surrounding a bladder. Each weighted strip may have a uniform thickness along its length and width.
[0032] Disclosed in other embodiments is a sportsball having a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the sportsball into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to one end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least 1.5 times greater than the weight of one end portion.
[0033] The weight of the middle portion may also be at least four times greater than the weight of one end portion, or from at least two times greater to about five times greater than the weight of one end portion.
[0034] The ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) may be at least 2.
[0035] The middle portion length may be from about 2.5 inches to about 3.5 inches.
[0036] The middle portion may comprise a plurality of weighted strips surrounding a bladder. Each weighted strip may have a uniform thickness along its length and width.
[0037] Also disclosed in embodiments is a sportsball having a major axis and a minor axis. Two planes which are perpendicular to the major axis are located equally distant from the center of the major axis so as to divide the sportsball into a middle portion and two end portions. The middle portion has a middle portion weight and a middle portion length, and each end portion has an end portion weight and an end portion length. The ratio of the middle portion length to one end portion length is from about 0.5 to about 0.95; and the weight of the middle portion is at least 45% of the total weight of the sportsball.
[0038] The weight of the middle portion may be at least 65%, or even 70%, of the total weight of the sportsball bladder.
[0039] The middle portion length may be from about 2.5 inches to about 3.5 inches.
[0040] The middle portion may comprise a plurality of weighted strips surrounding a bladder. Each weighted strip may have a uniform thickness along its length and width.
[0041] These and other non-limiting characteristics are more particularly described below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0042] The following is a brief description of the drawings, which are presented for the purpose of illustrating the exemplary embodiments disclosed herein and not for the purpose of limiting the same.
[0043] FIG. 1 is an exterior view of a typical American styled football.
[0044] FIG. 2 is a cross-sectional view of the same football.
[0045] FIG. 3 is a cross-sectional diagram of a football, football bladder, or football casing of the present disclosure.
[0046] FIG. 4 is a simplified cross-sectional view from the top of a sportsball of the present disclosure.
[0047] FIG. 5 is a simplified cross-sectional view from one end of a sportsball of the present disclosure, i.e. along line A-A of FIG. 4 .
[0048] FIG. 6 illustrates the thickness of one variation of a weighted strip located in a weighted football of the present disclosure.
[0049] FIG. 7 illustrates the thickness of another variation of a weighted strip located in a weighted football of the present disclosure.
DETAILED DESCRIPTION
[0050] A more complete understanding of the components, processes and apparatuses disclosed herein can be obtained by reference to the accompanying drawings. These figures are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments.
[0051] Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings, and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.
[0052] The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity). When used with a specific value, it should also be considered as disclosing that value. For example, the term “about 2” also discloses the value “2” and the range “from about 2 to about 4” also discloses the range “from 2 to 4.”
[0053] Current American styled footballs may be constructed with an inflatable, generally prolate spheroid shaped bladder. The bladder is covered by a cover layer usually made from four generally oval-shaped panels which are sewn, stitched, or seamed together along their edges. If desired, additional layers may be placed between the bladder and the cover layer by the use of additional oval-shaped panels. For example, a foam layer and/or a cloth layer may also be present. One of the seams is not stitched along a central extent, thereby forming an opening to allow the bladder to be inserted within the cover layer during fabrication. After insertion, the opening is closed by the use of lacing and associated components, such as a lacing liner placed to prevent the lacing from contacting the bladder.
[0054] Another means of constructing a football is through molding. Briefly, a bladder is inserted into a molding assembly along with a seam material. The molding assembly applies heat and/or pressure to mold the seam material into a cover layer having outwardly projecting seams. Cover panels are then laid in the areas between seams and lacing is applied to finish the football. This method of construction is more completely described in U.S. Patent Publication No. 2007/0129188, the disclosure of which is hereby fully incorporated by reference herein.
[0055] FIG. 1 is an exterior view of a typical American football 10 . FIG. 2 is a cross-sectional view of the same football 10 . The bladder 20 is inside the football casing 50 . Surrounding the bladder 20 is a cloth liner 22 , then a foam liner 4 , then the cover layer 30 . The cloth liner, foam liner, and cover layer are generally combined to make a panel 34 ; four panels 34 make up the football casing 50 and are used to cover the football 10 . The four panels are joined together by stitching at three edges and by a combination of stitching and lacing at the fourth edge. The lacing area includes the lacing 40 , a patch material 42 stitched to the underside of panels 34 through which lacing 40 penetrates, and a tongue 44 located between the bladder 20 and the lacing 40 which has penetrated the patch material 42 . The lacing, patch material, and tongue cause the football to be asymmetrically weighted.
[0056] For purposes of this application, the term “weighted football” refers to the football without the lacing, patch material, and tongue. Put another way, the term “weighted football” refers to the combination of bladder and football casing and excludes the lacing, patch material, and tongue. The term “weighted football” also excludes any incidental weight due to air within the bladder. Weighted footballs are generally symmetrically weighted about the major axis of the football.
[0057] The term “bladder” refers to the balloon located inside a football for the purpose of containing air and the layer(s) that make up that balloon. Again, the weight of any air in the bladder would not be included.
[0058] The term “football casing” refers to the material which surrounds the bladder, excluding the lacing, patch material, and tongue. For example, the combination of four panels 34 is considered a football casing. As another example, when the football is made by molding, the cover layer having outwardly projecting seams plus the cover panels is considered a football casing.
[0059] The weighted footballs of the present disclosure are weighted so that the middle of the weighted football is significantly heavier than the ends. This weight distribution aids the spiraling motion of the football, enhancing stability and traveling distance. The concentration of weight in the middle increases the moment of inertia about the weighted football's major axis, which helps improve the rotation of the football around that axis.
[0060] Several standards for footballs are shown in the following Table 1:
[0000]
TABLE 1
Pee-
Junior
Full
CFL
Wee
Size
Size
NCAA
NFL
Foot-
Standard
Football
Football
Football
Football
Football
ball
Minimum Minor
44.5
47
52.7
52.7
53.3
53.0
Axis
Circumference
(cm)
Maximum Minor
46
48.3
54
54.0
54.0
53.7
Axis
Circumference
(cm)
Minimum Major
60
64.6
70.8
70.5
71.1
70.5
Axis
Circumference
(cm)
Maximum Major
61.5
65.9
72.9
71.8
72.4
71.8
Axis
Circumference
(cm)
Minimum Length
24
25.7
27.6
27.6
27.9
27.9
(cm)
Maximum Length
25.5
26.7
29
28.4
28.6
28.6
(cm)
Minimum Weight
290
320
397
397
397
397
(g)
Maximum Weight
320
350
425
425
425
425
(g)
[0061] The minor axis may also be referred to as the short axis or the girth. The length refers to the length of the major axis, which may also be referred to as the long axis. Generally, the footballs of the present disclosure will still meet these standards, although differing in the weight distribution.
[0062] One method of making the weighted football of the present disclosure is by providing a bladder which is preferentially weighted in its middle portion. FIG. 3 is a cross-sectional diagram of a weighted football 100 , football bladder 200 , or football casing 300 of the present disclosure. All terms refer equally to the various aspects of the football, bladder, or casing.
[0063] The football, bladder, or casing has a major axis 110 , a minor axis 120 , and a generally elliptical cross-section. The major axis 110 and minor axis 120 intersect at the center 130 of the football, bladder, or casing. The center 130 is also the center of the major axis and the minor axis. Two imaginary planes 140 , 145 are perpendicular to the major axis 110 and are located equally distant from the center 130 . The two planes divide the football, bladder, or casing into a middle portion 150 and two end portions 160 . The middle portion 150 has a middle portion weight 153 , while each end portion 160 has an end portion weight 163 . The two planes can also be considered as dividing the major axis 110 into a middle portion length 155 and two end portion lengths 165 . In other words, the lengths are measured parallel to the major axis. The two planes 140 , 145 are always located equidistant from the center 130 of the major axis. Put another way, the end portion lengths 165 are always the same. There are two ends 170 which are included in the end portions. The circle formed by the intersection of the minor axis with the surface of the football, bladder, or casing defines a surface center 175 .
[0064] The football bladder may be weighted by providing a middle portion that has a higher weight per length value than the end portions. In embodiments, the football bladder has a ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) that is at least 3. In further embodiments, the ratio is at least 5 or at least 5.5. In some embodiments, the ratio may be at least 7 or even at least 8.
[0065] Alternatively, the ratio of (middle portion length/end portion length) for the bladder is from about 0.5 to about 0.95; and the weight of the middle portion is at least four times greater than the weight of one end portion. In further specific embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.95; and the weight of the middle portion is about five times greater than the weight of one end portion. In yet further embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.7, or from about 0.8 to about 0.95.
[0066] In yet other embodiments, the ratio of (middle portion length/end portion length) for the bladder is from about 0.5 to about 0.95; and the weight of the middle portion is at least 65% of the total weight of the football bladder. In more specific embodiments, the ratio of (middle portion length/end portion length) for the bladder is from about 0.5 to about 0.95; and the weight of the middle portion is at least 70% of the total weight of the football bladder. In other embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.7. In particular embodiments, the middle portion length is from about 2.5 inches to about 3.5 inches.
[0067] The bladder, when properly inflated, provides the primary resilience to a finished football. The bladder can be made from latex or butyl rubber and fitted with a valve stem (not shown) for introducing air into the ball as inflated pressure to the structure. Butyl rubber bladders retain air for longer periods of time and offer an excellent combination of contact quality and air retention. Latex bladders tend to provide better surface tension, give proper bounce, feel softer, and provide same angle rebounce characteristics. Natural latex rubber bladders usually offer the softest feel and response, but do not provide the best air retention because they contain micro-pores. Micro-pores are tiny holes that slowly allow air to escape. Balls with natural rubber bladders need to be reinflated (at least once a week) more often than balls with butyl bladders (stay properly inflated for weeks at a time) due to these micro-pores. Some balls use carbon-latex bladders, where carbon powder is added to the latex to plug some of the microscopic holes that are in pure latex bladders. Carbon latex bladders retain air longer than bladders made from latex rubber. Some manufacturers also use bladders made from multiple layers of polyurethane. The bladder can be of appropriate thickness as to reasonably protect against loss of air due to puncture, temperature change, or other foreseeable occurrences.
[0068] The additional weighting of the middle portion of the football bladder can be accomplished by several different means. Additional weight could be applied by, for example, adding a high-density filler, such as barium sulfate or a tungsten powder, to a polymer binder and forming the middle portion of the bladder from that high density polymer while the end portions are formed from a lower-density polymer. Similarly, additional strips, patches, or layers of higher-density material could be used to form the bladder. Some bladders are made as multi-layer concentric balloons (one balloon inside another balloon) which are joined to each other along seams that parallel the major axis. Additional seams could be used to form pockets within the bladder between balloons which are then filled with a high-density filler or liquid as well. In particular embodiments, two or more weighted strips or patches are placed around the middle portion of the bladder. The weighted strips surround the bladder, or in other words extend around the circumference of the middle portion. The gaps between the weighted strips may be located at the seams of the bladder to allow for expansion as the bladder is inflated. The thickness of the weighted strips can vary, being thickest near the middle and tapering off as they progress towards an end 170 or end portion of the bladder. The tapering may be gradual (i.e. at a constant rate from surface center 175 to end 170 ) or sharp (i.e., transitioning immediately from one thickness to a second thickness, such as near or at the intersection of the surface with the two planes 140 , 145 ). Generally, the weighted strips have a uniform thickness along their entire length and width.
[0069] The fact that the middle portion is weighted compared to the end portions should not be construed as requiring the middle portion to be evenly or homogeneously weighted throughout its entirety.
[0070] Another method of making the weighted football of the present disclosure is by providing a football casing which is preferentially weighted in its middle portion. Again, the football casing has the major axis 110 , a minor axis 120 , center 130 , two imaginary planes 140 , 145 , middle portion 150 and two end portions 160 , middle portion weight 153 , end portion weight 163 , middle portion length 155 , and two end portion lengths 165 as described in FIG. 3 .
[0071] The football casing may be weighted by providing a middle portion that has a higher weight per length value than the end portions. In embodiments, the football casing has a ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) that is at least 3. In further embodiments, the ratio is at least 5 or at least 5.5. In other embodiments, the ratio may be at least 7 or even at least 8.
[0072] Alternatively, the ratio of (middle portion length/end portion length) for the casing is from about 0.5 to about 0.95; and the weight of the middle portion is at least four times greater than the weight of one end portion. In further specific embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.95; and the weight of the middle portion is about five times greater than the weight of one end portion. In yet further embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.7, or from about 0.8 to about 0.95.
[0073] In yet other embodiments, the ratio of (middle portion length/end portion length) for the casing is from about 0.5 to about 0.95; and the weight of the middle portion is at least 65% of the total weight of the football casing. In more specific embodiments, the ratio of (middle portion length/end portion length) for the casing is from about 0.5 to about 0.95; and the weight of the middle portion is at least 70% of the total weight of the football casing. In particular embodiments, the middle portion length is from about 2.5 inches to about 3.5 inches.
[0074] The cover layer of the football casing is generally made from different materials, such as leather and composite material. Leather is generally used by professional athletes, and is considered best for grip, feel, and control. One disadvantage of a leather cover on a football is that the ball can be damaged if scraped against a hard surface like asphalt or concrete. Composite footballs generally attempt to simulate the look and feel of a real leather ball. They can be made of polyurethane (PU) or polyvinyl chlorides (PVC), natural or synthetic rubbers, synthetic composites, microfiber composites, etc. Some advantages of a composite cover are that they are durable and less expensive than a leather cover. Synthetic leather can also be made by, for example, impregnating a fibrous mat made from nylon or polyester with a coating resin such as thermoplastic rubbers, natural rubber, polyether urethanes, metallocene polyethylenes, polyureas, PVC plastisols, EPDM rubber, and the like. Some synthetic leathers suitable for the cover layer include those described in U.S. Pat. No. 5,669,838, the contents of which are hereby fully incorporated by reference herein.
[0075] The foam layer and cloth layer may also be formed from materials known in the art. For example, the foam layer can be made from styrene butadiene rubber (SBR); polybutadiene rubbers; polyurethane foams; ethylene vinyl acetate (EVA) foams; polypropylene foams; ethylene propylene diene monomer (EPDM); and combinations and blends thereof.
[0076] The additional weighting of the middle portion of the football casing can be accomplished by several different means. Additional strips, patches, or layers of higher-density material, made by incorporating high-density fillers into a polymeric binder, may be placed as needed to change the weight distribution. The thickness of the various layers could vary, being thickest near the middle and tapering off as the layer progresses to an end 170 of the casing. The tapering may be gradual (i.e. at a constant rate from surface center 175 to end 170 ) or sharp (i.e., transitioning immediately from one thickness to a second thickness, such as near or at the intersection of the surface with the two planes 140 , 145 ). Again, weighted strips may be part of the football casing, and the weighted strips surround the bladder. In embodiments, two or more weighted strips are used. Typically, four weighted strips are used as the football casing is generally made from four separate panels. A weighted strip is located on each panel. Generally, the weighted strips have a uniform thickness along their entire length and width.
[0077] Again, the fact that the middle portion is weighted compared to the end portions should not be construed as requiring the middle portion to be evenly or homogeneously weighted throughout its entirety.
[0078] A weighted football of the present disclosure could thus be made from a combination of: (a) weighted bladder plus normal football casing; (b) normal bladder plus weighted football casing; and (c) weighted bladder plus weighted football casing. Again, the weighted football has the major axis 110 , a minor axis 120 , center 130 , two imaginary planes 140 , 145 , middle portion 150 and two end portions 160 , middle portion weight 153 , end portion weight 163 , middle portion length 155 , and two end portion lengths 165 as described in FIG. 3 . The middle portion of the weighted football would include the middle portion of the bladder and the middle portion of the football casing.
[0079] In embodiments, the weighted football has a ratio of (middle portion weight/middle portion length) to (end portion weight/end portion length) that is at least 2, including 2.1. In further embodiments, the ratio is at least 2.2, at least 2.5, or from at least 2 to about 2.5.
[0080] Alternatively, the ratio of (middle portion length/end portion length) for the weighted football is from about 0.5 to about 0.95; and the weight of the middle portion is at least 1.5 times greater than the weight of one end portion. In further specific embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.95; and the weight of the middle portion is at least 2 times greater, at least four times greater, or about five times greater than the weight of one end portion. In another embodiment, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.95; and the weight of the middle portion is from at least 2 times greater to about five times greater than the weight of one end portion. In yet further embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.7, or from about 0.8 to about 0.95.
[0081] In yet other embodiments, the ratio of (middle portion length/end portion length) for the weighted football is from about 0.5 to about 0.95; and the weight of the middle portion is at least 45% of the total weight of the weighted football. In more specific embodiments, the ratio of (middle portion length/end portion length) for the casing is from about 0.5 to about 0.95; and the weight of the middle portion is at least 50%, at least 65%, or at least 70% of the total weight of the weighted football. In other embodiments, the ratio of (middle portion length/end portion length) is from about 0.5 to about 0.7. In particular embodiments, the middle portion length is from about 2.5 inches to about 3.5 inches.
[0082] FIGS. 4 and 5 illustrate a weighted football having both a weighted bladder and a weighted football casing. FIG. 4 is a simplified cross-sectional view from the top (i.e. through the lacing) of the weighted football 100 , while FIG. 5 is a simplified cross-sectional view from one end of the weighted football 100 along line A-A of FIG. 4 . The bladder 200 has two seams 202 generally oriented at the top (i.e. where the lacing 40 is placed) and bottom. Two weighted strips 400 are placed around the bladder, with the gaps located with the bladder seams 202 . As seen in FIG. 4 , the weighted strips 400 are located in the middle portion of the football, with imaginary planes 140 , 145 shown for reference. The football casing 300 surrounds the bladder, and is made from four panels 304 . Each panel 304 includes a cloth liner 306 , a foam liner 308 , and a cover layer 310 . Four weighted strips 400 are present, one on each panel, shown here as being attached to the cloth liner 306 on the side facing the bladder 200 . The gaps between the weighted strips are located with the panel seams 302 . However, the weighted strips could be placed between any layer of the panel 304 as desired. In addition, not all layers in the panel 304 are required. For example, in some embodiments, no foam liner 308 is included.
[0083] The weighted strips 400 can be considered part of the bladder or part of the casing, depending on how the football is manufactured. For example, in some embodiments, the bladder is made from a plurality of elastomeric layers, and weighted strips are located between adjacent elastomeric layers. For example, in a bladder made from four layers of polyurethane film, the weighted strips are placed between the second and third layers of film.
[0084] FIGS. 6 and 7 show two variations of the weighted strip 400 . In one variation shown in FIG. 6 , the weighted strip has a relatively constant thickness, with the middle height 402 being about equal to the end height 404 . In the variation shown in FIG. 7 , the weighted strip tapers towards each end of the football, with the middle height 402 being greater than the end height 404 .
[0085] The weighted strip(s) may have a length of from about 3.0 to about 7.0 inches. The strip(s) may have a width of from about 1.5 inches to about 3.5 inches, particularly a width of from about 2.5 inches to about 3.5 inches, or about 2.75 inches. The strip(s) may have a thickness of from about 0.01 inches to about 0.3 inches, particularly about 0.05 inches. Each strip may have a weight of from about 5 grams to about 25 grams, particularly from about 10 grams to about 20 grams. They are used in a quantity sufficient to add a weight of about 80 to about 90 grams to the middle section of the weighted football. Please note that the length and width orientations for the weighted strip do not necessarily correlate with the length and width orientations for the weighted football, bladder, or casing.
[0086] The weighted strips, when used on the bladder, may more particularly have a length of about 6 to about 7 inches and a width of from about 1.5 to about 2 inches. Each strip may weigh about 20 grams.
[0087] The weighted strips, when used on the football casing, may more particularly have a length of about 3 to about 4 inches and a width of from about 1.5 to about 2 inches. Each strip may weigh about 10 grams.
[0088] In some particular embodiments, the weighted football uses two weighted strips on the bladder and four weighted strips on the football casing.
[0089] The following example is provided to illustrate the weighted footballs and methods of the present disclosure. The examples are merely illustrative and are not intended to limit the disclosure to the materials, conditions, or process parameters set forth therein.
EXAMPLE
[0090] A weighted football bladder is made and is combined with a conventional or “normal” football casing. The football bladder has a major axis length of 11.5 inches and a total weight of 166.4 grams. The end portion has a length of 4.0 inches and a weight of 24.0 grams. The middle portion has a length of 3.5 inches and a weight of 118.4 grams. The football casing has a total weight of 196.4 grams. The football itself has a total weight of 410.0 grams. The discrepancy in weight is attributed to the lacing and components which are not considered for the weighted football.
[0091] Next, a weighted football casing is made and is combined with a “normal” football bladder. Again, the bladder has a total weight of 166.4 grams and the weighted casing has a total weight of 196.4 grams. The weight distribution of the football casing is the same as that of the weighted football bladder described above.
[0092] For the “normal” bladder and casing, it is assumed that the weight is distributed evenly along the length of the major axis. For the weighted casing, it is assumed that the weight is distributed in the same ratio as in the weighted bladder. Table 2 provides the various ratios for these weighted football bladders, skins, and footballs.
[0000]
TABLE 2
Weighted Bladder or
Weight per
Weighted Football
Length
Length
Length
Casing
Weight (g)
(in)
(cm)
(g/cm)
End
24
4
10.16
2.36
Middle Portion
118.4
3.5
8.89
13.32
Weight/Weight Ratio
4.93
(Middle/End)
Weight/Length Ratio
5.64
(Middle/End)
Length/Length Ratio
0.88
(Middle/End)
Weight
Bladder
Casing
Total
per
Weight
Weight
Weight
Length
Length
(g)
(g)
(g)
(cm)
(g/cm)
Weighted Bladder
plus Normal Football
Casing
End Portion
24
68.31
92.31
10.16
9.09
Middle Portion
118.4
59.77
178.17
8.89
20.04
Weight/Weight Ratio
1.93
(Middle/End)
Weight/Length Ratio
2.21
(Middle/End)
Length/Length Ratio
0.88
(Middle/End)
Normal Bladder plus
Weighted Football
Casing
End Portion
57.88
28.33
86.21
10.16
8.48
Middle Portion
50.64
139.75
190.39
8.89
21.42
Weight/Weight Ratio
2.21
(Middle/End)
Weight/Length Ratio
2.52
(Middle/End)
Length/Length Ratio
0.88
(Middle/End)
[0093] The weighted footballs and methods of the present disclosure have been described with reference to exemplary embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the exemplary embodiments be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. | A sportsball, such as a football, is preferentially constructed to enhance spiral rotation when thrown or kicked, allowing enhanced stability and distance. | 8 |
FIELD OF THE DISCLOSURE
The embodiments described herein relate to a packer having a thermal memory spacing system that includes a portion of the system that that changes the outer diameter due to temperature and method of using the thermal memory spacing system.
BACKGROUND
Description of the Related Art
Packing devices, such as straddle packers, may be conveyed into a wellbore to be used to selectively isolate a portion of the wellbore. The isolation of a portion of the wellbore may be done for various reasons such as treating and/or fracturing the formation adjacent to the casing of the portion being isolated by the packer. While the packer is set against the casing it is quite common for debris and/or material to accumulate in the annulus between the packer and the casing as well as above the packer. In some instances, the accumulation of debris and/or material can cause it to be difficult to unset the packer when the treatment process has finished. Further, the debris and/or material can cause the packer to become stuck within the wellbore, not permitting the packer to be moved to another location within the wellbore.
SUMMARY
The present disclosure is directed to a packer that includes a thermal memory sub and method of using the thermal memory sub that overcomes some of the problems and disadvantages discussed above.
One embodiment is a packer comprising an upper sealing element, a lower sealing element, and a first sub positioned between the upper and lower sealing elements, the first sub being comprised of a memory shape material. At a first temperature the first sub has a first outer diameter and at a second temperature the first sub has a second outer diameter, the second outer diameter being larger than the first outer diameter.
The first temperature may be greater than the second temperature. The packer may include a fluid displacement sub positioned between the upper and lower sealing elements, the fluid displacement sub may have at least one port that permits fluid communication between an interior of the fluid displacement sub and an exterior of the fluid displacement sub. The packer may comprise a second sub positioned between the upper and lower sealing element, the second sub may be comprised of a memory shape material. The second sub may have a first outer diameter at the first temperature and may have a second outer diameter at the second temperature. The second outer diameter of the second sub may be larger than the first outer diameter. The fluid displacement sub may be positioned between the first sub and the second sub. The packer may comprise a third sub positioned above the upper sealing element. The third sub may be comprised of a memory shape material and may have a first outer diameter at the first temperature and may have a second outer diameter at the second temperature. The second diameter of the third sub may be larger than the first diameter. The first temperature may be greater than the second temperature.
The memory shape material may be a memory shape alloy. The memory shape alloy may be nickel titanium alloy, nickel titanium zirconium alloy, titanium nickel copper alloy, copper aluminum manganese alloy, iron nickel cobalt aluminum tantalum boron alloy, copper aluminum niobium alloy, nickel manganese gallium alloy, zirconium copper alloy, polycrystalline iron nickel cobalt aluminum alloy, polycrystalline iron manganese aluminum nickel alloy, polycrystalline nickel titanium zirconium niobium alloy, or combination thereof. The memory shape material may be a memory shape polymer. The first temperature may be at least approximately five degrees Fahrenheit greater than the second temperature. The second diameter of the first sub may be at least 5% larger than the first diameter of the first sub.
One embodiment is a method of treating a portion of a wellbore. The method comprises positioning a packer connected to a tubing string adjacent a first portion of a wellbore, the packer comprising an upper sealing element, a lower sealing element, a fluid displacement sub, and at least one sub comprised of a memory shape material having a first outer diameter at a first temperature and having a second outer diameter at a second temperature. The fluid displacement sub and the at least one sub each positioned between the upper and lower sealing elements. The method comprises actuating the upper and lower sealing elements to selectively isolate the first portion of the wellbore and treating the first portion of the wellbore. The method comprises changing a temperature of the isolated first portion of the wellbore to the second temperature, wherein the at least one sub as the second outer diameter which is different than the first outer diameter.
The second outer diameter of the at least one sub may be larger than the first outer diameter of the at least one sub. Treating the first portion of the wellbore may comprise pumping fluid down the tubing string and out the fluid displacement sub. Treating the first portion of the wellbore may comprise fracturing a formation by pumping fluid down the tubing string and out the fluid displacement sub. The formation may have been previously fractured and the formation may be re-fractured by the treatment.
The method may include changing the temperature of the isolated first portion of the wellbore to the first temperature after treating the first portion of the wellbore, wherein the at least one sub moves to the first outer diameter. The method may include unsetting the upper and lower sealing elements and moving the packer to a second portion of the wellbore. The at least one sub may have the first outer diameter as it is positioned adjacent to the first portion of the wellbore. The at least one sub may comprise a first sub positioned above the fluid displacement sub and a second sub positioned below the fluid displacement sub, wherein the first and second subs are both positioned between the upper and lower sealing elements. The method may include changing a temperature of the isolated first portion of the wellbore to the second temperature, which may actuate the first and second subs to their second outer diameters being larger than their first outer diameters. The method may include changing the temperature of the isolated first portion of the wellbore to the first temperature after treating the first portion of the wellbore, wherein the first temperature actuates the first and second subs to their first outer diameters being smaller than their second outer diameters.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an embodiment of a packer having thermal memory subs isolating and treating a portion of a wellbore.
FIG. 2 shows an embodiment of a packer having thermal memory subs positioned within a wellbore.
FIG. 3 shows a cross-section of a portion of one embodiment of a packer with a thermal memory sub in an expanded state within a wellbore.
FIG. 4 shows a cross-section of a portion of a one embodiment of a packer with a thermal memory sub in a contracted state within a wellbore.
FIG. 5 shows a cross-section of a portion of one embodiment of a thermal memory sub in an expanded state.
FIG. 6 shows a cross-section of a portion of one embodiment of a thermal memory sub in a contracted state.
FIG. 7 shows a cross-section of a portion of one embodiment of a thermal memory sub in an expanded state.
FIG. 8 shows a cross-section of a portion of one embodiment of a thermal memory sub in a contracted state.
FIG. 9 shows a flow chart of an embodiment of a method of treating a portion of a wellbore.
While the disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and will be described in detail herein. However, it should be understood that the disclosure is not intended to be limited to the particular forms disclosed. Rather, the intention is to cover all modifications, equivalents and alternatives falling within the scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION
FIG. 1 shows an embodiment of a packer 100 having thermal memory subs 140 A, 140 B, and 140 C positioned within a wellbore. The packer 100 may be connected to a tubing string 10 and run into a wellbore, which may include a casing 1 . The packer 100 may be positioned adjacent to perforations 2 in the casing 1 that permits fluid communication with the adjacent formation 5 and the wellbore. The formation 5 may be fractured 6 adjacent the perforations 2 in an attempt to increase the production of hydrocarbons from the formation 5 .
The packer 100 may include an upper sealing element 110 , upper slips 111 , upper blocks 112 , and an upper j-slot track 113 . The upper sealing element 110 may be set against the casing 1 to create a seal, as shown. The packer 100 may include a lower sealing element 120 , lower slips 121 , lower blocks 122 , and a lower j-slot track 123 . The lower sealing element 120 may be set against the casing 1 to create a seal, as shown. The packer 100 , including the various components, is for illustrative purposes only as various downhole packers may be used in connection with the thermal memory subs 140 A, 140 B, and 140 C disclosed herein. The upper and lower sealing elements 110 and 120 may be used to isolate a portion of the wellbore. The packer 100 may include a fluid displacement sub 130 with a port 131 or plurality of ports 131 that permit fluid communication from the tubing string 10 to the exterior of the fluid displacement sub 130 . The fluid displacement sub 130 may be connected between two thermal memory subs 140 B and 140 C.
The thermal memory subs 140 A, 140 B, and 140 C are configured so that the exterior of the subs 140 A, 140 B, and 140 C is comprised of a memory shape material that changes shape depending on the temperature. The thermal memory subs 140 A, 140 B, and 140 C may be configured so that the subs 140 A, 140 B, and 140 C have a first smaller outer diameter at a first temperature and have a second larger outer diameter at a second temperature. The second diameter may be approximately 10%, or more, larger or than the first diameter. However, the actual change in diameters may be configured based on the intended application. For example, a 5%, or even less, change in diameter may be sufficient in certain circumstances. The subs 140 A, 140 B, and 140 C may be comprised of various materials as would be appreciated by one of ordinary skill in the art having the benefit of this disclosure. The memory shape material may be comprised of a memory shape alloy. For example, the subs 140 A, 140 B, and 140 C may be comprised of, but not limited to, nickel titanium alloy, nickel titanium zirconium alloy, titanium nickel copper alloy, copper aluminum manganese alloy, iron nickel cobalt aluminum tantalum boron alloy, copper aluminum niobium alloy, nickel manganese gallium alloy, zirconium copper alloy, polycrystalline iron nickel cobalt aluminum alloy, polycrystalline iron manganese aluminum nickel alloy, and polycrystalline nickel titanium zirconium niobium alloy. Alternatively, the sub 140 may be comprised of a memory shape polymer that permits the actuation between different shapes as would be appreciated by one or ordinary skill in the art having the benefit of this disclosure.
At a first temperature, the outer diameter of the thermal memory subs 140 A, 140 B, and 140 C may be smaller than the outer diameter of the thermal memory subs 140 A, 140 B, and 140 C at a second temperature. The first temperature may be hotter than the second temperature. In one embodiment, there may be at least a 5 degree Fahrenheit difference between the first and second temperatures. However, the difference between the first and second temperatures may be larger than 5 degrees Fahrenheit. For example, the difference between the first and second temperatures may be 10, 20, 25, 50, or more degrees Fahrenheit. As the temperature of the thermal memory subs 140 A, 140 B, and 140 C decreases the outer diameter of the thermal memory subs 140 A, 140 B, and 140 C may increase. FIG. 1 shows the packer 100 positioned within the wellbore during treatment of the first portion of the wellbore, which may represent the second temperature. Thus, the outer diameter of the subs 140 A, 140 B, and 140 C is increased presenting less annular area between the subs 140 A, 140 B, and 140 C and the casing 1 . A smaller annular area between the subs 140 A, 140 B, and 140 C and the casing 1 may provide less area for the buildup of debris within the wellbore. As discussed herein, the later decrease in the outer diameter of the subs 140 A, 140 B, and 140 C may reduce the chance that the packer 100 becomes stuck within the wellbore as it is unset and attempted to be moved to another location. The treatment pumped through the port 131 of the fluid diversion sub 130 may comprise the injection of fluid into the formation or the fracturing, or re-fracturing, of a formation 5 adjacent the portion of the wellbore isolated by the sealing elements 110 and 120 of the packer 100 .
Once the treatment of the wellbore is completed, the temperature of the thermal memory subs 140 A, 140 B, and 140 C may raise to normal well temperatures, which may represent the first temperature. Thus, the outer diameter of the thermal memory subs 140 A, 140 B, and 140 C decreases enlarging the annular area between the subs 140 A, 140 B, and 140 C and the casing 1 as shown in FIG. 2 . This enlarged area, in comparison to the annular area during the treatment process, may reduce the chance that the packer 100 will become stuck within the wellbore due to debris between the packer 100 and the casing 1 . The packer 100 may include a thermal memory sub 140 A above the upper sealing element 110 as well as multiple thermal memory subs 140 B and 140 C between the upper and lower sealing elements 110 and 120 . The packer 100 could also include a thermal memory sub below the lower sealing element 120 , if desired. The number and configuration of the thermal memory subs 140 A, 140 B, and 140 C is for illustrative purposes only and may be varied as would be appreciated by one of ordinary skill in the art having the benefit of this disclosure. The thermal memory sub 140 provides a smaller annular area for the buildup of debris between the packer 100 and casing 1 during the treatment of the wellbore. The thermal memory sub 140 then provides a larger annular area when the packer 100 is to be unset and moved within the wellbore decreasing the likelihood that debris will cause the packer 100 will become stuck within the casing 1 .
FIG. 3 and FIG. 4 shows a cross-section view of a packer 100 positioned within casing 1 of a wellbore. In FIG. 3 , the packer 100 is at a first or lower temperature and the packer is at a second or higher temperature in FIG. 4 . In FIG. 4 , the outer diameter of the thermal memory sub 140 has contracted due to the movement of memory shape material so that the annular area 15 between the casing 1 and the sub 140 is larger in comparison to the annular area 15 of FIG. 3 .
FIG. 5 and FIG. 6 show a cross-section view of an embodiment of a thermal memory sub 140 having a core 141 and a memory shape material 142 positioned around the core 141 . The core 141 may have an inner diameter 143 . FIG. 5 shows the thermal memory sub 140 at a first or lower temperature at which the thermal memory sub 140 has an outer diameter 144 A. FIG. 6 shows the thermal memory sub 140 at a second or higher temperature at which the outer diameter 144 B has reduced in comparison to the outer diameter of FIG. 5 . The inner diameter 143 of the core 141 does not change significantly in either the first or second temperatures. FIG. 6 shows one embodiment on the potential change in shape of the memory shape material 142 to reduce the overall outer diameter of the thermal memory sub 140 .
FIG. 7 and FIG. 8 show a cross-section view of an embodiment of a thermal memory sub 140 having a core 141 and a memory shape material 142 positioned around the core 141 . FIG. 7 shows the thermal memory sub 140 at a first or lower temperature so that the memory shape material 142 extends away from the core 141 to increase the outer diameter or outer perimeter of the sub 140 . FIG. 8 shows the thermal memory sub 140 at a second or higher temperature at which the memory shape material 142 contracts towards the core 141 reducing the outer diameter in comparison to the outer diameter of FIG. 7 .
FIG. 9 shows a flow chart of one embodiment of a method 200 of treating a portion of a wellbore. The first step 210 is positioning a packer adjacent a first portion of the wellbore. The sealing elements of the packer are actuated to isolate the first portion of the wellbore in step 220 . The first portion of the wellbore is treated in step 230 and the temperature of the first portion of the wellbore is changed during the treatment process in step 240 . For example, the temperature may be lowered during the treatment process. However, the temperature could instead be raised during the treatment process. Optionally the treatment of the wellbore may comprise fracturing the wellbore in step 250 or re-fracturing the portion of the wellbore in step 260 if the wellbore has already been previously fractured. The changing of the temperature in step 240 , which is done contemporaneously with the treatment of the wellbore in step 230 , causes the increasing of an outer diameter of at least a portion, such as a sub comprised of a memory shape material, of the packer. Upon finishing the treatment process 230 of the wellbore, the temperature of the first portion of the wellbore is changed again in step 270 . For example, the temperature may be increased causing a reduction in an outer diameter of at least the portion of the packer, such as the sub comprises of the memory shape material. Alternatively, a reduction in the temperature may cause the reduction in an outer diameter of at least a portion of the packer. Treating the wellbore with the sub having a larger diameter reduces the annular area between the sub and the wellbore decreasing the amount of debris and other material that may collect in this area. After treating the wellbore has finished and the temperature increases, the outer diameter of the sub will reduce enlarging the annular area, which will decrease the chance that the packer will become stuck due to the debris within the annular area adjacent the sub.
Although this disclosure has been described in terms of certain preferred embodiments, other embodiments that are apparent to those of ordinary skill in the art, including embodiments that do not provide all of the features and advantages set forth herein, are also within the scope of this disclosure. Accordingly, the scope of the present disclosure is defined only by reference to the appended claims and equivalents thereof. | A packer having a thermal memory spacing system that includes a portion of the system that that selectively changes an outer diameter due. The packer may include upper and lower sealing elements, and at least one thermal memory shape material sub positioned between the sealing elements. The thermal memory shape material sub may have a first outer diameter at a first temperature and a second larger outer diameter at a second temperature. The first temperature may be greater than the second temperature. The outer diameter of the sub may be selectively increased to temporarily decrease the annular area in which debris and/or materials may collect and potentially cause the packer to become stuck within the wellbore. Prior to moving the packer to a different location, the outer diameter of the sub may be decreased to increase the annular area. | 4 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application is based upon and claims priority from U.S. provisional patent application serial No. 60/282,120 filed Apr. 6, 2001, the disclosure of which is incorporated herein by reference, in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention is directed to methods for treating the inflammatory component of brain disorders in mammalian patients, and more particularly for treating those neurological brain disorders in which reactive oxygen species play a significant role in the underlying inflammatory pathology.
[0004] 2.State of the Art
[0005] The events that lead to neurological disorders with a significant inflammatory component (including myasthenia gravis, GBS, CIDP, and multiple sclerosis) are not clear, but the following sequential steps appear to be critical. (1) The breaking of tolerance, a process in which cytokines, molecular mimicry, or superantigens may play a role in rendering previously anergic T-cells to recognize neural autoantigens. (2) Antigen recognition by the T-cell receptor complex and processing of the antigen via the major histocompatibility complex class I or II. (3) Costimulatory factors, especially B7 and B7-binding proteins (CD28, CTLA-4) and intercellular adhesion molecule (ICAM-1) and its leukocyte function-associated (LFA)-1 ligand. (4) Traffic of the activated T cells across the blood-brain or blood-nerve barrier via a series of adhesion molecules that include selectins, leukocyte integrins (LFA-1, Mac-1, very late activating antigen (VLA)-4) and their counterreceptors (ICAM-1, vascular cell adhesion molecule (VCAM)) on the endothelial cells. (5) Tissue injury when the activated T cells, macrophages, or specific autoantibodies find their antigenic targets on glial cells, myelin, axon, calcium channels, or muscle.
[0006] In designing specific immunotherapy, the main components involved in every step of the immune response need to be considered. Targets for specific therapy in neurological disease include agents and treatments that (a) interfere or compete with antigen recognition or stimulation; (b) inhibit costimulatory signals or cytokines; (c) inhibit the traffic of the activated cells to tissues; and (d) intervene at the antigen recognition sites in the targeted organ.
[0007] Reactive oxygen species (ROS) are activated forms of oxygen, including superoxide anion (O 2 . − ) and hydroxyl radicals (HO.) together with hydrogen peroxide (H 2 O 2 ) and various unstable intermediates of lipid peroxidation. They are generated as a result of aerobic metabolism. Neuronal brain tissue is particularly susceptible to oxidative damage due its to high consumption of oxygen and its limited antioxidant defense system. Reactive oxygen species formation is thought to have an impact on synaptic plasticity, cell signaling and the aging process. An age-related increase in reactive oxygen species production has been demonstrated (Martin et al., 2000) and the accumulation of reactive oxygen species has also been shown to be increased in the hippocampus as a consequence of peripheral LPS administration (Vereker et al., 2000a). This is mimicked by IL-1β administration (Vereker et al., 2000b). O'Donnell and colleagues (2000) have reported parallel changes in reactive oxygen species formation and IL-1βproduction; reactive oxygen species formation was shown to cause an increase in IL-1β production while IL-1β has the ability to induce reactive oxygen species formation thus suggesting the existence of a positive feedback loop which is potentially damaging to cells.
[0008] Increased concentrations of IL-1β have also been closely linked with neuronal degeneration (Mogi et al., 1996; Tenneti et al., 1998).
[0009] Enhanced activity of the stress-activated kinase c-Jun NH 2 -terminal kinase (JNK) is associated with cell degeneration and death (Park et.al., 1996; Maroney et.al., 1998), and has been shown to be activated in the hippocampus by several agents, including hydrogen peroxide, an inducer of reactive oxygen species production, and pro-inflammatory cytokines.
[0010] Another example of a neuronal brain deficit induced by IL-1β and LPS, is the impairment of long term potentiation (LTP) in the hippocampus (Vereker et al 2000a; Murray & Lynch, 1998). LTP is a form of synaptic plasticity that was originally described in the hippocampus, a brain region that is particularly vulnerable to degeneration which is associated with cognitive dysfunction. On the basis of this and other observations, LTP has been proposed as a biological substrate for learning and memory (Bliss & Collingridge, 1993).
[0011] Certain neurological brain disorders such as Downs syndrome (Layton et.al., Kedziora et.al., Schuchmann et. al.), epilepsy, brain trauma (e.g. physical damage to the brain such as concussion)(Layton et.al., Wildburgur et.al., Trembovler et.al.) and Huntington's disease (chorea)(Green) are currently understood to involve inflammation of brain cells as a significant component of the underlying pathology of the disorder. This inflammation could be the consequence of one or more of a variety of biological processes, such as the generation of excess-amounts of inflammatory cytokines such as IL-1β and TNF-α, in the brain cells or other components of the brain tissue, perhaps associated with the presence of high concentrations of reactive oxygen species in the brain tissue, which correlates to high levels of tissue damage or exacerbation of the disease. Reactive oxygen species are one of the effectors of inflammation in tissue such as brain tissue.
[0012] Other neurological disorders which have a significant inflammatory component include Guillain-Barré syndrome (GBS), chronic inflammatory demyelinating polyneuropathy (CIDP), myasthenia gravis (MG), dermatomyositis, polymyositis, inclusion body myositis, post stroke, neurosarcoidosis, vascular dementia, closed head trauma, vasospasm, subarachnoid hemorrhage, adrenal leukocytic dystrophy (storage disorders), inclusion body dermatomyostis, minimal cognitive impairment and duchenne muscular dystrophy.
[0013] Chronic inflammatory demyelinating polyneuropathy (CIDP) is a neurological disorder characterized by slowly progressive weakness and sensory dysfunction of the legs and arms. The disorder, which is sometimes called chronic relapsing polyneuropathy, is caused by damage to the myelin sheath of the peripheral nerves. CIDP can occur at any age and in both genders, is more common in young adults, and in men more so than women. The primary symptoms include slowly progressive muscle weakness and sensory dysfunction affecting the upper and lower extremities. Other symptoms may include fatigue; abnormal sensations including burning, numbness and/or tingling sensations (beginning in the toes and fingers); paralysis of the arms and/or legs; weakened or absent deep tendon reflexes (areflexia); and, aching pain affecting various muscle groups.
[0014] CIDP is closely related to the more common, acute demyelinating neuropathy known as Guillain-Barré syndrome (GBS). CIPD is considered the chronic counterpart of the acute disease GBS. CIDP is distinguished from GBS, chiefly by clinical course and prognosis. However, both disorders have similar clinical features, and both share the CSF albuminocytological dissociation and the pathological abnormalities of multi-focal inflammatory segmental demyelination with associated nerve conduction features reflecting demyelination.
[0015] Guilain-Barré Syndrome (GBS) is an acute predominately motor polyneuropathy with spontaneous recovery that may lead to severe quadriparesis and requires artificial ventilation in 20-30% of patients. The diseases that underlie this syndrome have been classified as acute inflammatory demyelinating polyneuropathy (AIDP), the most common form, acute motor and sensory axonal neuropathy (AMSAN), and acute motor axonal neuropathy (AMAN). Fisher syndrome is a cranial nerve variant of GBS which characteristically results in opthalmoplegia, ataxia and areflexia. GBS is often preceded by infection with either Campylobacterjejuni, which is most common, cytomegalovirus (CMV), Epstein-Barr virus or Mycoplasma pneumoniae.
[0016] Autoimmune myasthenia gravis (MG) is a disorder of neuromuscular transmission leading to fluctuating weakness and abnormal fatigueability. Weakness is attributed to the blockade of acetylcholine receptors (AChRs) at the neuromuscular endplate by circulating autoantibodies, followed by local complement activation and destruction of acetylcholine receptors (Stangel et al, J. Neurol. Sci. 153(2):203-14 (1998)). AchR is expressed on regenerating myoblasts but in normal adult muscle the AChR is only expressed at the motor endplate. In patients with early onset MG however the thymic medulla is infiltrated by lymph node-like T cells and germinal centres and there are myoblast-like myoid cells in the thymic medulla which express AChR. Therefore the presentation of the AChR antigen by these cells or by myoblasts is likely to be involved in the disease process (Curnow et al, J. Neuroimmunol. 115(1-2):127-134 (2001)). In studies of experimental autoimmune myasthenia gravis (EAMG) the Th2 cytokine, INF-γ, has been shown to be involved in disease progression and has been reported to be capable of inducing the production by myoblasts of class I and II major histocompatibility antigens, AChR and ICAM-1. IL-1 has also been shown to play a role in EAMG where disruption of the IL-1 beta gene was shown to diminish acetylcholine receptor-induced responses (Garcia et al, J. Neuroimmunol 120(1-2):103-11 (2001); Stegall et al, J. Neuroimmunol. 119(2):377-386 (2001)).
[0017] The causes of inflammatory muscle diseases dermatomyositis, polymyositis and inclusion body myositis (IBM) are unknown, but immune mechanisms are strongly implicated. Although clinically and immunopathologically distinct, these diseases share three dominant histological features: inflammation, fibrosis and loss of muscle fibres. In dermatomyositis, the endomysial inflammation and muscle fiber destruction is preceded by activation of the complement system of plasma proteins, and deposition of membranolytic attack complex on the endomysial capillaries (Dalakas, Curr. Opin. Pharmacol. 1(3):300-306 (2001)). There is evidence that this attack may also involve the blood vessels in the dermis (Dalakas et al, Curr. Opin. Pharmacol. 9(3):235-239 (1996)). Transforming growth factor beta, shown to be overexpressed in the perimysial connective tissue in dermatomyositis, is down-regulated after successful immunotherapy and reduction of inflammation and fibrosis (Dalakas, Arch. Neurol. 55(12):1509-1512 (1998)).
[0018] In polymyositis and IBM the disease begins with the activation of CD8 + T cells. These cytotoxic T cells reach the endomysial parenchyma to recognise muscle antigen(s) associated with the upregulation of the major histocompatibility complex (MHC) I on muscle fibres. The autoinvasive T cells exhibit gene rearrangement of their T-cell receptors (TCR) and are specifically selected and clonally expanded in situ by heretofore previously unknown antigens. Muscle cells do not normally express MHC I and II but in cases of polymyositis and IBM over expression of MHC is an early event that can be detected even in areas remote from the inflammation. INFγ and TNFα, cytokines that induce MHC, have been found in patients with active polymyositis (Dalakas, Curr. Opin. Pharmacol. 1(3):300-306 (2001)).
[0019] No signs of apoptosis have been detected in patients with inflammatory myopathies and in fact two strong anti-apoptotic molecules have recently been found to be expressed in the muscle fibers. One is the Fas-associated death domain-like IL-1-converting enzyme inhibitory protein (FLIP) and the other human IAP (inhibitor of apoptosis protein)-like protein. The result of unsuccessful apoptotic clearance of inflammatory cells is likely to be the cause of the sustained chronic cytotoxic muscle fiber damage (Vattemi et al, J. Neuroimmunol. 111(1-2):146-151 (2000)).
[0020] Sarcoidosis is a multisystem chronic disorder with unknown cause and a worldwide distribution. Neurosarcoidosis is a complication of sarcoidosis involving inflammation and abnormal deposits in the tissues of the nervous system. Sudden, transient facial palsy is common with involvement of cranial nerve VII. Other manifestations include aseptic meningitis, hydrocephalus, parenchymatous disease of the central nervous system, peripheral neuropathy and myopathy. Intracranial sarcoid may mimic various forms of meningitis, including carcinomatous and intracranial mass lesions such as meningioma, lymphoma and glioma, based on neuroradiological imaging. A lumbar puncture may show signs of inflammation. Elevated levels of angiotensin converting enzyme may be found in the blood or CSF. Therapy consists of immunosuppressive agents and corticosteroids (Nowak et al, J. Neurol. 248(5):363-372 (2001); Stern et al, Arch. Neurol. 42(9):909-917 (1985)).
[0021] Vascular dementia (VaD) is the general term for dementia caused by organic lesions of vascular origin, such as cerebral infarction, intracerebral haemorrhage or ischemic changes in subcortical white matter. It is the most frequent cause of dementia after AD accounting for about 20% of cases and 50% in subjects over 80 years (Dib, Arch. Gerontol. Geriatr. 33(1):71-80 (2001); Parnetti et al, Int. J. Clin. Lab Res. 24(1):15-22 (1994)). The clinical distinction between AD and VaD may be difficult and there are standard guidelines for research studies. VaD and AD can coexist as “mixed dementia” where the presence of cerebrovascular disease may worsen Alzheimer dementia. Traditionally AD is characterized by the insidious onset of memory loss, followed by a gradual progression to dementia in the face of normal findings on neurological examination. VaD on the other hand, is characterized by stepwise cognitive decline punctuated by episodes of stroke that are accompanied by focal deficits on neurological examination, and evidence of stroke on computed topography (CI) or magnetic-resonance imaging (Jagust, Lancet 358(9299):2097-2098 (2001)). It is assumed that the risk factors for stroke and vascular disease are also factors for VaD. These include hypertension, smoking, diabetes, obesity, cardiac rhythm disorders, hyperlipidaemia, hypercholesterolaemia and hyperhomocysteinaemia. The apolipoprotein E4 genotype is also considered as a risk factor for VaD, AD and ischemic stroke (Dib, Arch. Gerontol. Geriatr. 33(1):71-80 (2001)). Current treatments of vascular dementia include anti-platelet agents and/or surgery, and the treatment of cognitive symptoms (Parnetti et al, Int. J. Clin. Lab. Rews. 24(1):15-22 (1994)).
[0022] Head trauma is associated with a variety of physiological and cellular phenomena such as ischemia, increased permeability of the blood-brain barrier (BBB), edema, necrosis and motor and memory dysfunction (Moor et al, Neurosci. Lett. 316(3):169-172 (2001); Shohami et al, J. Neuroimmunol. 72(2):169-177 (1997)). Ischemia caused by the initial brain injury induces a cascade of secondary events and the release of excitatory amino acids (EAA) such as glutamate and aspartate. Alteration in the levels of ions and neuromodulators lead to oxidation and cellular membrane damage and ultimately cellular death (Stahel et al, Brain Res. Rev. 27(3):243-256 (1998)). Experimental models for closed head injury (CHI) developed in the rat show the spatial and temporal induction of IL-1, IL-6 and TNF-α gene MRNA transcription along with an induction of IL-6 and TNF-α activity in the rat brain (Shohami et al, J. Neuroimmunol. 72(2):169-177 (1997)). IL-1β has also been shown to be released and it is the presence of these cytokines along with damage to endothelial cells that result in disruption of the BBB integrity. This disruption allows the recruitment of neutrophils into the subarachnoid space (Stahel et al (1998)).
[0023] TNF-α has been identified in the brain in several pathological conditions and inhibitors of TNF-α such as dexanabinol (HU-211) have been shown to improve neurological outcome following CHI (Shohami et al, J. Neuroimmunol. 72(2):169-177 (1997)).
[0024] Cerebral vasospasm is delayed onset cerebral artery narrowing in response to blood clots left in the subaracbnoid space after spontaneous aneurysmal subarachnoid hemorrhage (SAH) (Ogihara et al, Brain Res. 889(1-2):89-97 (2001)). It is angiographically characterized as the persistent luminal narrowing of the major extraparenchymal cerebral arteries and affects the cerebral microcirculation and causes decreased cerebral blood flow (CBF) and delayed ischemic neurological deficits. A number of studies have demonstrated morphological changes in cerebral arteries after SAH. Smooth muscle cells showed necrotic changes, such as dense bodies, degeneration of mitochondria, condensed lysosomes and dissolution of nuclear substances and the appearance of cell debris (Sobey et al, Clin. Exp. Pharmacol. Physiol. 25(11):867-876 (1998)). The impaired dilator and increased constrictor mechanisms that occur after SAH may be caused by oxyhaemoglobin produced by erythrocytes that inactivates NO in the subarachnoid space. Alternatively it may be due to an impaired activity of soluble guanylate cyclase resulting in reduced basal levels of cGMP in cerebral vessels and so a reduced responsiveness to NO (Ogihara et al, Brain Res. 889(1-2):89-97 (2001)). Production of IL-6 and IL-8 in the cerebrospinal fluid following SAH has also been demonstrated. It is thought that IL-6 may play a particular role in vasospasm as in induced vasoconstriction in a canine cerebral artery (Osuka et al, Acta Neurochir 140(9):943-951 (1998)).
[0025] Duchenne muscular dystrophy (DMD) is one of the most common, inherited, lethal disorders in childhood. It is an X-linked neuromuscular disease that affects 1 in 3500 males. Progressive muscle weakness begins between 2 and 5 years of age and ultimately leads to premature death by respiratory or cardiac failure during the middle to late twenties. Approximately 30% of cases are due to spontaneous mutation of the dystrophin genes while the remainder are inherited (Spencer et al, Neuromuscul. Disord. 11(6-7):556-564 (2001)). DMD patients therefore lack the protein dystrophin which is an essential link in the complex of proteins that connect the cytoskeleton to the extracellular matrix (Alderton et al, Trends Cardiovascular Med. 10(6):268-272 (2000)). Although gene therapy is the only cure for DMD it is believed that immune interventions may slow the progress of the disease. The reason for this is that there is evidence that immune cell interactions with dystrophin-deficient muscle can contribute to cell death in dystrophinopathies. It has also been shown that the population of immune cells in dystbrophic muscle are not only different from those found that invade mechanically-damaged tissue; they are similar to those found in inflammatory disease such as polymyositis. Current research indicates that T cells may play a role in the pathology of dystrophin deficiency and that there may be an autoimmune component to the disease in which T cells are activated by a common antigen (Spencer et al, Neuromuscular Disord. 11(6-7):556-564 (2001)).
[0026] U.S. Pat. No. 5 , 834 , 030 (Bolton) describes a process for treating a patient to combat peripheral vascular disease, which comprises extracting an aliquot of the patient's blood, treating the blood aliquot extracorporeally with stressors such as an oxidative environment (ozone/oxygen gas mixture bubbled there through), incident UV light and an elevated temperature.
[0027] U.S. Pat. No. 5,980,954 (Bolton) describes similar processes for treating autoimmune diseases in mammalian patients.
[0028] It is an object of the present invention to provide a novel treatment or prophylaxis of neurological disorders which have a significant inflammatory component, such as chronic inflammatory demyelinating polyneuropathy and Guillain-Barré syndrome.
[0029] “Immune modulation therapy” as the term is used herein, is an ex vivo treatment protocol which involves exposure of autologous peripheral blood to combinations of at least two physicochemical stressors, namely heat, oxidative stress such as ozonation and electromagnetic radiation such as ultraviolet irradiation and subsequent administration of the treated blood to the patient, suitably by intramuscular injection. There is recent evidence that such immune modulation therapy suppresses contact hypersensitivity (Shivji et al., 2000) as well as demonstrating an attenuated hyperthermic response to immobilisation stress in spontaneously hypertensive rats (Kouamé et al., 1997) thus suggesting a possible protective role. In support of this is the report that following such immune modulation therapy a reduction in the relative number of pro-inflammatory TH1 cells and an increase in TH2 cells have been observed in humans, signifying a reduction in the inflammatory response (Rabinovitch et al., 1998).
SUMMARY OF THE INVENTION
[0030] This invention is directed to the surprising and unexpected discovery that such immune modulation therapy can exert beneficial anti-inflammatory effects across the blood-brain barrier of a mammalian patient, apparently through a significant reduction of the accumulation of reactive oxygen species and/or a significant down-regulation of associated inflammatory cytokines such as TNF-α, particularly in the cortical tissue of mammals. Accordingly, the therapy is suitable for either prophylactic or therapeutic treatment of the inflammatory component of neurological brain diseases such as Downs syndrome, epilepsy, Huntington's disease and brain traumas, through mediation of the development or activity of reactive oxygen species which play a role in the development or manifestation of such inflammation.
[0031] The present invention also provides for a method for the prophylactic or therapeutic treatment of inflammatory components and inflammatory aspects of a neurological disease in a mammalian patient diagnosed with or at risk of a neurological disease, which method comprises:
[0032] administering to said patient an aliquot of blood which has been treated ex vivo with at least two stressors selected from the group consisting of an oxidative environment, thermal stress and electromagnetic radiation, wherein the concentration of the reactive oxygen species in neuronal cells or tissues of said patient is reduced, with associated reduction of harmful inflammatory effects therein.
[0033] From another aspect, the present invention provides a process for alleviating the symptoms of a neurological brain disorder having a significant inflammatory component associated with excess active oxygen species (reactive oxygen species and oxidative free radicals), such as Down's syndrome, Huntington's disease, epilepsy and brain traumas, which comprises scavenging of active oxygen species from the brain of a mammalian patient by administering to said patient an aliquot of blood which has been treated ex vivo with at least two stressors selected from the group consisting of an oxidative environment, thermal stress and electromagnetic radiation.
[0034] Accordingly, the present invention is also a method of alleviation, prophylaxis against or preconditioning to hinder the onset and progression of neurodisorders which have a significant inflammatory component, such as Guillain-Barré syndrome (GBS), chronic inflammatory demyelinating polyneuropathy (CIDP), myasthenia gravis (MG), dermatomyositis, polymyositis, inclusion body myositis, post stroke, neurosarcoidosis, vascular dementia, closed head trauma, vasospasm, subarachnoid hemorrhage, adrenal leukocytic dystrophy (storage disorders), inclusion body dermatomyostis, minimal cognitive impairment and duchenne muscular dystrophy, wherein said method comprises treating a patient suffering from or at risk to contract such a disorder and having impaired endothelial function at the blood vessels, to improve the performance of endothelial function at the blood-brain barrier or at the blood-nerve barrier towards restoration of normal endothelial function. This represents a novel and innovative approach to the management and treatment of neurological disorders.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] In the accompanying drawing:
[0036] [0036]FIG. 1 is a graphical presentation of the effect of the treatment according to a preferred embodiment of the invention on the body weight of test animals, as described in the specific experimental section below;
[0037] [0037]FIG. 2 is a graphical presentation of the results of testing LPS-induced impairment of LTP described in the experimental section below;
[0038] FIGS. 3 is a graphical presentation of the measurements of reactive oxygen species accumulation described in the experimental section below;
[0039] [0039]FIG. 4 is a graphic presentation of the inflammatory cytokine TNF 2 measurements and anti-inflammatory cytokine IL-10 measurements in the cortex of test animals, described in the experimental section below;
[0040] [0040]FIG. 5 is a graphical presentation of the measurements of c-Jun NH 2 -terminal kinase (JNK) activity in the cortex of experimental animals treated as described in the experimental section below; FIG. 6 is a graphical presentation of the results of measurements of IL-1 Receptor Type 1 concentration in cortical tissue of test animals treated as described in the experimental section below.
THE PREFERRED EMBODIMENTS
[0041] In one of the preferred methods of this invention, a patient having a neurological disease condition with a significant inflammatory component mediated by reactive oxygen species, or at risk of developing such a brain disease condition, is first identified. Such patient may have a risk which is significantly greater than the risk in the average population, e.g. as a result of prior trauma, hereditary indication and the like. That patient is then evaluated to determine whether that disease condition or risk of disease condition can be effectively treated by reducing the concentration of reactive oxygen species. If in the opinion of the attending clinician, a reduction in the concentration of reactive oxygen species and associated reduction in neurological inflammation would be suitable for the prophylactic or therapeutic treatment of such a neurological disease, Immune modulation therapy is administered to said patient.
[0042] Accordingly, in one of its preferred aspects, this invention is directed to a method for the prophylactic or therapeutic treatment of the inflammation-associated aspects of a neurological disease having a significant inflammatory component and mediated at least in part by reactive oxygen species, which method comprises:
[0043] (a) identifying a patient having a neurological brain disease condition or at risk of developing a neurological brain disease condition having a significant inflammatory component and mediated by reactive oxygen species;
[0044] (b) evaluating the patient identified in (a) above to determine whether that disease condition or risk of disease condition can be effectively treated by reducing the concentration of reactive oxygen species; and
[0045] (c) if a reduction in the concentration of reactive oxygen species would be suitable for the prophylactic or therapeutic treatment of such a disease, then
[0046] (d) administering to said patient an aliquot of blood which has been treated ex vivo with at least two stressors selected from the group consisting of an oxidative environment, thermal stress and electromagnetic radiation,
[0047] wherein, following such administration, the neurological brain tissue inflammation and/or the concentration of the reactive oxygen species in the neurological brain tissue of said patient is reduced.
[0048] The patient is a mammal and preferably a human.
[0049] The aliquot of blood is treated by being subjected to stressors which have been found to modify the blood. According to the present invention, the blood aliquot can be modified by subjecting the blood, or separated cellular or non-cellular fractions of the blood, or mixtures of the separated cells and/or non-cellular fractions of the blood, to stressors selected from temperature stressors, electromagnetic emissions and oxidative environments, or any combination of such stressors, simultaneously or sequentially.
DETAILED DESCRIPTION OF THE INVENTION
[0050] The following terms are defined with respect to this invention:
[0051] “Therapeutic treatment” refers to the treatment of a disease wherein the treatment reduces or eliminates the symptoms of that disease.
[0052] “Prophylactic treatment” or “prophylaxis” refers to the prevention or hindrance of development of disease.
[0053] The terms “aliquot,” “aliquot of blood” or similar terms used herein include whole blood, separated cellular fractions of the blood including platelets, separated non-cellular fractions of the blood including plasma, and combinations thereof.
[0054] Methodology
[0055] The method of this invention provides for the prophylactic or therapeutic treatment of a neurological brain disease mediated by reactive oxygen species. In this method a patient is first identified as having such a disease condition or is at risk of having such a disease condition mediated by reactive oxygen species. The patient is then evaluated to determine whether that disease condition or risk of disease condition can be effectively treated by reducing the concentration of reactive oxygen species. Such evaluation is made by the attending clinician based upon the disease to be treated and the progression of the disease. Such factors are well within the skill of the art. If, in the opinion of the attending clinician, a reduction in the concentration of reactive oxygen species would be suitable for the prophylactic or therapeutic treatment of such a disease, then the patient is administered an aliquot of blood which has been treated ex vivo with at least two stressors selected from the group consisting of an oxidative environment, thermal stress and electromagnetic radiation. The ex vivo treatment of the aliquot of blood is described below. The method provides a reduced concentration of the reactive oxygen species in said patient.
[0056] In this preferred method, the patient is evaluated to determine whether the neurological brain disease condition or risk of neurological brain disease condition could be effectively treated by reducing the concentration of reactive oxygen species, e.g. whether its inflammation component associated with the presence of reactive oxygen species can be effectively reduced by reducing the concentration of reactive oxygen species. In this regard, the reduction of the reactive oxygen species is reduced in the patient at the time when a reduction of reactive oxygen species effectively treats (either prophylactically or therapeutically) the disease.
[0057] The concentration of reactive oxygen species may be measured by a variety of methods known in the art. For example, one can determine them from measurements of depletion of anti-oxidative enzymes (glutathione, catalase) in the patient's blood (see Layton et. al.). An alternative is to test the serum of a patient for oxidized low density lipoproteins, using anti-oLDL ELISA immunoassay (see Wilburgur et. al.). One can also measure lipid peroxidation products such as tiabarbituric acid and its derivatives in plasma, or measure arachidonic acid oxidation products in a patient's blood.
[0058] The treated blood is administered to the mammal by a method suitable for vaccination selected from the group consisting of intra-arterial injection, intramuscular injection, intravenous injection, subcutaneous injection, intraperitoneal injection, and oral, nasal or rectal administration. Intramuscular injection is preferred.
[0059] Ex vivo Treatment of Blood
[0060] According to a preferred process of the present invention, an aliquot of blood is extracted from a mammalian subject, preferably a human, and the aliquot of blood is treated ex vivo with certain stressors, described in more detail below. The effect of the stressors is to modify the blood, and/or the cellular or non-cellular fractions thereof, contained in the aliquot. The modified aliquot is then re-introduced into the subject's body by any route suitable for vaccination.
[0061] The stressors to which the aliquot of blood is subjected ex vivo according to the method of the present invention are selected from temperature stress (blood temperature above or below body temperature), an oxidative environment and an electromagnetic emission, individually or in any combination, simultaneously or sequentially. Suitably, in human subjects, the aliquot has a volume sufficient that, when re-introduced into the subject's body, at least partial alleviation of the reactive oxygen species mediated disorder is achieved in the subject.
[0062] Preferably, the volume of the aliquot is up to about 400 ml, preferably from about 0.1 to about 100 ml, more preferably from about 5 to about 15 ml, even more preferably from about 8 to about 12 ml, and most preferably about 10 ml, along with an anticoagulant, e.g., 2 ml sodium citrate.
[0063] It is preferred, according to the invention, to apply all three of the aforementioned stressors simultaneously to the aliquot under treatment, in order to ensure the appropriate modification to the blood. It may also be preferred in some embodiments of the invention to apply any two of the above stressors, for example to apply temperature stress and oxidative stress, temperature stress and an electromagnetic emission, or an electromagnetic emission and oxidative stress. Care must be taken to utilize an appropriate level of the stressors to thereby effectively modify the blood to alleviate the reactive oxygen species mediated disorder in the subject.
[0064] The temperature stressor warms the aliquot being treated to a temperature above normal body temperature or cools the aliquot below normal body temperature. The temperature is selected so that the temperature stressor does not cause excessive hemolysis in the blood contained in the aliquot and so that, when the treated aliquot is injected into a subject, alleviation of the reactive oxygen species mediated disorder will be achieved. Preferably, the temperature stressor is applied so that the temperature of all or a part of the aliquot is up to about 55° C., and more preferably in the range of from about −5° C. to about 55° C.
[0065] In some preferred embodiments of the invention, the temperature of the aliquot is raised above normal body temperature, such that the mean temperature of the aliquot does not exceed a temperature of about 55° C., more preferably from about 40° C. to about 50° C., even more preferably from about 40° C. to about 44° C., and most preferably about 42.5±1° C.
[0066] In other preferred embodiments, the aliquot is cooled below normal body temperature such that the mean temperature of the aliquot is within the range of from about −5° C. to about 36.5° C., more preferably from about 10° C. to about 30° C., and even more preferably from about 15° C. to about 25° C.
[0067] The oxidative environment stressor can be the application to the aliquot of solid, liquid or gaseous oxidizing agents. Preferably, it involves exposing the aliquot to a mixture of medical grade oxygen and ozone gas, most preferably by bubbling through the aliquot, at the aforementioned temperature range, a stream of medical grade oxygen gas having ozone as a minor component therein. The ozone content of the gas stream and the flow rate of the gas stream are preferably selected such that the amount of ozone introduced to the blood aliquot, either on its own or in combination with other stressors, does not give rise to excessive levels of cell damage such that the therapy is rendered ineffective.
[0068] Suitably, the gas stream has an ozone content of up to about 300 μg/ml, preferably up to about 100 μg/ml, more preferably about 30 μg/ml, even more preferably up to about 20 μg/ml particularly preferably from about 10 μg/ml to about 20 μg/ml, and most preferably about 14.5±1.0 μg/ml. The gas stream is suitably supplied to the aliquot at a rate of up to about 2.0 liters/min, preferably up to about 0.5 liters/min, more preferably up to about 0.4 liters/min, even more preferably up to about 0.33 liters/min, and most preferably about 0.24±0.024 liters/min, at STP. The lower limit of the flow rate of the gas stream is preferably not lower than 0.01 liters/min, more preferably not lower than 0.1 liters/min, and even more preferably not lower than 0.2 liters/min.
[0069] The electromagnetic emission stressor is suitably applied by irradiating the aliquot under treatment from a source of an electromagnetic emission while the aliquot is maintained at the aforementioned temperature and while the oxygen/ozone gaseous mixture is being bubbled through the aliquot. Preferred electromagnetic emissions are selected from photonic radiation, more preferably UV, visible and infrared light, and even more preferably UV light. The most preferred UV sources are UV lamps emitting primarily UV-C band wavelengths, i.e., at wavelengths shorter than about 280 nm. Such lamps may also emit amounts of visible and infrared light. Ultraviolet light corresponding to standard UV-A (wavelengths from about 315 to about 400 nm) and UV-B (wavelengths from about 280 to about 315) sources can also be used. For example, an appropriate dosage of such UV light, applied simultaneously with the aforementioned temperature and oxidative environment stressors, can be obtained from lamps with a combined power output of from about 15 to about 25 watts, arranged to surround the sample container holding the aliquot, each lamp providing an intensity at a distance of one meter, of from about 45-65 mW/cm 2 . Up to eight such lamps surrounding the sample bottle, with a combined output at 253.7 nm of 15-25 watts, operated at an intensity to deliver a total UV light energy at the surface of the blood of from about 0.025 to about 10 joules/cm 2 , preferably from about 0.1 to about 3.0 joules/cm 2 , may advantageously be used. Preferably, four such lamps are used.
[0070] The time for which the aliquot is subjected to the stressors is normally within the time range of up to about 60 minutes. The time depends to some extent upon the chosen intensity of the electromagnetic emission, the temperature, the concentration of the oxidizing agent and the rate at which it is supplied to the aliquot. Some experimentation to establish optimum times may be necessary on the part of the operator, once the other stressor levels have been set. Under most stressor conditions, preferred times will be in the approximate range of from about 2 to about 5 minutes, more preferably about 3 or about 3½ minutes. The starting blood temperature, and the rate at which it can be warmed or cooled to a predetermined temperature, tends to vary from subject to subject. Such a treatment provides a modified blood aliquot which is ready for injection into the subject.
[0071] In the practice of the preferred process of the present invention, the blood aliquot may be treated with the stressors using an apparatus of the type described in U.S. Pat. No. 4,968,483 to Mueller. The aliquot is placed in a suitable, sterile, UV light-transmissive container, which is fitted into the machine. The UV lamps re switched on for a fixed period before the gas flow is applied to the aliquot providing the oxidative stress, to allow the output of the UV lamps to stabilize. The UV lamps are typically switched on while the temperature of the aliquot is adjusted to the predetermined value, e.g., 42.5±1° C. Then the oxygen/ozone gas mixture, of known composition and controlled flow rate, is applied to the aliquot, for the predetermined duration of up to about 60 minutes, preferably 2 to 5 minutes and most preferably about 3 minutes as discussed above, so that the aliquot experiences all three stressors simultaneously. In this way, blood is appropriately modified according to the present invention to achieve the desired effects.
[0072] A subject preferably undergoes a course of treatments, such individual treatment comprising removal of a blood aliquot, treatment thereof as described above and re-administration of the treated aliquot to the subject. A course of such treatments may comprise daily administration of treated blood aliquots for a number of consecutive days, or may comprise a first course of daily treatments for a designated period of time, followed by an interval and then one or more additional courses of daily treatments.
[0073] In one preferred embodiment, the subject is given an initial course of treatments comprising the administration of 4 to 6 aliquots of treated blood. In another preferred embodiment, the subject is given an initial course of therapy comprising administration of from 2 to 4 aliquots of treated blood, with the administration of any pair of consecutive aliquots being either on consecutive days, or being separated by a rest period of from 1 to 21 days on which no aliquots are administered to the patient, the rest period separating one selected pair of consecutive aliquots being from about 3 to 15 days. In a more specific, preferred embodiment, the dosage regimen of the initial course of treatments comprises a total of three aliquots, with the first and second aliquots being administered on consecutive days and a rest period of 11 days being provided between the administration of the second and third aliquots.
[0074] It may be preferred to subsequently administer additional courses of treatments following the initial course of treatments. Preferably, subsequent courses of treatments are administered at least about three weeks after the end of the initial course of treatments. In one particularly preferred embodiment, the subject receives a second course of treatment comprising the administration of one aliquot of treated blood every 30 days following the end of the initial course of treatments, for a period of 6 months.
[0075] It will be appreciated that the spacing between successive courses of treatments should be such that the positive effects of the treatment of the invention are maintained, and may be determined on the basis of the observed response of individual subjects.
EXAMPLES
[0076] The invention is demonstrated and illustrated by the following animal experiments, conducted on Wistar rats, according to ethically-approved procedures and protocols.
[0077] The experiments investigated the effect of pre-treatment of peripheral blood exposed to immune modulation therapy on LPS-induced impairment of LTP in rat hippocampal tissue. Preliminary studies were also carried out in cortical tissue to explore the consequence of immune modulation therapy on the accumulation of ROS, the concentration of the cytokines TNFα and IL-10, as well as IL-1 receptor type I, and on the activity of the stress-activated protein kinase, JNK.
EXPERIMENTAL PROCEDURE
[0078] Animals
[0079] Four groups of eight male Wistar rats (300-350 g; BioResources Unit, Trinity College Dublin, Republic of Ireland) were used in these experiments. Animals were housed in groups of four under a 12-hour light schedule, ambient temperature was controlled between 22 and 23° C. and rats were maintained under veterinary supervision.
[0080] Treatment Protocol
[0081] Whole blood was obtained by cardiac puncture from donor rats and anticoagulated with sodium citrate (10 ml of blood+2 ml of 3.13% sodium citrate solution). The anticoagulated blood was divided into two aliquots; 2 ml to be used for sham treatment and 10 ml to undergo immune modulation treatment. For immune modulation treatment, 10 ml of anticoagulated blood was transferred to a custom-built sterile, low-density polyethylene disposable blood container (Vasogen Inc, Toronto, ON, Canada) and exposed to a combination of controlled physiochemical stress factors in a medical device (Vasogen Inc).
[0082] During processing, the temperature of the blood was raised to 42.5° C., during which time blood was exposed to UV light (maximum emission spectrum at 254 nm). When this temperature was reached, a gas mixture of 14.5±1.0 μg/mL of ozone in medical oxygen was bubbled through the blood at a flow rate of 240±24 mL per min for 3 minutes, after which time the heat and UVC light sources were turned off. The foaming action caused by bubbling the gas through the blood increased the surface area exposed to the UVC light. The blood was then allowed to settle to the bottom of the blood container and was then ready to be used. Two groups of 16 rats were treated by intramuscular injection with 150 μL of processed blood or untreated blood (sham treatment). Injections were administered 14 days, 13 days and 1 day before LPS challenge/induction of LTP.
[0083] Induction of LTP in Perforant Path-Granule Cell Synapses in vivo
[0084] Rats were anesthetized by intraperitoneal injection of urethane (1.5 g/kg). All rats received LPS (100 μg/kg) or saline, intraperitoneally and monitored for 3 h. A bipolar stimulating electrode and a unipolar recording electrode were placed in the perforant path (4.4 mm lateral to Lambda) and in the dorsal cell body region of the dentate gyrus (2.5 mm lateral and 3.9 mm posterior to Bregma), respectively, and 0.033-Hz test shocks were given for 10 min before, and 40 min after, titanic stimulation (three trains of stimuli delivered at 30-s intervals, 250 Hz for 200 ms (McGahon & Lynch, 1996)). Rats were killed by decapitation; cross-chopped slices (350×350 μm) were prepared from dentate gyri, entorhinal cortex, hippocampus and cortex and used to prepare dissociated cells (see below) or frozen separately in Krebs solution containing 10% dimethyl sulfoxide (Haan & Bowen, 1981) and stored at −80° C. For analysis, slices were thawed rapidly and rinsed in fresh oxygenated Krebs solution before preparation of homogenate or the crude synaptosomal pellet P 2 (McGahon & Lynch, 1996).
[0085] Analysis of Reactive Oxygen Species Formation
[0086] The formation of reactive oxygen species was assessed by analyzing formation of the highly-fluorescent 2′,7-dichlorofluorescein (DCF) from the non-fluorescent probe, 2′,7-dichlorofluorescein diacetate (DCFH-DA; Molecular Probes, USA; LeBel et al., 1992). The synaptosomal pellet, P 2 , prepared from cortex, was resuspended in 1 mL ice-cold 40 mM Tris buffer (pH 7.4), incubated at 37° C. for 15 min with DCFH-DA (10 μL; final concentration 5 μM; from a stock solution of 500 μM in methanol) and the reaction was terminated by centrifugation at 13,000×g for 8 min at 4° C. Pellets were resuspended in 1.5 mL of ice-cold 40 mM Tris buffer, pH 7.4, and monitored for fluorescence at 37° C. (excitation, 488 nm; emission, 525 nm). Reactive oxygen species formation was quantified from a standard curve of DCF in methanol (range 0 to 5 μM). Protein concentration was determined (Bradford, 1976) and the results were expressed as nmol/mg protein/min.
[0087] Analysis of TNFα and IL-10 Concentration
[0088] A commercially available Enzyme-linked immunosorbent assay was used to analyze cortical TNFα (Biosource International Inc.) and cortical IL-10 was measured using an IL-10 Cytoset Antibody Pair (Biosource International Inc.). Each tissue was added to 1 mL of Iscove's culture medium containing 5% fetal bovine serum and a cocktail enzyme inhibitor (100 mM amino-n-caproic acid, 10 mM Na 2 EDTA, 5 mM Benzamidine HCl, 0.2 mM phenylmethylsulfonyl fluoride). Tissue was homogenized and centrifuged at 10,000 rpm at 4° C. for 10 min. Supernatants were removed and analyzed for TNFα using ELISA. Protein concentration was determined (Bradford, 1976) and the results were expressed as pg/mg protein.
[0089] Analysis of JNK Activity and IL-1 Receptor Type I Concentration
[0090] JNK activity and IL-1 Receptor Type I concentration was analyzed using Western Blotting technique in samples prepared from cortical tissue. Tissue homogenates were diluted to equalize for protein concentration (Bradford, 1976) and 10 μL aliquots (1 mg/mL) were added to 5 μL of sample buffer (0.5 mM Tris-HCl, pH 6.8, 10% glycerol, 10% SDS, 5% b-mercaptoethanol, 0.05% bromophenol blue, w/v) and boiled for 5 min. Samples were frozen until Western Blotting was performed. 10 μL of each sample was loaded onto gels (10% SDS) for each analysis. Proteins were separated by application of a 32-mA constant current for 25-30 min, transferred onto nitrocellulose strips (225 mA for 75 min), and immunoblotted with the appropriate antibody. To assess JNK activity, proteins were immunoblotted with an antibody that specifically targets phosphorylated JNK (Santa Cruz Biotechnology, Inc; 1:100 in TBS and 0.1% Tween 20 containing 1% BSA) for 2 h at room temperature.
[0091] IL-1 Receptor Type I concentration was assessed by immunoblotting proteins with a rabbit polyclonal antibody raised against an epitope mapping at the carboxy terminus of IL-1RI of mouse origin (Santa Cruz Biotechnology, Inc.; 1:2000 in PBS and 0.1% Tween 20 containing 2% non-fat dried milk) for 45 min at room temperature and 45 min at 37° C. Nitrocellulose strips were washed and incubated with secondary antibody [peroxide-linked anti-mouse IgG; 1:300 dilution (Sigma) for 2 h at room temperature in the case of JNK and with HRP-linked anti-rabbit antibody; 1:2000 dilution (Amersham, UK) for 60 min at room temperature and 30 min at 37° C. in the case of IL-1 Receptor Type I. Visualization of phosphorylated JNK was achieved using SuperSignal West Dura Extended Duration Substrate (Pierce, USA). Immunoblots were immersed in substrate for 5 min and subsequently exposed to film for 1 s. Protein complexes of IL-1 Receptor Type I were visualized by ECL detection (Amersham, UK) and immunoblots were exposed to film overnight at 4° C. In both cases films were processed using a Fuji x-ray processor. Quantification of protein bands was achieved by densitometric analysis using two software packages, Grab It (Grab It Annotating Grabber, version 2.04.7, Synotics; UVP Ltd) and Gelworks (Gelworks ID, version 2.51; UVP Ltd) for photography and densitometry, respectively. Gelworks provides a single value (in arbitrary units) representing the density of each blot.
[0092] Analysis of Glutamate Release
[0093] Glutamate release was assessed in the impure synaptosomal preparation, P 2 , obtained from dentate gyrus; either freshly-prepared tissue was used or alternatively, P 2 was prepared from frozen slices of dentate gyri which were obtained from rats in which electrophysiological recordings were made (McGahon and Lynch, 1996). In both cases, P 2 preparations were resuspended in oxygenenated Krebs solution containing 2 mM CaCl 2 and glutamate release was assessed as described previously (McGahon et al., 1996). Briefly, synaptosomal tissue was aliquotted onto Millipore filters (o45 μm), rinsed under vacuum and the filtrate was discarded. Synaptosomes were then incubated in 250 μl oxygenated Krebs solution at 37° C. for 3 min, in the presence or absence of 40 mM KCl, and filtrate was collected and stored for analysis as described (Ordronneau et al., 1991). in some experiments, synatosomes were incubated at 37° C. for 20 min in Krebs solution containing IL-1β (1 ng/ml) in the presence or absence of Vasoactive Intestinal Peptide (VIP; 1 μM). Triplicate samples (50 μl) or glutamate standards (50 μl; 25 nM to 1 μM prepared in 100 mM NaH 2 PO 4 buffer, pH 8.0) were added to glutaraldehyde-coated 96-well plates, incubated for 60 min at 37° C., and washed with 100 mM NaH 2 PO 4 buffer. Ethanolamine (250 μl; 0.1 M in 100 mM NaH 2 PO 4 4 buffer) was used to bind unreacted aldehydes and donkey serum (200 μl; 3 % in PBS-T) was added to block non-specific binding. Samples were incubated overnight at 4° C. in the presence of antiglutamate antibody (raised in rabbit; 100 μl; 1:5,000 in PBS-T; Sigma, UK), washed and reacted with secondary antibody (anti-rabbit horseradish peroxidase (HRP)-linked secondary antibody; 100 μl; 1:10,000 in PBS-T; Amersham, UK) for 60 min at room temperature. 3.3′, 4.4′-Tetramethylbenzidine liquid substrate was added as chromogen and incubation continued for exactly 60 min at room temperature, at which time the reaction was stopped by H 2 SO 4 (4 M; 30 μl). Optical densities were determined at 450 mm using a multiwell plate reader and values were calculated with reference to the standard curve, corrected for protein (Bradford, 1976) and expressed as μmol glutamate/mg protein.
[0094] Analysis of IL-1β Concentration
[0095] IL-β concentration in hippocampal was analysed by ELISA (R & D Systems, UK). Antibody-coated (100 μl; 1.0 μg/ml final concentration, diluted in phosphate buffered saline (PBS), pH 7.3; goat anti-rat IL-1βantibody) 96=well plates were incubated overnight at room temperature, washed several times with PBS containing 0.05% Tween 20, blocked for 1 hour at room temperature with 300 μl blocking buffer, (PBS, pH 7.3 containing 5% sucrose, 1% bovine serum albumin (BSA), and 0.05% NaN 3 ). After several washes, plates were incubated with IL-1β standards (100 μl; 0-1000 pg/ml in PBS containing 1% BSA) or samples (homogenized in Krebs solution containing 2 mM CaCl 2 ) for 2 hours at room temperature. Samples were incubated with secondary antibody (100 μl; final concentration 350 ng/ml in PBS containing 1% BSA and 2% normal goat serum; biotinylated goat anti-rat IL-1β antibody) for 2 hours at room temperature, washed and incubated in detection agent (100 μl; horseradish peroxidase conjugated streptavidin; 1:200 dilution in PBS containing 1% BSA) for 20 min at room temperature. Substrate solution (100 μl; 1:1 mixture of H 2 O 2 and tetramethylbenzidine) was added, samples were incubated at room temperature in the dark for 1 hour after which time the reaction was stopped using 50 μl 1 M H 2 SO 4 . Absorbance was read at 450 nm, values were corrected for protein (Bradford, 1976) and expressed as pg IL-1β/mg protein.
[0096] TUNEL Staining
[0097] Dissociated cells were prepared by enzymatic and mechanical digestion of fresh hippocampal slices. Slices were incubated with collagenase (0.125%) in PBS for 30 min at room temperature, washed with PBS to terminate collagenase digestion, and then gently triturated with a glass Pasteur pipette, before passing through a nylon mesh filter to remove tissue clumps. Cells were than cytospun onto glass microscope slides, fixed with methanol and stored until use.
[0098] TUNEL (Terminal deoxynucleotidyl Transferase (TdT)-mediated dUTP Nick-End Labeling) staining, which identifies nuclei with fragmented DNA (a characteristic of apoptotic cells), was performed according to the manufacturer's instructions. Briefly, fixed cytospun cells were washed and permeabilized. Cells were equilibrated in buffer (200 mM potassium cacodylate (pH 6.6 at 25° C.), 25 mM Tris-HCl (pH 5.5 at 25° C.), 0.2 mM DTT, 0.25 mg/ml BSA, 2.5 mM CoCl 2 ) for 5 min at room temperature and incubated in TdT reaction mixture (30 μl; 98 μl equilibration buffer, 1 μl biotinylated nucleotide mix, 1 μl TdT enzyme) at 37° C. for 1 hour. The reaction was terminated by adding 100 μl 2×SCC (1:10; 2×SCC:deionized water), endogenous peroxidases were blocked by incubating with H 2 O 2 (100 μl; 0.3% in PBS) for 5 min at room temperature, and washed cells were incubated for 30 min at room temperature in streptavidin HRP solution (100 μl; 1:500 in PBS) to allow binding to biotinylated nucleotides. Diaminobenzidine solution was added to washed cells, and the incubation proceeded fo 10 min at room temperature. Cells were washed with deionised water, dehydrated through graded ethanol, and then cleared with xylene after which slides were mounted in DPX mounting medium and coverslipped. TUNEL positive cells were expressed as a percentage of the total.
[0099] Statistical Analysis
[0100] Data were analyzed, as appropriate, using either the Student's t-test for independent means, or by using a one-way analysis of variance (ANOVA) followed by post hoc analysis using the Student Newman Keuls test.
RESULTS
[0101] A: Hippocampus
[0102] Mean body weight, dose of urethane administered to induce anaesthesia, and stimulus strength required to induce an epsp spike were calculated. There was no significant difference between groups in body weight (FIG. 1A) or urethane concentration (FIG. 1B) administered due to immune modulation therapy.
[0103] [0103]FIG. 1 demonstrates that immune modulation therapy does not significantly alter body weight (a) or dose of urethane administered to induce anaesthesia (b). There is however an increase in the amplitude required to induce an action potential (c). The data are expressed as means with standard errors.
[0104] Tetanic stimulation delivered to the perforant path 3 h after intraperitoneal injection of LPS resulted in an increase in the mean slope of the population excitatory post-synaptic potential (epsp). The mean percentage change in the 2 min immediately following tetanic stimulation (±SEM; compared with the 5 min immediately before tetanic stimulation) was 114.49 (±2.79), but this was not maintained so that the mean percentage change in population epsp slope in the last 5 min of the experiment was 90.32 (±2.42). The corresponding values in the saline-treated control rats were 170.15 (±10.16) and 121.28 (±1.20), respectively (FIG. 2). The LPS induced inhibition of LTP was blocked by pre-treatment with immune modulation therapy.
[0105] [0105]FIG. 2 demonstrates that the LPS-induced impairment of LTP, was inhibited by pre-treatment with immune modulation therapy. The mean population epsp slope immediately after tetanic stimulation was attenuated in LPS-treated rats compared with saline-treated rats and was close to baseline at the end of the 40 min post-tetanus recording period. The inhibitory effect of LPS on LTP was blocked by pre-treatment with immune modulation therapy, which exerted no significant effect in saline-challenged rats. The data presented are means of seven to eight observations in each treatment group.
[0106] The mean percentage change in population epsp slope (±SEM) in the 2 min immediately after tetanic stimulation was 166.85 (±4.54) in the sham pretreated, saline challenged group compared with 147.44 (±5.84) in the group pretreated with immune modulation therapy and challenged with LPS. In the last 5 min of the experiment the values were 121.96 (±0.85) and 128.07 (±1.46), respectively (n=7-8).
[0107] Dissocated cells prepared form fresh hippocampal tissue displayed an increased number of apoptotic cells after LPS injection as evidenced by increased number of cells displaying dark brown stained nuclei i.e. TUNEL positive cells. This contrasts with cells prepared from hippocampus of saline-treated rats and rats treated with immune modulation therapy. Treatment with immune modulation therapy reversed the effects of LPS as shown by a reduction in the number of cells displaying TUNEL positive staining. The precentage of TUNEL positive cells was significantly increased in the LPS-treated group compared with the control treated group (p<0.01; ANOVA) and demonstrates that the immune modulation therapy reversed the degenerative effect of LPS (p<0.01; ANOVA).
[0108] B: Cortex
[0109] Animals were administered either immune modulation therapy or sham treatments, as previously described, and the following measurements were made in the cortex: ROS accumulation, TNF-α and IL-10 levels. These experiments were performed without LPS stimulation of the animals.
[0110] [0110]FIG. 3 indicates that immune modulation therapy significantly reduces reactive oxygen species accumulation in the cortex (p<0.05; student's t-test for independent means, n=7-8). The data are expressed as means with standard errors.
[0111] The concentration of pro-inflammatory cytokine, TNFα is significantly reduced in the cortex as a result of immune modulation therapy (p<0.01; student's t-test for independent means, FIG. 4 a ). In contrast, IL-10 concentration is significantly increased (p<0.01; student's t-test for independent means) (FIG. 4 b ). FIGS. 4 a and 4 b show that immune modulation therapy significantly reduces TNFα concentration (a) and significantly increases IL-10 concentration (b) in the cortex (p<0.01; student's t-test for independent means; n=7-8). The data are expressed as means with standard errors.
[0112] [0112]FIG. 5 illustrates that immune modulation therapy decreased JNK activity as indicated by a decrease in the phosphorylated form of JNK. Analysis of the mean data obtained from densitometric analysis indicated that VasoCare™ therapy significantly reduced kinase activity (p<0.05; student's t-test for independent means). FIG. 5 shows that immune modulation therapy significantly reduces JNK activity in the cortex (p<0.05; student's t-test for independent means; n=7-8). The data are expressed as means with standard errors.
[0113] With respect to the concentration of IL-1 Receptor Type I in cortical tissue, pilot work indicates that immune modulation therapy reduces IL-1 Receptor Type I expression (FIG. 6). The concentration of ligand pro-inflammatory IL-1β itself is expected to be lower, and is under examination. FIG. 6 shows that immune modulation therapy reduces the concentration of IL-1 Receptor Type I (preliminary data; n=3). The data are expressed as means with standard errors.
[0114] Analysis of endogenous glutamate release in synatosomes prepared from tetanized and untetanized tissue obtained from these rats revealed a significant effect of LPS injection. Addition of 40 mM KCl to synaptosomes prepared from untetanized dentate gyrus obtained from saline-treated control rats, significantly increased glutamate release (p<0.05; Student t-test for paired means) albeit to an attenuated degree. This immune modulation therapy reversed the LPS-induced blockage of KCl stimulated glutamate release in untetanized dentate gyrus and to a more significant degree in tetanized tissue (p<0.01; Student t-test for paired means). This immune modulation therapy may exert its protective effect on syncystic function by acting to prevent this LPS-induced signaling event.
BIBLIOGRAPHY
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[0137] Wildburger R, Borovic S, Zarkovic N, and Tatzber F. Post-traumatic dynamic changes in the antibody titer against oxidized low density lipoproteins. Wien Klin Wochenshr Sep. 29, 2000; 112(18) 798-803. | Disclosed are methods for treating and preventing neurological disorders which have a significant inflammatory component. The methods of the present invention involve extracting blood from a patient, subjecting the blood ex vivo to at least one stressor selected from the group consisting of an oxidative environment, thermal stress and UV light, and then re-administering the blood to the patient, thereby reducing inflammation. | 0 |
[0001] The present application is a continuation of International Application PCT/SE2004/000154 filed Feb. 6, 2004, which claims priority to Swedish Application No. 0300497-5, filed Feb. 25, 2003, both of which are hereby incorporated by reference.
[0002] The present invention relates to a motor vehicle transmission, comprising an input shaft intended for drivable coupling to a motor, a first intermediate shaft having a first primary gearwheel mounted rotatably on the shaft, a second intermediate shaft having a second primary gearwheel mounted rotatably on the shaft, first and second clutch members coordinated with the first and second primary gearwheel respectively and enabling the primary gearwheels to be locked alternately onto an associated shaft so as to transmit torque from the input shaft to the respective intermediate shaft, a main shaft, and gearwheels supported by the intermediate shafts and the main shaft, which gearwheels engage with one another in pairs so as to transmit torque from one or other intermediate shaft to the main shaft and whereof at least one gearwheel in each pair is a disengageable running wheel.
[0003] Dual intermediate shafts are used, on the one hand, in transmissions in which, for a given transmission length, there is a wish to obtain more gears than is practically possible in a conventional transmission construction having a single intermediate shaft and, on the other hand, in so-called “powershift” transmissions, i.e. transmissions having dual input shafts, which are driven by their respective clutch and drive their respective intermediate shaft. In such transmissions the gear positions are preselected, according to which the actual gearshift is effected by the disengagement of one clutch and engagement of the other clutch. The gearshift can here be performed, without interruption of torque, by the gradual engagement of one clutch simultaneous with the gradual disengagement of the other clutch. In a six-speed transmission, for example, the first, third and fifth gears can be obtained through one input shaft and one intermediate shaft, whilst the second, fourth and sixth gears are obtained through the other input shaft and the other intermediate shaft.
[0004] In order to obtain one or more reverse gears, two fundamentally different solutions are known. In one solution, an intermediate gearwheel on a separate reverse shaft is used to transmit torque from one intermediate shaft to the main shaft/output shaft so as to reverse the rotational direction of the shaft. In the other solution, torque is transmitted from one intermediate shaft to the other intermediate shaft and from there to the main shaft. In this case, therefore, the said other intermediate shaft is used as the reverse shaft, thereby eliminating the need for a separate reverse shaft. Examples of the latter solution are illustrated and described in SE-A-506 223. This transmission is a “powershift” transmission having dual concentric input shafts driven by the respective output shaft of a motor-driven clutch. Even forward gear steps are engaged through the one clutch and odd forward gear steps through the other clutch. Powershift transmissions of the type described above are used, for example, in heavy trucks.
[0005] It is desirable to produce a transmission of the type stated in the introduction, which is especially suitable for use in working machines, such as, for example, dumpers and loaders, which require just as many reverse gears as forward gears, often change the direction of travel between forward and reverse and in which the torque requirement is often altered directly after reversal of the direction of travel.
[0006] According to an aspect of the invention, a first drive gearwheel, upon engagement of a first clutch device, is arranged to transmit torque from the input shaft to both the primary gearwheels simultaneously for driving of the primary gearwheels in a first direction, and a second drive gearwheel, upon disengagement of the first clutch device and engagement of a second clutch device, is arranged to transmit torque from the input shaft to both the primary gearwheels simultaneously for driving of the primary gearwheels in a direction opposite to the said first direction.
[0007] By, according to an aspect of the invention, coordinating the clutches for the alternate driving of the intermediate shafts directly with the respective intermediate shaft and coordinating a clutch for reversal of the rotation of the intermediate shafts with the input shaft, a transmission can be produced having just as many reverse gears as forward gears, in which the gearshift between different reverse gears, like the gearshift between forward and reverse, can be executed without interruption of torque. The realization according to an aspect of the invention makes it possible, by means of a single intermediate gear between a gearwheel on the input shaft and one primary gearwheel, easily to achieve a gear differential between the various forward and reverse gears, so that, for example, higher torque and lower speed are obtained in a certain forward gear than in a corresponding reverse gear, which is especially advantageous as regards loaders, which are often driven faster backwards following acceptance of a load.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The invention is described in greater detail with reference to illustrative embodiments shown in the appended drawings, in which:
[0009] FIG. 1 shows a diagrammatic representation of an embodiment of a transmission according to the invention especially intended for a loader; and
[0010] FIG. 2 shows a corresponding representation of an embodiment of a transmission especially intended for a dumper.
DETAILED DESCRIPTION
[0011] The transmission shown in FIG. 1 has a casing 1 , containing a rotatably mounted input shaft 2 , which, in a manner which is known per se, is coupled in a drivable manner to a conventional torque converter 3 .
[0012] Mounted rotatably on the input shaft 2 are a first drive gearwheel 4 and a second drive gearwheel 5 , which can be locked onto and disconnected from the shaft 1 by means of first and second friction clutches 6 and 7 respectively, preferably wet-plate multi-disk clutches.
[0013] Also mounted rotatably in the casing 1 are a first intermediate shaft 8 , a second intermediate shaft 9 and a main shaft 10 .
[0014] Mounted rotatably on the first intermediate shaft 8 are three running gearwheels 11 , 12 and 13 . The gearwheel 11 can be locked onto and disconnected from its shaft 8 by means of a clutch sleeve 14 mounted displaceably but non-rotatably on the shaft and having synchronizing devices (not shown) which are known per se. The gearwheels 12 and 13 can be locked onto and disconnected from the shaft 8 by means of a clutch sleeve 15 having corresponding synchronizing devices (not shown).
[0015] Mounted rotatably on the second intermediate shaft 9 are three running gearwheels 16 , 17 and 18 . The gearwheel 16 can be locked onto and disconnected from its shaft 9 by means of a clutch sleeve 19 mounted displaceably but non-rotatably on the shaft and having synchronizing devices (not shown) which are known per se. The gearwheels 17 and 18 can be locked onto and disconnected from the shaft 9 by means of a clutch sleeve 20 having corresponding synchronizing devices (not shown).
[0016] Also mounted rotatably on the respective intermediate shaft 8 and 9 are primary gearwheels 24 and 25 , which, by means of their respective multi-disk plate clutch 26 and 27 , are lockable on their respective shaft. The primary gearwheels 24 and 25 engage, on the one hand, directly with the drive gearwheel 4 and, on the other hand, with an intermediate gearwheel 28 , which is disposed in a rotationally secure manner on a third intermediate shaft 29 mounted rotatably in the casing 1 , which intermediate shaft also has a further gearwheel 30 , which is disposed in a rotationally secure manner on the shaft 29 and engages with the drive gearwheel 5 . The engagement between the drive gearwheels 4 and 5 and the primary gearwheels 24 and 25 , respectively, is illustrated by arrows in the figures.
[0017] Upon the engagement of the clutch 6 , the input shaft 2 , via the drive gearwheel 4 , directly drives the two primary gearwheels 24 and 25 in a first rotational direction and with a first gear ratio between the input shaft 2 and the primary gearwheels 24 and 25 . Upon disengagement of the clutch 6 and engagement of the clutch 7 , the input shaft 2 drives, via the gearwheel 30 , the third intermediate shaft 29 and, [via] the intermediate gearwheel 28 , the two primary gearwheels 24 and 25 in a direction opposite to the first rotational direction and with a second gear ratio higher than the first gear ratio, since, as is evident from the figures, the intermediate gearwheel 28 is smaller than the drive gearwheel 4 .
[0018] The gearwheels 11 , 12 and 13 on the intermediate shaft 8 and the gearwheels 16 , 17 and 18 on the intermediate shaft 9 engage in the said order with gearwheels 21 , 22 and 23 disposed in a rotationally secure manner on the main shaft 10 . As a result of the described arrangement, a transmission is obtained which offers first, third and fifth gear via the intermediate shaft 8 and second, fourth and sixth gear via the intermediate shaft 9 , as marked in FIG. 1 .
[0019] Necessary speed difference between first and second, third and fourth and fifth and sixth gears for a given rotation speed of the input shaft 2 is obtained by the primary gearwheels 24 and 25 of the intermediate shafts 8 and 9 having different diameters, with the result that the intermediate shafts are driven at different rotation speeds. As regards the gear differential between the respective drive gearwheel 4 and 5 and the associated primary gearwheel 24 and 25 , in loaders the higher gearing, which gives lower speed and higher drive force for a given rotation speed of the input shaft 2 than the lower gearing, is preferably used for the forward gears, and hence the lower gearing for the reverse gears, since loading normally gives rise to greater resistance to the motion of the loader than does mere driving with raised load. Consequently, the clutch 7 is engaged and the clutch 6 disengaged in forward travel and, conversely, the clutch 7 disengaged and the clutch 6 engaged in reversing.
[0020] The gearshift between forward and reverse can be realized without interruption of torque and using the torque converter 3 , which is braked by gradual engagement of the clutch 6 before the clutch 7 is fully disengaged. When changing between the various gear steps during driving, it is the case both in reversing and in forward travel that the primary shaft clutch 26 or 27 of the, momentarily, driving primary gearwheel 24 or 25 is gradually disengaged, at the same time as the clutch 27 or 26 of the, momentarily, non-driving primary gearwheel 25 or 24 is gradually engaged, thereby achieving a soft gearshift without interruption of torque.
[0021] The transmission which is described above and illustrated in FIG. 1 , especially intended for a loader, has on its main shaft 10 a rotationally secure gearwheel 31 , which engages with a gearwheel 32 on an output shaft 33 , in which output torques to front and rear driving wheels of the vehicle are marked by arrows.
[0022] FIG. 2 shows an embodiment of a transmission according to the invention especially intended for a so-called dumper. Parts with correspondence in the realization in FIG. 1 have been given the same reference notations as in FIG. 1 . The transmission in FIG. 2 differs from the one described above only in that it has two additional gear steps seven and eight, which are obtained by a further gearwheel 40 , 41 and 42 on the respective intermediate shaft 8 and 9 and the main shaft 10 , respectively. The clutches 14 and 19 are here twin clutches for the engagement of first, second, third and fourth gears. Here the main shaft 10 is also the output shaft to a driving pair of wheels of the vehicle.
[0023] The transmission casing 1 is indicated in the figures by dashed lines. As can be seen from FIG. 1 , the casing is here divided into a module Ia, which encloses the torque converter 3 and the input shaft 2 with associated drive gearwheels 4 , 5 , clutches 26 , 27 , and intermediate shaft 29 with associated gearwheels 28 and 30 . The embodiment in FIG. 2 has a separate module Ic solely for the torque converter 3 , whilst all other components of the transmission are accommodated in a module Id.
[0024] The modular construction made possible by the realization described above offers simple adaptation to different installations and different power and torque requirements.
[0025] In the present application, the use of terms such as “including” is open-ended and is intended to have the same meaning as terms such as “comprising” and not preclude the presence of other structure, material, or acts. Similarly, though the use of terms such as “can” or “may” is intended to be open-ended and to reflect that structure, material, or acts are not necessary, the failure to use such terms is not intended to reflect that structure, material, or acts are essential. To the extent that structure, material, or acts are presently considered to be essential, they are identified as such.
[0026] While this invention has been illustrated and described in accordance with a preferred embodiment, it is recognized that variations and changes may be made therein without departing from the invention as set forth in the claims. | A motor vehicle transmission having two intermediate shafts, which can alternately be driven via disengageable primary gearwheels, and drive a main shaft, via gearwheels on the respective main shaft and intermediate shaft, which gearwheels engage with one another in pairs. Mounted on an input shaft are two lockable and disconnectable drive gearwheels, one of which directly drives the primary gearwheels in a first rotational direction, whilst the other of which, via an intermediate gearwheel, drives the primary gearwheels in an opposite direction. The realization produces a transmission having an equal number of forward and reverse gears, which can be shifted without interruption of torque. | 8 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a division of our co-pending application, entitled MOVEABLE SHELF AND PARTITIONING SYSTEM, Ser. No. 10/248,686, filed Feb. 9, 2003 and assigned to the assignee hereof.
DETAILED DESCRIPTION
[0002] This invention relates to a moveable shelf and support therefore that offers greater flexibility and versatility than those presently in use.
[0003] There are known storage systems that include one or more moveable shelves that are supported for movement along a work area on tracks or guide rails that are affixed to the floor of the area. When there are a plurality of these shelves, they can be compressed in abutting relationship to open up space and then moved to offer access to the individual shelf areas for the insertion and removable of articles therefrom. These types of devices have wide application and considerable utility.
[0004] However, the requirement for having rails or tracks in the floor by which the shelves can be moved means that the area must be specially adapted to utilize this type of system. Also, once converted to this arrangement, the utility of the area is somewhat compromised.
[0005] In addition, once in position the types of moveable shelves aforedescribed are not easily moved to another location. If they are to be moved, then that location must also be modified to provide the necessary guide rails on which the shelves can be mounted.
[0006] It is, therefore, a principal object to this invention to provide an improved moveable shelf arrangement that does not require guide rails for its operation.
[0007] It is a further object to this invention to provide a moveable shelf that can be supported on any type of floor and can be freely moved from position to position to optimize space utilization.
[0008] It is a still further object of the invention to provide an improved moveable base system for such shelves that will offer a predictable movement along a floor of any conventional type including carpeted ones that will insure parallel movement of the individual shelves.
SUMMARY OF THE INVENTION
[0009] A first feature of the invention is adapted to be embodied in a storage arrangement comprising a shelf adapted to receive articles. The shelf has a base and a drive unit disposed beneath the base and adapted to support the shelf on a floor for movement there along. Each drive unit is comprised of pairs of transversely spaced wheels supported for rotation upon the base about parallel, spaced axes. Each drive unit includes a support belt trained around the wheels and having a lower flight for engaging the floor and supporting the shelf thereupon. At least drive unit further includes a drive for rotating at least one of the wheels for driving the belt and effecting movement of the shelf along the floor.
BRIEF DESCRIPTION OF DRAWINGS
[0010] FIG. 1 is a side elevational view of a moveable partitioning and shelving system constructed in accordance with a first embodiment of the invention.
[0011] FIGS. 2, 3 and 4 are bottom views of the supporting frame for the shelf shown in FIG. 1 looking at the left-hand edge, the center and the right-hand edge, respectively.
[0012] FIGS. 5, 6 and 7 are side elevational views of the frame supporting portion showing the same areas illustrated in FIGS. 2, 3 and 4 , respectively.
[0013] FIG. 8 is a top plan view showing two pairs of drive belts.
[0014] FIG. 9 is a side elevational view of the drive belts.
[0015] FIG. 10 is a view, in part similar to FIG. 9 , but only shows one drive belt and in another type of arrangement therefore.
[0016] FIG. 11 is a cross sectional view taken along the line 11 - 11 of FIG. 10 .
[0017] FIG. 12 is a view, in part similar to FIG. 9 , and shows another embodiment of the invention and illustrates the arrangement supported on the floor.
[0018] FIG. 13 is a graphical view showing how the driving load depends upon the width of the drive belt.
[0019] FIG. 14 is an enlarged view, in part similar to FIG. 10 , and shows how the drive belt supports the shelving and acts as a cushion between the driving wheels and the floor.
[0020] FIG. 15 is a view, in part similar to FIG. 3 , but shows another embodiment of the invention.
[0021] FIG. 16 is a view looking in the direction of the arrow 16 in FIG. 15 .
[0022] FIG. 17 is a view looking the direction of the arrow 17 in FIG. 15 and is in part similar to FIG. 6 .
DETAILED DESCRIPTION
[0023] Referring now in detail to the drawings and initially to the embodiment of FIGS. 1 through 9 and beginning by specific reference to FIG. 1 , a moveable shelf constructed in accordance with this embodiment of the invention is identified generally by the reference numeral 31 . The moveable shelf 31 is adapted to be supported for movement along a floor 32 of any common type in a manner to be described.
[0024] The shelf 31 includes an upper shelf assembly 33 that is mounted on a base, indicated generally by the reference numeral 34 . The shelf assembly 33 can be of any material and construction and, for example, can include adjustable shelves that are held by side pieces. Since those skilled in the art will readily understand the various forms that the shelving may take, further description of that is believed to be unnecessary.
[0025] The base 34 has a construction as best shown and as will be described later by reference to FIGS. 2 through 7 . However, it includes driving wheels 35 and driven wheels 36 that are interconnect by an endless belt 37 which provides the direct support for the shelf 31 on the floor 32 .
[0026] Referring now primarily to FIGS. 2 through 6 , the base 34 is comprised of a sheet metal assembly comprised of a planar type upper surface 38 and a pair of folded down side surfaces. Reinforcing U-channels 39 may be affixed at spaced locations along the horizontal surface 38 to add rigidity to the construction. A driving shaft 41 and driven shaft 42 are journaled in spaced transverse relationship by means of a plurality of pillow blocks 43 that are affixed to and form a part of the base 34 . Specifically, these pillow blocks 43 are fixed to the under side of the panel surface 38 . Bearings 44 carried by these pillow blocks 43 complete the journaling of the shafts 41 and 42 in the base 34 .
[0027] The driving wheels 35 are affixed at spaced locations and between pairs of the pillow blocks 43 and bearings 44 to the driving shaft 41 . In a like manner, the driven wheels 36 are affixed to the driven shaft 42 . In order to facilitate assembly and machining, the shafts 41 and 42 need not be continuous shafts but can constitute shaft segments that are joined together by couplings 45 .
[0028] The drive belts 37 may be of the toothed type and can cooperate with sprocket teeth on the driving wheels 35 and driven wheels 36 . In addition and if desired, a plurality of sprockets 46 may be fixed along the lengths of the shafts 41 and 42 and interconnected by a chain (not shown).
[0029] The driving shaft 41 is driven by one or more electric motors 47 that are mounted on a mounting bracket assembly 48 on the underside of the plate 38 . These electric motors 47 have pinion gears 49 affixed to their drive shafts. The pinion gears 49 cooperate with gears 51 fixed to the driving shaft 41 so as to drive it. These motors 47 are of the reversible variable speed type and are control by a suitable control panel 49 mounted on the side of the shelves 31 ( FIG. 1 ).
[0030] Although the drive belts 37 may be made of any suitable material and may, as noted above, have their inner flight toothed to provide a non-slip driving relationship with the driving wheels 35 and driven wheel 36 , it may be desirable to provide an arrangement for retaining the drive belt against axial movements. FIGS. 10 and 11 show an embodiment to how this may be accomplished. Aside from this anti-slipping arrangement, the construction is the same as that previously described and, therefore, the components which are the same have been identified by the same reference numerals and will not be described again, except insofar as is necessary to understand the construction and operation of this embodiment.
[0031] In this embodiment, the driving and driven wheels 35 and 36 have annular members 51 affixed to their outer periphery and which extend radially outwardly beyond the outer periphery of the wheels 35 and 36 . Thus, as seen in FIG. 1 , these extending portions provided by the annular members 51 will insure that the belts 37 are maintained in axial position on the wheels 35 and 36 .
[0032] Depending upon the width or depth of the shelves 31 , it may be desirable to provide further support on the floor 32 and specifically for the back up side of the belt 37 . FIG. 12 shows such an arrangement where, in addition to the driving wheel 35 and driven wheel 36 mounted on the shafts 41 and 42 , respectively, there are a plurality of back up rollers 61 that are carried by shafts 62 that are journaled in the pillow blocks 43 and bearings 44 . Thus, more back up contact is provided between the drive belt 37 and the floor 32 .
[0033] Also, the width of the belts 37 may be changed from a narrow width to a wide width as shown in FIG. 13 where the different widths are shown at 37 a , 37 b and 37 c . Although the support is greater when the width is increased, this provides a larger resistance to driving and requires larger driving motors.
[0034] FIG. 14 shows how the inter-positioning of the belt 37 between the driving and driven wheels 35 and 36 and the floor 32 provides a cushioning between the wheels 35 and 36 and the floor 32 . Hence, the device can be utilized on a wide variety of floor materials and, special rails embedded in or mounted on the floor 32 are not required. The supporting portion of the drive belt is indicated in FIG. 14 by the reference numeral 63 .
[0035] It has been noted in the embodiment as thus far described, there are provided two electric drive motors 47 spaced transversely across the length of the shelf 31 . Of course, the number of drive motors can be changed. Also although electric motors are illustrated, other means for rotating the driving shaft 41 can be employed. These can include providing a manual crank handle mounted on the side of shelf 31 for rotating the shaft 41 .
[0036] In the embodiment as thus far described, all of the drive wheels 35 are mounted on a common shaft and are driven. Depending upon the loads to be expected and the specific environment, it is not necessary that all wheels be directly driven.
[0037] FIGS. 15 through 17 are partial views which can be considered to be similar to FIGS. 3 and 6 and show how some wheels, again indicated by the reference numerals 35 and 36 , can be mounted on stub shafts 81 which are journaled in the pillow blocks 43 and bearings 44 . In this case, these drive belts 37 are only driven through their contact with the floor.
[0038] In connection with an arrangement wherein the driving wheels that are driven by an electrical motor or other force are not all coupled to each other, it would be possible to provide controls whereby one motor can be driven and the other remains stationary or is rotated in a reverse direction. In this way, it is actually possible for the shelf to be driven in an arcuate fashion. The possibilities of such various movements should be readily apparent to those skilled in the art without further description or illustration.
[0039] Thus, from the foregoing description it should be readily apparent that the described embodiments permit the use of storage devices that can be easily moved and employed in any closed area without the necessity of guide rails. This offers substantially greater versatility and a wider variety of types of storage systems. Of course, the foregoing description is that of preferred embodiments of the invention and various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims. | A number of embodiments of moveable storage racks and/or partitions that can be installed in existing buildings without the necessity of installing guide rails for them. In addition, the movement may be controlled so that the partitions move either in a parallel fashion or they can be rotated through an arc. The partitions are supported on drive and guide belts that are mounted on the underside thereof and which eliminate the need for the guide rails and spread the weight of the partition over a greater area of the floor so as to permit use in buildings which were not originally designed for such systems. | 4 |
FIELD OF THE INVENTION
[0001] The invention relates to radio navigation in general, and, more particularly, to generating an accurate estimate of the location of a wireless terminal despite apparently reasonable but misleading or erroneous data.
BACKGROUND
[0002] FIG. 1 depicts a diagram of the salient components of wireless telecommunications system 100 in accordance with the prior art. Wireless telecommunications system 100 comprises: wireless terminal 101 , cellular base stations 102 - 1 , 102 - 2 , and 102 - 3 , Wi-Fi base stations 103 - 1 and 103 - 2 , wireless switching center 111 , assistance server 112 , location client 113 , and Global Positioning System (“GPS”) constellation 121 . Wireless telecommunications system 100 provides wireless telecommunications service to all of geographic region 120 , in well-known fashion.
[0003] The salient advantage of wireless telecommunications over wireline telecommunications is the mobility that is afforded to the user of the wireless terminal. On the other hand, the salient disadvantage of wireless telecommunications lies in that fact that because the wireless terminal is mobile, an interested party might not be able to readily ascertain the location of the wireless terminal.
[0004] Such interested parties might include both the user of the wireless terminal and remote parties. There are a variety of reasons why the user of a wireless terminal might be interested in knowing his or her location. For example, the user might be interested in telling a remote party where he or she is or the user might seek advice in navigation.
[0005] In addition, there are a variety of reasons why a remote party might be interested in knowing the location of the user. For example, the recipient of an 9-1-1 emergency call from a user might be interested in knowing the location of the wireless terminal so that emergency services vehicles can be dispatched to the user.
[0006] There are many techniques in the prior art for estimating the location of a wireless terminal. The common theme to these techniques is that location of the wireless terminal is estimated based on the electromagnetic (e.g., radio, etc.) signals—in one form or another—that are processed (i.e., transmitted or received) by the wireless terminal.
[0007] In accordance with one family of techniques, the location of a wireless terminal is estimated based on the transmission range of the base stations with which it is communicating. Because the range of a base station is known to be N meters, this family of techniques provides an estimate for the location that is generally accurate to within N meters. A common name for this family of techniques is “cell identification” or “cell ID.”
[0008] There are numerous tricks that can be made to the basic cell ID technique to improve the accuracy of the estimate for the location, and numerous companies like Ericsson, Qualcomm, and Google each tout their own flavor. The principal disadvantage of the family of cell ID techniques is that there are many applications for which the accuracy of the estimate for the location it generates is insufficient.
[0009] In accordance with a second family of techniques, the location of a wireless terminal is estimated by analyzing the angle of arrival or time of arrival of the signals transmitted by the wireless terminal. A common, if somewhat inaccurate, name for this family of techniques is called “triangulation.”
[0010] There are numerous tricks that can be made to the basic triangulation technique to improve the accuracy of the estimate for the location, and numerous companies like TruePosition each tout their own flavor. The principal disadvantage of the triangulation techniques is that there are many applications for which the accuracy of the estimate for the location it generates is insufficient.
[0011] In accordance with a third family of techniques, the location of a wireless terminal is estimated by a receiver in the wireless terminal that receives signals from satellites in orbit. A common name for this family of techniques is “GPS.”
[0012] There are numerous tricks that can be made to the basic GPS technique to improve the accuracy of the estimate for the location, and numerous companies like Qualcomm each tout their own flavor. The principal advantage of the GPS techniques is that when it works, the estimate for the location can be accurate to within meters. The GPS techniques are disadvantageous in that they do not work consistently well indoors, in heavily-wooded forests, or in urban canyons.
[0013] In accordance with a fourth family of techniques, the location of a wireless terminal is estimated by pattern matching one or more location-dependent traits of one or more electromagnetic signals that are processed (i.e., transmitted and/or received) by the wireless terminal. Common names for this family of techniques include “Wireless Location Signatures,” “RF Pattern Matching,” and “RF Fingerprinting.”
[0014] The basic idea is that some traits of an electromagnetic signal remain (more or less) constant as a signal travels from a transmitter to a receiver (e.g., frequency, etc.) and some traits change (e.g., signal strength, relative multi-path component magnitude, propagation delay, etc.). A trait that changes is considered a “location-dependent” trait. Each location can be described or associated with a profile of one or more location-dependent traits of one or more electromagnetic signals. A wireless terminal at an unknown location can observe the traits and then attempt to ascertain its location by comparing the observed traits with a database that correlates locations with expected or predicted traits.
[0015] There are numerous tricks that can be made to the basic Wireless Location Signatures technique to improve the accuracy of the estimate for the location, and numerous companies like Polaris Wireless each tout their own flavor. The principal advantage of the Wireless Location Signatures technique is that it is highly accurate and works well indoors, in heavily-wooded forests, and in urban canyons.
[0016] All of these techniques rely on empirical data as their basis, and the accuracy of these techniques suffer when some or all of the data is misleading or erroneous. Typically, it is easy to identify and disregard data that is clearly unreasonable. For example, if one datum indicates that a wireless terminal is inside of the Sun, that datum is clearly erroneous and can be disregarded. In some cases a reasonable estimate for the location of the wireless terminal can be generated with the remaining data, and sometimes it cannot.
[0017] In contrast, it is difficult to identify data that is apparently reasonable, but misleading or erroneous. For example, if one datum in a set of data suggests a wireless terminal is on a lake near a highway, the datum appears reasonable, but it might or might not be erroneous. For example, the datum might be entirely correct because the wireless terminal is on a boat on the lake. Alternatively, the datum might be erroneous because the wireless terminal is in a car on the highway next to the lake. In either case, it is not easy to know whether using that datum is improving or degrading the overall accuracy of the estimate.
[0018] Unfortunately, apparently reasonable, but erroneous or misleading empirical data is commonly used as the basis for estimating the location of a wireless terminal, and, therefore, a technique is needed that ameliorates or eliminates the effect of such data.
SUMMARY OF THE INVENTION
[0019] The present invention enables an estimate of the location of a wireless terminal to be generated without some of the costs and disadvantages of techniques for doing so in the prior art. For example, some embodiments of the present invention are adept at discounting the contribution of apparently reasonable but erroneous or misleading data.
[0020] For example, the illustrative embodiment of the present invention receives data that is evidence of the location of a wireless terminal at each of a plurality of different times. The illustrative embodiment then generates an initial hypothesis for the location of the wireless terminal at each time assuming that all of the data is correct and equally probative. Next, the illustrative embodiment generates an alternative hypotheses for each initial hypothesis on the assumption that each proper subset of datum is erroneous. This is accomplished by underweighting or discarding each datum in the proper subset.
[0021] For example, if the set of data for time t(1) is {A, B, C}, then the initial hypothesis for time t(1) is based on an equal weighting of A, B, and C. Because the set comprises three datum, there are six non-empty subsets of datum: {A}, {B}, {C}, {A, B}, {A, C}, and {B, C}. Each alternative hypothesis for time t(1) can be generated by using the data in each of the non-empty subsets and by underweighting or discarding the data not included in the subset.
[0022] These alternative hypothesis can be “snapped” or moved to a nearby road or transportation path, or they can be left alone.
[0023] Finally, the illustrative embodiment generates the estimate for the location of the wireless terminal at each time in a time frame by determining which combination of initial hypotheses and alternative hypothesis is the most self-consistent during the entire time frame.
[0024] The illustrative embodiment comprises:
receiving, at a location engine, a first signal value whose value is evidence of the location of the wireless terminal at time t(1); receiving, at the location engine, a second signal value whose value is evidence of the location of the wireless terminal at time t(1); receiving, at the location engine, a third signal value whose value is evidence of the location of the wireless terminal at time t(2); generating, at the location engine, a first hypothesis for the location for the wireless terminal at time t(1) based on the first signal value having first weight and the second signal value having second weight, wherein the first weight is greater than the second weight; generating, at the location engine, a second hypothesis for the location for the wireless terminal at time t(1) based on the first signal value having third weight and the second signal value having fourth weight, wherein the third weight is less than the fourth weight; generating, at the location engine, a first hypothesis for the location for the wireless terminal at time t(2) based on the third signal value; and generating, at the location engine, an estimate for the location of the wireless terminal at time t(2) based on:
the first hypothesis for the location for the wireless terminal at time t(1), the second hypothesis for the location for the wireless terminal at time t(1), and the first hypothesis for the location for the wireless terminal at time t(2); and
transmitting, from the location engine, the estimate for the location of the wireless terminal at time t(2) for use by a location-based application; wherein the first weight, the second weight, the third weight, and the fourth weight are all real non-negative numbers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 depicts a diagram of the salient components of wireless telecommunications system 100 in accordance with the prior art.
[0038] FIG. 2 depicts a diagram of the salient components of wireless telecommunications system 200 in accordance with the illustrative embodiment of the present invention.
[0039] FIG. 3 depicts a block diagram of the salient components of location engine 214 in accordance with the illustrative embodiment.
[0040] FIG. 4 depicts a flowchart of the salient processes performed in accordance with the illustrative embodiment of the present invention.
[0041] FIG. 5 depicts a road map of geographic region 220 that indicates the four initial hypotheses from Table 2.
[0042] FIG. 6 depicts a road map of geographic region 220 that indicates the nine alternative hypotheses generated in task 403 .
[0043] FIG. 7 depicts a road map of geographic region 220 that indicates the nine snapped alternative hypotheses generated in task 403 .
[0044] FIG. 8 depicts the weighted directed graph that corresponds the initial hypotheses and snapped alternative hypotheses generated in task 406 .
[0045] FIG. 9 depicts the minimum weight path through the weighted directed graph depicted in FIG. 8 .
[0046] FIG. 10 depicts the road map of geographic region 220 that indicates the final refined hypotheses of the location of wireless terminal at time t, for all t.
DETAILED DESCRIPTION
[0047] Overview
[0048] FIG. 2 depicts a diagram of the salient components of wireless telecommunications system 200 in accordance with the illustrative embodiment of the present invention. Wireless telecommunications system 200 comprises: wireless terminal 201 , cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 , Wi-Fi base stations 203 - 1 and 203 - 2 , wireless switching center 211 , assistance server 212 , location client 213 , location engine 214 , and GPS constellation 221 , which are interrelated as shown. The illustrative embodiment provides wireless telecommunications service to all of geographic region 220 , in well-known fashion, hypothesizes the location of wireless terminal 201 within geographic region 220 at different times, and uses those hypotheses in a location-based application.
[0049] In accordance with the illustrative embodiment, wireless telecommunications service is provided to wireless terminal 201 in accordance with the air-interface standard of the 3 rd Generation Partnership Project (“3GPP”). After reading this disclosure, however, it will be clear to those skilled in the art how to make and use alternative embodiments of the present invention that operate in accordance with one or more other air-interface standards (e.g., Global System Mobile “GSM,” UMTS, CDMA-2000, IS-136 TDMA, IS-95 CDMA, 3G Wideband CDMA, IEEE 802.11 Wi-Fi, 802.16 WiMax, Bluetooth, etc.) in one or more frequency bands. As will be clear to those skilled in the art, a wireless terminal is also known as a “cell phone,” “mobile station,” “car phone,” “PDA,” and the like.
[0050] Wireless terminal 201 comprises the hardware and software necessary to be 3GPP-compliant and to perform the processes described below and in the accompanying figures. For example and without limitation, wireless terminal 201 is capable of:
a. measuring one or more location-dependent traits of each of one of more electromagnetic signals (transmitted by cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 and Wi-Fi base stations 203 - 1 and 203 - 2 ) and of reporting the measurements to location engine 214 , and b. transmitting one or more signals and of reporting the transmission parameters of those signals to location engine 214 , and c. receiving GPS assistance data from assistance server 212 to assist wireless terminal 201 in acquiring and processing GPS ranging signals.
[0054] Wireless terminal 201 is mobile and can be at any location within geographic region 220 at any time. Although wireless telecommunications system 200 comprises only one wireless terminal, it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention that comprise any number of wireless terminals.
[0055] Cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 communicate with wireless switching center 211 via wireline and with wireless terminal 201 via radio in well-known fashion. As is well known to those skilled in the art, base stations are also commonly referred to by a variety of alternative names such as access points, nodes, network interfaces, etc. Although the illustrative embodiment comprises three base stations, it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention that comprise any number of base stations.
[0056] In accordance with the illustrative embodiment of the present invention, cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 are terrestrial, immobile, and within geographic region 220 . It will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which some or all of the base stations are airborne, marine-based, or space-based, regardless of whether or not they are moving relative to the Earth's surface, and regardless of whether or not they are within geographic region 220 .
[0057] Cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 comprise the hardware and software necessary to be 3GPP-compliant and to perform the processes described below and in the accompanying figures. For example and without limitation, cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 are capable of:
a. measuring one or more location-dependent traits of each of one of more electromagnetic signals (transmitted by wireless terminal 201 ) and of reporting the measurements to location engine 214 , and b. transmitting one or more signals and of reporting the transmission parameters of those signals to location engine 214 .
[0060] Wi-Fi base stations 203 - 1 and 203 - 2 communicate with wireless terminal 201 via radio in well-known fashion. Wi-Fi base stations 203 - 1 and 203 - 2 have a shorter range than cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 , but have a higher bandwidth. The location of Wi-Fi base stations 203 - 1 and 203 - 2 is only known to within approximately 30 meters by detecting their signals through drive testing. Wi-Fi base stations 203 - 1 and 203 - 2 are terrestrial, immobile, and within geographic region 220 .
[0061] Wi-Fi base stations 203 - 1 and 203 - 2 are capable of:
c. measuring one or more location-dependent traits of each of one of more electromagnetic signals (transmitted by wireless terminal 201 ) and of reporting the measurements to location engine 214 , and d. transmitting one or more signals and of reporting the transmission parameters of those signals to location engine 214 .
[0064] Wireless switching center 211 comprises a switch that orchestrates the provisioning of telecommunications service to wireless terminal 201 and the flow of information to and from location engine 214 , as described below and in the accompanying figures. As is well known to those skilled in the art, wireless switching centers are also commonly referred to by other names such as mobile switching centers, mobile telephone switching offices, routers, etc.
[0065] Although the illustrative embodiment comprises one wireless switching center, it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention that comprise any number of wireless switching centers. For example, when a wireless terminal can interact with two or more wireless switching centers, the wireless switching centers can exchange and share information that is useful in estimating the location of the wireless terminal. For example, the wireless switching centers can use the IS-41 protocol messages HandoffMeasurementRequest and HandoffMeasurementRequest2 to elicit signal-strength measurements from one another. The use of two or more wireless switching centers is particularly common when the geographic area serviced by the wireless switching center is small (e.g., local area networks, etc.) or when multiple wireless switching centers serve a common area.
[0066] In accordance with the illustrative embodiment, all of the base stations servicing wireless terminal 201 are associated with wireless switching center 211 . It will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which any number of base stations are associated with any number of wireless switching centers.
[0067] Assistance server 212 comprises hardware and software that is capable of performing the processes described below and in the accompanying figures. In general, assistance server 212 generates GPS assistance data for wireless terminal 201 to aid wireless terminal 201 in acquiring and processing GPS ranging signals from GPS constellation 221 . In accordance with the illustrative embodiment, assistance server 212 is a separate physical entity from location engine 214 ; however, it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which assistance server 212 and location engine 214 share hardware, software, or both.
[0068] Location client 213 comprises hardware and software that uses the hypothesis for the location of wireless terminal 201 —provided by location engine 214 —in a location-based application, as described below and in the accompanying figures.
[0069] Location engine 214 comprises hardware and software that generates one or more hypotheses of the location of wireless terminal 201 as described below and in the accompanying figures. It will be clear to those skilled in the art, after reading this disclosure, how to make and use location engine 214 . Furthermore, although location engine 214 is depicted in FIG. 2 as physically distinct from wireless switching center 211 , it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which location engine 214 is wholly or partially integrated with wireless switching center 211 .
[0070] In accordance with the illustrative embodiment, location engine 214 communicates with wireless switching center 211 , assistance server 212 , and location client 213 via a local area network; however it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which location engine 214 communicates with one or more of these entities via a different network such as, for example, the Internet, the Public Switched Telephone Network (PSTN), a wide area network, etc.
[0071] In accordance with the illustrative embodiment, wireless switching center 211 , assistance server 212 , location client 213 , and location engine 214 are physically located within geographic region 220 . It will be clear to those skilled in the art, however, after reading this disclosure, how to make and use alternative embodiments of the present invention in which some or all of wireless switching center 211 , assistance server 212 , location client 213 , and location engine 214 are physically located outside of geographic region 220 .
[0072] Location Engine 214
[0073] FIG. 3 depicts a block diagram of the salient components of location engine 214 in accordance with the illustrative embodiment. Location engine 214 comprises: processor 301 , memory 302 , and local-area network transmitter/receiver 303 , which are interconnected as shown.
[0074] Processor 301 is a general-purpose processor that is capable of executing operating system 311 and application software 312 , and of populating, amending, using, and managing Location-Trait Database 313 , as described in detail below and in the accompanying figures. For the purposes of this specification, a “processor” is defined as one or more computational elements, whether co-located or not and whether networked together or not.
[0075] For the purposes of this specification, the “Location-Trait Database” is defined as a database that associates one or more location-dependent traits of electromagnetic signals processed (i.e., transmitted and/or received) by wireless terminal 201 with each of a plurality of locations. In general, the Location-Trait Database is what enables location engine 214 to convert observed location-dependent traits into an estimate for the location of wireless terminal 201 . It will be clear to those skilled in the art how to make and use processor 301 .
[0076] Memory 302 is a non-volatile memory that stores:
[0077] a. operating system 311 , and
[0078] b. application software 312 , and
[0079] c. Location-Trait Database 313 .
[0000] It will be clear to those skilled in the art how to make and use memory 302 .
[0080] Transmitter/receiver 303 enables location engine 214 to transmit and receive information to and from wireless switching center 211 , assistance server 212 , and location client 213 . In addition, transmitter/receiver 303 enables location engine 214 to transmit information to and receive information from wireless terminal 201 and cellular base stations 202 - 1 through 202 - 3 via wireless switching center 211 . It will be clear to those skilled in the art how to make and use transmitter/receiver 303 .
[0081] Operation of the Illustrative Embodiment
[0082] FIG. 4 depicts a flowchart of the salient processes performed in accordance with the illustrative embodiment of the present invention.
[0083] At task 401 , location engine 214 receives signals from wireless switching center 211 whose values are evidence of the location of wireless terminal 201 at different times. Each signal radiates from a different source (e.g., cellular base stations 202 - 1 , 202 - 2 , and 202 - 3 , Wi-Fi base stations 203 - 1 and 203 - 2 , wireless terminal 201 , etc.). Table 1 depicts three signals, S(1), S(2), and S(3), and the values of those signals at times t(1), t(2), t(3), and t(4).
[0000] TABLE 1 Nine signals whose values are evidence of the location of wireless terminal 201 in geographic region 220 at four different times. time Signal S(1) Signal S(2) Signal S(3) t(1) SV(1, 1) SV(1, 2) Not Available t(2) SV(2, 1) SV(2, 2) SV(2, 3) t(3) SV(3, 1) Not Available SV(3, 3) t(4) Not Available SV(4, 2) SV(4, 3)
In the signal value SV(t, j), t represents the time for which the signal is evidence, and j represents the source of the signal.
[0084] In accordance with the illustrative embodiment, the value of each signal is a signal-strength measurement made by wireless terminal 201 of a radio signal transmitted by one of cellular base stations 202 - 1 and 202 - 2 and Wi-Fi base station 203 - 1 . It will be clear to those skilled in the art, however, after reading this disclosure, how to make and use alternative embodiments of the present invention in which the value of each received signal is a measurement of any location-dependent trait of an electromagnetic signal that is evidence of the location of wireless terminal 201 . For example and without limitation, each signal can be:
i. evidence of the propagation delay—in either one-direction or round-trip—between wireless terminal 120 and another entity (e.g., a cellular base station, a GPS satellite, a Wi-Fi base station, etc.), or ii evidence of the time difference of arrival of a signal transmitted by wireless terminal 201 and two other entities (e.g., a cellular base station, a GPS satellite, a Wi-Fi base station, etc.), or iii. evidence of the angle of arrival of a signal transiting between wireless terminal 201 and another entity (e.g., a cellular base station, a GPS satellite, a Wi-Fi base station, etc.), or iv. evidence that wireless terminal 201 can receive and decode a signal from another entity (e.g., a cellular base station, a GPS satellite, a Wi-Fi base station, etc.), or v. evidence that an entity (e.g., a cellular base station, a GPS satellite, a Wi-Fi base station, etc.) can receive and decode a signal from wireless terminal 201 , or vi. evidence of any location-dependent trait (e.g., signal strength, rake receiver coefficients, phase delay, etc.) of an electromagnetic signal that is processed by wireless terminal 201 , or vii. any combination of i, ii, iii, iv, v, or vi.
[0092] In accordance with the illustrative embodiment, three signals are received for time t(2) but only two signals are received for times t(1), t(3), and t(4) because signal value SV(1, 3), SV(3, 2) and SV(4, 1) were not measured or reported. It will be clear to those skilled in the art, however, after reading this disclosure, how to make and use alternative embodiments of the present invention in which any number of signals are received and used for each moment of time.
[0093] In accordance with the illustrative embodiment, all of the signals are evidence of the same type of physical quantity (i.e., received signal strength), but it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which the type of physical quantity represented varies (e.g., three signal-strength measurements are received for one moment, one signal-strength measurement and two time-difference of arrival measurements are received for the next moment, etc.). In accordance with the illustrative embodiment, there is signal data available for four moments of time, but it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which data is available for any number of moments.
[0094] At task 402 , location engine 214 generates an “initial” hypothesis for the location of wireless terminal 201 at each of times t(1), t(2), t(3), and t(4). Each hypothesis and each estimate of the location of wireless terminal 201 is a latitude-longitude pair.
[0095] Each initial hypothesis for the location of wireless terminal 201 is a hypothesis that does not discount the probative value of any signal value. In other words, all of the signals that are evidence of the location of wireless terminal 201 at one time are accorded equal probity for the purposes of creating the initial hypotheses. In practice, this is achieved by weighting each signal value SV(t, j) with weight W(t, j, 0), wherein W(t, j, 0) are equal and non-negative real values for all t and all j.
[0096] In accordance with the illustrative embodiment, location engine 215 generates the initial hypotheses using the signals received at task 401 and the technique of wireless location signatures. The wireless location signatures technique is well-known to those skilled in the art and is taught, for example, in U.S. Pat. No. 7,257,414 B2, which is incorporated by reference. It will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which the initial hypotheses are generated using:
[0097] i. wireless location signatures, or
[0098] ii. triangulation, or
[0099] iii. trilateration, or
[0100] iv. cellular-base-station cell identification, or
[0101] v. Wi-Fi-base-station cell identification, or
[0102] vi. any combination of i, ii, iii, iv, and v.
[0103] At time t(2), the initial hypothesis is based on three signals, but at times t(1), t(3), and t(4) the initial hypotheses are based on only two signals. Table 2 depicts the values of each of the four initial hypotheses.
[0000]
TABLE 2
The initial locations of wireless terminal 201 in geographic region 220 at
four different times.
time
Initial Hypothesis
t(1)
IH(1)
t(2)
IH(2)
t(3)
IH(3)
t(4)
IH(4)
[0104] FIG. 5 depicts a road map of geographic region 220 that indicates the four initial hypotheses from Table 2. In the map the initial hypothesis for the location of wireless terminal 201 at time t(i) is depicted by a bull's-eye with the identifier IH(i).
[0105] Therefore, the initial hypothesis IH(1) for wireless terminal 201 at time t(1) is on West Street, just south of Left Street. The initial hypothesis IH(2) at time t(2) is between Top Street and North Street, just east of West Street. The ambiguity of whether wireless terminal 201 was on Top Street or North Street at time t(2) is undesirable because a known drug-dealer operates on Top Street and it would be advantageous to know whether the operator of wireless terminal 201 might be involved with the drug dealer or not. The illustrative embodiment of the present invention resolves that ambiguity beginning in task 403 below. The initial hypothesis IH(3) for wireless terminal 201 at time t(3) is between Lakeside Road, North Street, and East Street. The initial hypothesis IH(4) at time t(4) is unambiguously on Lakeside Road.
[0106] In accordance with the illustrative embodiment, the initial hypotheses are used as is, but it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which one or more of the initial hypotheses are “snapped” or repositioned to one or more roadways or other transportation paths in the vicinity of the initial hypothesis.
[0107] Referring again to FIG. 4 , at task 403 location engine 214 generates additional “alternative” hypotheses for the location of wireless terminal 201 at each time for which two or more signal values are available. Each alternative hypothesis is also a hypothesis for the location of wireless terminal 201 .
[0108] In accordance with the illustrative embodiment, location engine 214 uses the same location technique to generate the alternative hypotheses as it did to generate the initial hypotheses in task 402 . It will be clear to those skilled in the art, however, after reading this disclosure, how to make and use alternative embodiments of the present invention in which the candidates hypotheses are generated using an alternative method, such as:
[0109] i. wireless location signatures, or
[0110] ii. triangulation, or
[0111] iii. trilateration, or
[0112] iv. cellular-base-station cell identification, or
[0113] v. Wi-Fi-base-station cell identification, or
[0114] vi. any combination of i, ii, iii, iv, and v.
[0115] In accordance with the illustrative embodiment, each alternative hypothesis for a given time is generated by discounting as unreliable exactly one signal value. For example, when there are N>1 signal values available for a given time, there are N alternative hypotheses generated for that time. When there is only one signal available for a given time, no alternative hypotheses are generated because the one signal value cannot be discounted with respect to itself.
[0116] It will be clear to those skilled in the art, however, how to make and use alternative embodiments of the present invention in which there are a different number of alternative hypotheses generated for a given time (e.g., 1, 2, 3, N−1, 2 N −2, N!, etc.). For example, it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which each alternative hypothesis for a given time is generated by discounting as unreliable every combination of signal values. This would generate 2 N −2 alternative hypotheses. Furthermore, some alternative embodiments of the present invention could discount each signal value by a continuous value, which would generate up to N! alternative hypotheses.
[0117] In practice, the illustrative embodiment generates each alternative hypothesis AH(t, k) for the location of wireless terminal 201 at time t by weighting each signal value SV(t, j) with weight W(t, j, k), wherein W(t, j, k) is a non-negative real value for all times i, all signals j, and all hypotheses k. It will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which some or all of the discounted signal's values have a weight of zero (0).
[0118] Table 3 depicts signals SV(1, 1) and SV(1, 2) and their associated weights for the purposes of generating alternative hypotheses AH(1, 1) and AH(1, 2).
[0000]
TABLE 3
The weights and their relationships for generating the alternative
hypotheses at time t(1).
Alternative
Signal
Signal
Signal
Weight
Hypothesis
SV(1, 1)
SV(1, 2)
SV(1, 3)
Relationship
AH(1, 1)
W(1, 1, 1)
W(1, 2, 1)
Not
W(1, 1, 1) <
Available
W(1, 2, 1)
AH(1, 2)
W(1, 1, 2)
W(1, 2, 2)
Not
W(1, 1, 2) >
Available
W(1, 2, 2)
Not Applicable
Not Applicable
Not
Not
Not Applicable
Applicable
Available
[0119] Table 4 depicts signals SV(2, 1), SV(2, 2), and SV(2, 3) and their associated weights for the purposes of generating alternative hypotheses AH(2, 1), AH(2, 2), and AH(2, 3).
[0000]
TABLE 4
The weights and their relationships for generating the alternative
hypotheses at time t(2).
Alter-
native
Hy-
Signal
Signal
Signal
Weight
pothesis
SV(2, 1)
SV(2, 2)
SV(2, 3)
Relationship
AH(2, 1)
W(2, 1, 1)
W(2, 2, 1)
W(2, 3, 1)
W(2, 1, 1) < W(2, 2, 1)
W(2, 1, 1) < W(2, 3, 1)
W(2, 2, 1) = W(2, 3, 1)
AH(2, 2)
W(2, 1, 2)
W(2, 2, 2)
W(2, 3, 2)
W(2, 2, 2) < W(2, 1, 2)
W(2, 2, 2) < W(2, 3, 2)
W(2, 1, 2) = W(2, 3, 2)
AH(2, 3)
W(2, 1, 3)
W(2, 2, 3)
W(2, 3, 3)
W(2, 3, 3) < W(2, 1, 3)
W(2, 3, 3) < W(2, 2, 3)
W(2, 1, 3) = W(2, 2, 3)
[0120] In Table 4, W(2, 2, 1)=W(2, 3, 1), W(2, 1, 2)=W(2, 3, 2), and W(2, 1, 3)=W(2, 2, 3), but it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which some or all of these relationships are not true in order to partially discount some signal values. For example, W(2, 2, 1)<W(2, 3, 1), W(2, 1, 2)<W(2, 3, 2), W(2, 1, 3)<W(2, 2, 3), W(2, 2, 1)>W(2, 3, 1), W(2, 1, 2)>W(2, 3, 2), and W(2, 1, 3)>W(2, 2, 3).
[0121] Table 5 depicts signals SV(3, 1) and SV(3, 3) and their associated weights for the purposes of generating alternative hypotheses AH(3, 1) and AH(3, 3).
[0000]
TABLE 5
The weights and their relationships for generating the alternative
hypotheses at time t(3).
Alternative
Signal
Signal
Signal
Weight
Hypothesis
SV(3, 1)
SV(3, 2)
SV(3, 3)
Relationship
AH(3, 1)
W(3, 1, 1)
Not
W(3, 3, 1)
W(3, 1, 1) <
Available)
W(3, 3, 1)
Not Applicable
Not Applicable
Not
Not
Not Applicable
Available
Applicable
AH(3, 3)
W(3, 1, 3)
Not
W(3, 3, 3)
W(3, 1, 3) >
Available
W(3, 3, 3)
[0122] Table 6 depicts signal values SV(4, 2), and SV(4, 3) and their associated weights for the purposes of generating alternative hypotheses AH(4, 2), and AH(4, 3).
[0000]
TABLE 6
The weights and their relationships for generating the alternative
hypotheses at time t(4).
Alternative
Signal
Signal
Signal
Weight
Hypothesis
SV(4, 1)
SV(4, 2)
SV(4, 3)
Relationship
Not Applicable
Not
Not Applicable
Not
Not Applicable
Available
Applicable
AH(4, 2)
Not
W(4, 2, 2)
W(4, 3, 2)
W(4, 2, 2) <
Available
W(4, 3, 2)
AH(4, 3)
Not
W(4, 2, 3)
W(4, 3, 3)
W(4, 2, 3) >
Available
W(4, 3, 3)
[0123] FIG. 6 depicts a road map of geographic region 220 that indicates the four initial hypotheses generated in task 402 plus the nine alternative hypotheses generated in task 403 . In the map the alternative hypotheses of the location of wireless terminal 201 are represented by a bull's-eye with the identifier AH(t, k).
[0124] In general, the alternative hypotheses for time t(t) are in the general vicinity of the initial hypotheses for the same time, as generally would be expected. But the generation and mapping of the alternative hypotheses does not, per se, resolve the ambiguities presented by the initial hypotheses. For example, the alternative hypothesis AH(1,2) on Left Street and the alternative hypothesis AH(1, 1) on West Street do not unambiguously resolve the question presented by the initial hypothesis IH(1) of whether wireless terminal 201 was on West Street or Left Street at time t(1). Ambiguities like these are resolved beginning in task 404 below.
[0125] At task 404 , location engine 214 generates a snapped alternative hypothesis SAH(t, k) for each alternative hypothesis AH(t, k). The snapped alternative hypothesis SAH(t, k) is also a hypothesis for the location of wireless terminal 201 .
[0126] In accordance with the illustrative embodiment, the snapped alternative hypothesis SAH(t, k) is a location on a road that is the shortest Euclidean distance between the alternative hypothesis AH(t, k) and any point on any road. The snapped alternative hypothesis SAH(t, k) corresponding to each alternative hypothesis AH(t, k) is depicted in Table 7 and FIG. 7 .
[0000]
TABLE 7
The alternative hypotheses and their corresponding snapped alternative
hypotheses.
Snapped
Alternative
Alternative
Hypothesis
Hypothesis
AH(1, 1)
SAH(1, 1)
AH(1, 2)
SAH(1, 2)
AH(2, 1)
SAH(2, 1)
AH(2, 2)
SAH(2, 2)
AH(2, 3)
SAH(2, 3)
AH(3, 1)
SAH(3, 1)
AH(3, 3)
SAH(3, 3)
AH(4, 2)
SAH(4, 2)
AH(4, 3)
SAH(4, 3)
[0127] In accordance with the illustrative embodiment, there is one snapped alternative hypothesis for each alternative hypothesis, but it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which some or all of the alternative hypothesis have a plurality of snapped alternative hypotheses.
[0128] Referring again to FIG. 4 , at task 405 , location engine 214 generates a measure of distance between each snapped alternative hypothesis SAH(t, k) and the corresponding initial hypothesis B(t) to generate a measure of discrepancy MOD(t, k). In accordance with the illustrative embodiment, the measure of distance is the Euclidean distance. The measures of discrepancy are depicted in Table 8.
[0000]
TABLE 8
The alternative hypotheses and their associated measures of discrepancy.
Snapped
Corresponding
Alternative
Initial
Measure of
Hypothesis
Hypothesis
Discrepancy
SAH(1, 1)
B(1)
MOD(1, 1)
SAH(1, 2)
B(1)
MOD(1, 2)
SAH(2, 1)
B(2)
MOD(2, 1)
SAH(2, 2)
B(2)
MOD(2, 2)
SAH(2, 3)
B(2)
MOD(2, 3)
SAH(3, 1)
B(3)
MOD(3, 1)
SAH(3, 3)
B(3)
MOD(3, 3)
SAH(4, 2)
B(4)
MOD(4, 2)
SAH(4, 3)
B(4)
MOD(4, 3)
[0129] At task 406 , location server 214 generates a weighted directed graph that comprises:
(i) a node that corresponds to each initial hypothesis B(t), for all t, and (ii) a node that corresponds to each snapped alternative hypothesis SAH(t, k), for all t and all k, and (iii) a directed link from each initial hypothesis B(t) to initial hypothesis B(t+1), for all t, and (iv) a directed link from each initial hypothesis B(t) to each snapped alternative hypothesis SAH(t+1, k), for all t and all k, and (v) a directed link from each snapped alternative hypothesis SAH(t, k) to each initial hypothesis B(t+1), for all t and all k, and (vi) a directed link from each snapped alternative hypothesis SAH(t, k) to each snapped alternative hypothesis SAH(t+1, k), for all t and all k.
The result is a directed graph, as shown in FIG. 8 , that represents every possible combination of paths from time t(1) to time t(4). All of the nodes that correspond to the same time t are depicted in a single column, and the nodes corresponding to time t are depicted in a column to the left of the nodes corresponding to time t+1.
[0136] In accordance with the illustrative embodiment,
(i) each node that corresponds to a initial hypothesis B(t) has an associated cost of zero (0), and (ii) each node that corresponds to a snapped alternative hypothesis SAH(t, k) has an associated cost equal to its associated measure of discrepancy MOD(t, k), and (iii) each directed link from node X to node Y has a cost equal to a measure of the distance between the location associated with node X and the location associated with node Y.
[0140] In accordance with the illustrative embodiment, the measure of distance from node X to node Y is the road travel time, but it will be clear to those skilled in the art, after reading this disclosure, how to make and use alternative embodiments of the present invention in which the measure of distance is another metric, such as for example and without limitation, the Euclidean distance from node X to node Y, the road travel time, etc.
[0141] At task 407 , location server 214 generates an estimate E(t) for the location of wireless terminal 201 for all t. To accomplish this, location server 214 determines the minimum-cost path through the graph constructed in task 406 using well-known dynamic programming techniques.
[0142] Once the minimum-cost path has been determined, the nodes in the minimum-cost path constitute the final, best estimates of the location of wireless terminal 201 at each time.
[0143] The minimum-cost path through the directed graph is depicted in FIG. 9 as beginning at snapped alternative hypothesis SAH(1, 1), proceeding to snapped alternative hypothesis SAH(2, 3), proceeding to snapped alternative hypothesis SAH(3, 3), and terminating at initial hypothesis IH(4). Therefore, E(1) is the location corresponding to snapped alternative hypothesis SAH(1, 1), E(2) is the location corresponding to base hypothesis SAH(2, 3), E(3) is the location corresponding to snapped alternative hypothesis SAH(3, 3), and E(4) is the location corresponding to snapped alternative hypothesis IH(4). This is summarized in Table 9.
[0000]
TABLE 9
The alternative hypotheses and their corresponding hypotheses.
Estimate
Hypothesis
E(1)
SAH(1, 1)
E(2)
SAH(2, 2)
E(3)
SAH(3, 3)
E(4)
IH(4)
[0144] FIG. 10 depicts the road map of geographic region 220 that indicates the final refined hypotheses of the location of wireless terminal at time t, for all t. As part of task 407 , each of the refined hypotheses is transmitted from location engine 214 to location client 213 for use in a location-based application. | A location engine is disclosed that estimates the location of a wireless terminal using (i) cell ID, (ii) triangulation, (iii) GPS, (iv) RF pattern-matching, or (v) any combination of them. The location engine is adept at discounting the contribution of apparently reasonable but erroneous data. The location engine receives data that are evidence of the location of a wireless terminal at each of a plurality of different times. The location engine then generates an initial hypothesis for the location of the wireless terminal at each time assuming that all of the data is correct and equally probative. Next, the location engine generates one alternative hypothesis for each initial hypothesis and each datum assuming that the datum is erroneous. Finally, the location engine generates the estimate for the location of the wireless terminal at each time by determining which combination of initial hypotheses and alternative hypothesis is the most self-consistent. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an asymmetry detection circuit for detecting the asymmetry of alternating current signals and a detection method of the same.
[0003] 2. Description of the Related Art
[0004] In an asymmetry correction circuit or the like, in order to correct the asymmetry of alternating current signals, first the asymmetry of an input signal must be detected.
[0005] Conventionally, the asymmetry of alternating current signals has been detected by comparing bias voltages of the signals with an intermediate potential of a signal amplitude. FIG. 4 shows an example of the conventional asymmetry detection circuit. As illustrated, this asymmetry detection circuit 200 is comprised by peak hold circuits 210 and 220 , an intermediate voltage detection circuit 230 , and an asymmetry processing circuit 240 .
[0006] The peak hold circuit 210 holds the upper limit value (positive peak level S PK1 ) of an input signal S in , while the peak hold circuit 220 holds the lower limit value (negative peak level S PK2 ) of the same input signal S in .
[0007] The intermediate voltage detection circuit 230 detects the intermediate voltage of the input signal S in in accordance with the positive peak level S PK1 and the negative peak level S PK2 found by the peak hold circuits 210 and 220 .
[0008] Here, assume that for example the input signal S in has the waveform shown in FIG. 5. The peak hold circuit 210 detects the positive peak level S PK1 of this input signal S in , while the peak hold circuit 220 detects the negative peak level S PK2 . The intermediate voltage detection circuit 230 finds an intermediate voltage V 2 of the input signal S in by the following equation based on the positive and negative peak levels S PK1 and S PK2 and outputs a signal S M indicating the intermediate voltage to the asymmetry processing circuit 240 .
V 2 =( S PK1 −S PK2 )/2 (1)
[0009] Namely, the intermediate voltage V 2 is the voltage in the middle of the positive peak level S PK1 and the negative peak level S PK2 of the input signal S in in the waveform of the input signal S in shown in FIG. 5 and is a voltage value where a=b stands as illustrated.
[0010] The asymmetry processing circuit 240 calculates the asymmetry of the signal S in according to the bias voltage V 1 of the input signal S in and the intermediate voltage V 2 thereof.
[0011] The asymmetry of alternating current signals is defined as a ratio of upper and lower peak voltages with respect to a direct current voltage level by which a duty ratio of the alternating current signals becomes 50%. The asymmetry processing circuit 240 can calculate the asymmetry of the input signal S in based on the bias voltage V 1 of the input signal S in and the intermediate voltage V 2 detected by the intermediate voltage detection circuit 230 according to this definition.
[0012] Summarizing the problem to be solved by the invention, in a conventional asymmetry detection circuit, in order to find the asymmetry of an input signal, first the positive and negative peak levels of the signal are detected by the peak hold circuits, then the intermediate voltage V 1 of the signal amplitude is detected in accordance with the result. Therefore, the positive peak hold circuit and the negative peak hold circuit become necessary. The precision of the found intermediate voltage is largely governed by the holding characteristics of these circuits.
[0013] On the other hand, there is no problem so far as the voltage applied to the alternating current signal as the reference bias voltage V 1 is clear, but if an offset or the like of the signal occurs in the middle of the path, the precision of the bias voltage V 1 is lowered. For example, when viewed by the path up to a comparison circuit for comparing the bias voltage V 1 and the intermediate voltage V 2 of the amplitude of the signal (not illustrated, for example existing inside the asymmetry processing circuit 240 ), the precision of the two are liable to differ and the precision of detection of the asymmetry is liable to fall due to an offset occurring in the peak hold circuit for finding the intermediate voltage V 2 .
[0014] In order to prevent such a fall of the precision of detection of asymmetry, correction must be carried out in each circuit or the precision of detection of each circuit block must be raised, so there are disadvantages of an increased complexity of the system, sensitivity to fluctuations of measurement conditions or the signal level, and a susceptability to interference.
SUMMARY OF THE INVENTION
[0015] An object of the present invention is to provide an asymmetry detection circuit having a simple circuit configuration, capable of realizing reliable detection without depending upon the signal level, and capable of realizing high precision asymmetry detection almost entirely free from the influence of voltage offset or the like, and a detection method of the same.
[0016] To attain the above object, according to a first aspect of the invention, there is provided an asymmetry detection circuit having an alternating current separation means for outputting an alternating current component of an input signal, a clamping means for adding a predetermined bias voltage to the alternating current signal obtained from said alternating current separation means, a comparing means for comparing the output of said clamping means with a reference voltage in accordance with said bias voltage and outputting a pulse signal in accordance with a duty ratio of the output signal of said clamping means in accordance with the related comparison result, a voltage/current converting means for converting said pulse signal to a current signal, an integrating means for integrating said current signal and outputting an integrated signal, and a filter for eliminating the alternating current component of said integrated signal and outputting a direct current component.
[0017] Preferably, said alternating current separation means comprises a capacitor cutting off the direct current component.
[0018] Preferably, said integrating means comprises a capacitor charged or discharged by said current signal.
[0019] Preferably, said filter comprises a low pass filter.
[0020] According to a second aspect of the present invention, there is provided an asymmetry detection method for detecting the asymmetry of an input signal, comprised by the steps of cutting off a direct current component of said input signal and outputting an alternating current component, adding a predetermined bias voltage to said alternating current component and clamping said input signal by the related bias voltage, comparing said clamped signal and the reference voltage in accordance with said bias voltage and outputting a pulse signal representing the duty ratio of said clamped signal in accordance with the related comparison result, converting said pulse signal to a current signal, integrating said current signal and outputting an integrated signal, and eliminating the alternating current component of said integrated signal and outputting the direct current component.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] These and other objects and features of the present invention will become clearer from the following description of the preferred embodiments given with reference to the attached drawings, wherein:
[0022] [0022]FIG. 1 is a circuit diagram of an embodiment of an asymmetry detection circuit according to the present invention;
[0023] [0023]FIG. 2 is a waveform diagram showing a definition of asymmetry;
[0024] [0024]FIG. 3 is a waveform diagram showing a principle of asymmetry detection in the present embodiment;
[0025] [0025]FIG. 4 is a circuit diagram showing an example of a conventional asymmetry detection circuit; and
[0026] [0026]FIG. 5 is a waveform diagram showing a principle of detection of the conventional asymmetry detection circuit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] [0027]FIG. 1 is a circuit diagram of an embodiment of an asymmetry detection circuit according to the present invention.
[0028] As illustrated, an asymmetry detection circuit 100 of the present embodiment is constituted by a duty ratio detection circuit 110 , a filter 120 , and a capacitor 130 (C 2 ).
[0029] The duty ratio detection circuit 110 is comprised by a capacitor 140 (C 1 ), resistor 150 (R 1 ), constant voltage source 160 (V 2 ), comparator 170 , and voltage/current converter (V/I converter) 180 .
[0030] Below, an explanation will be given of the configurations and functions of parts of the asymmetry detection circuit of the present invention by referring to FIG. 1.
[0031] In the duty ratio detection circuit 110 , the capacitor 140 cuts off the direct current component of the input signal S in and allows only the alternating current component to pass through.
[0032] The constant voltage source 160 supplies any constant voltage V 2 as the reference voltage.
[0033] The capacitor 140 , the resistor 150 , and the constant voltage source 160 give a bias voltage in accordance with the constant voltage V in to the input signal S in as an average picture level (APL) value. Namely, the input signal S in is clamped according to the constant voltage V 2 .
[0034] As illustrated, the input signal S in is input to one input terminal T in1 of the comparator 170 via the capacitor 140 . The resistor 150 and the constant voltage source 160 are connected in series between the input terminal T in1 of the comparator 170 and a reference potential (ground potential) GND. A middle point of connection of the resistor 150 and the constant voltage source 160 is connected to the other input terminal T in2 of the comparator 170 .
[0035] For this reason, a signal S AC obtained by APL clamping the input signal S in is applied to the input terminal T in1 of the comparator 170 , and the constant voltage V 2 is input as the reference voltage to the input terminal T in2 .
[0036] The comparator 170 compares the signal S AC and the reference voltage V 2 and outputs a pulse voltage signal V CMP in accordance with the result of comparison. In the comparator 170 , the reference voltage for comparison of the signal S AC is the APL value. Therefore, as a result of comparison of these signals, a voltage pulse V CMP in accordance with the duty ratio in the APL value is output.
[0037] The voltage/current conversion circuit 180 converts the input voltage signal to a current signal. Namely, the voltage/current conversion circuit 180 outputs a current I C in accordance with the voltage V CMP output by the comparator 170 .
[0038] The capacitor 130 is charged or discharged by the current I C output by the voltage/current conversion circuit 180 . Due to this, an integrated voltage V C is obtained from the terminal of the capacitor 130 in accordance with the output current I C .
[0039] The integrated voltage V C obtained by the capacitor 130 is input to the filter 120 . The filter 120 is comprised by for example a low pass filter. By the low pass filter, the alternating current signal component contained in the integrated voltage V C is eliminated. As a result, the direct current component contained in the integrated voltage V C is output. The direct current component is output as an asymmetry detection result S ASYM of the input signal S in .
[0040] Next, an explanation will be made of the principle of asymmetry detection in the present embodiment by referring to the waveform diagrams shown in FIG. 2 and FIG. 3.
[0041] [0041]FIG. 2 is a waveform diagram of the definition of asymmetry of alternating current signals. The asymmetry of the alternating current signals is defined as the ratio between the upper limit peak value and the lower limit peak value with respect to the direct current voltage value by which the duty ratio becomes 50%.
[0042] As illustrated, it is assumed that the duty ratio becomes 50% when the alternating current signal S in is clamped by the voltage V 1 . At this time, when the upper limit value of the signal S in that is, the positive peak level, is A, and the lower limit value, that is, the negative peak level, is B with respect to the voltage V 1 , the asymmetry ASYM of the signal S in is found by the following equation:
ASYM=( A−B )/( A+B )×100% (2)
[0043] According to equation (2), the case where the asymmetry ASYM is 0% arises when the upper limit value and the lower limit value are equal and A=B. Namely, when the asymmetry ASYM is 0%, the alternating current signals exhibit completely vertically symmetrical shapes.
[0044] Here, consider a triangle with a bottom side set at the duty ratio and with a height set at the peak value (upper limit value or lower limit value). As areas of this triangle, a positive side area S p and a negative side area S n can be found as follows.
S p =50 ×A /2 (3)
S n =50× A /2 (4)
[0045] [0045]FIG. 3 shows the area S p and the area S n with respect to the case where the input signal S in has the APL value (voltage V 2 ).
[0046] When the asymmetry is 0, S p and S n found according to equations (3) and (4) satisfy the following equation:
S p =S n (5)
[0047] On the other hand, when the asymmetry is a number other than 0, S p and S n found according to equations (3) and (4) satisfy the following equation:
S p ≠S n (6)
[0048] On the other hand, the APL value is the average value of the alternating current signals, so is a direct current voltage value always satisfying equation (5). When the asymmetry is a number other than 0, A is not equal to B. In the APL value, by equation (5), the duty ratio does not become equal to 50%.
[0049] Namely, even if the peak level of the alternating current signals is not monitored, by monitoring the duty ratio in the APL value of the alternating current signals, the asymmetry of the alternating current signals can be detected.
[0050] Below, an explanation will be made of the operation of the asymmetry detection in the asymmetry detection circuit of the present embodiment by referring to FIG. 1.
[0051] First, the input alternating current signal S in is input to the duty ratio detection circuit 110 . In the duty ratio detection circuit 110 , the direct current component of the input signal S in is cut off by the capacitor 140 . Further, by the resistor 150 and the constant voltage source 160 , the signal S AC APL clamped at the constant voltage V 2 is obtained and input to the input terminal T in1 of the comparator 170 . The constant voltage V 2 is input as a comparison reference voltage to the input terminal T in2 of the comparator 170 .
[0052] In the comparator 170 , signals input to the input terminals T in1 and T in2 are compared. As a result of comparison, a voltage pulse V CMP indicating the duty ratio in the APL value is output. Namely, the duty ratio of the input signal S in with respect to the APL value is represented by the pulse width of the output pulse signal V CMP of the comparator 170 .
[0053] The voltage pulse signal V CMP output from the comparator 170 is input to the voltage/current conversion circuit 180 . As a result of the conversion, a current signal I C in accordance with the voltage pulse signal V CMP is output.
[0054] The capacitor 130 is charged or discharged by the current signal I C . Namely, the current signal I C is integrated, and a voltage V C is obtained as the integrated signal from the terminal of the capacitor 130 .
[0055] By the filter 120 , the alternating current component of the integrated signal V C is eliminated, and only the direct current component is output. This output signal indicates the asymmetry of the input signal S in and is output as the asymmetry detection signal S ASYM .
[0056] As explained above, according to the present embodiment, by just using a simple circuit, it is possible to reliably detect the asymmetry of the input signal. Also, in the duty ratio detection circuit, since the APL value is given by the constant voltage source, the signal S AC obtained by clamping the input signal S in by the APL value is generated, and further the signal S AC and the voltage V 2 of the constant voltage source serving as the reference voltage are compared by the comparator 170 , the duty ratio can be correctly detected. By the voltage/current conversion circuit 180 , the duty ratio detection result is converted to the current signal I C , the integrated signal V C is found by the capacitor 130 in accordance with that, and the asymmetry can be detected in accordance with the direct current component of the integrated signal. For this reason, it is possible to reliably detect the asymmetry almost completely free of any influence from fluctuation of the signal. Further, the circuit configuration is extremely simple. For example, for the comparison circuit 170 , voltage/current conversion circuit 180 , and the filter 120 , it is not necessary to use particularly limited elements. Already existing elements can be used. Therefore, development and manufacturing costs of a system including an asymmetry detection circuit can be kept low.
[0057] Summarizing the effects of the invention, as explained above, according to the asymmetry detection circuit of the present invention and the detection method of the same, asymmetry can be reliably detected by a simple circuit configuration and the result of detection of asymmetry is obtained based on the result of integration of the signal, so not only can the detection result be output as a voltage signal, but also reliable detection can be realized without dependance on the fluctuation of level of the input signal.
[0058] Further, according to the present invention, there is almost no influence of direct current offset of the input signal and offset occurring in the signal processing circuit, so there is the advantage that a high precision can be held in the result of detection of asymmetry.
[0059] While the invention has been described with reference to specific embodiments chosen for purpose of illustration, it should be apparent that numerous modifications could be made thereto by those skilled in the art without departing from the basic concept and scope of the invention. | An asymmetry detection circuit having a simple circuit configuration, capable of realizing reliable detection without dependance on the signal level, and capable of realizing high precision asymmetry detection almost completely free of any influence from a voltage offset or the like, and a detection method of same, wherein a capacitor cuts off a direct current component of an input signal and passes alternating current component, a bias voltage is added to the alternating current component in accordance with a constant voltage of a constant voltage source to generate an APL clamp signal, a comparator compares the signal with a constant voltage and outputs a pulse voltage signal representing a duty ratio of the signal in the APL value, a voltage/current conversion circuit outputs a current signal to charge or discharge a capacitor to generate an integrated signal, and a filter eliminates the alternating current component of the integrated signal and outputs the direct current component as an asymmetry detection signal. | 6 |
FIELD OF THE INVENTION
The present invention relates generally to electric space heaters. More particularly, the present invention relates to controlling and defining the extent of focusing of infrared radiation from a space heater product.
BACKGROUND OF THE INVENTION
For a variety of reasons, a relatively small space such as a room may require heat. This heat may be in addition to that furnished from existing air treatment systems. One way to provide additional heat is with an electric portable heater. One type of such space heaters is a relatively small, sometimes floor-standing, heater that is configured to run on premises distribution circuits, that is, normal household and business wiring.
Heaters of various types may emit heat by radiation, convection, or conduction. A non-radiative electric heater may, for example, have one or more heating elements that release heat at comparatively low energy to raise the temperature of a quantity of air. Such heaters may then blow that heated air into a space using one or more fans or other circulation-promoting apparatus, so that a significant proportion of the heating performed by such heaters involves mixing heated air into ambient air, while direct radiation of heat may represent a secondary characteristic of such heaters.
Typical radiative electric heaters, by contrast, may release the majority of their heat in the form of infrared radiation emitted by one or more heating elements operated at comparatively high energy levels. Such heating elements typically combine infrared radiative heating of objects in the path of the radiation with a small amount of direct heating of the intervening air. Other heater types may combine these modes.
While some styles of heaters emit their heat from a front side only, the radiative heating elements within such front-radiating heaters typically radiate uniformly in all directions. As a consequence, it may be desirable to use an infrared reflector to redirect heating element radiation that would otherwise radiate upward, downward, or toward the rear of the heater so that as much of the heat as is practical may be directed out the front.
Radiative heaters may also have fans or other air circulation devices, which circulation devices may promote uniform heating of spaces in which the heaters are installed, may minimize temperature rise in the heater, and may improve the effectiveness of thermostat devices used as part of the heaters to maintain equilibrium temperature in a heated space.
In some instances, it may be desirable for a radiative heater to provide infrared heating that is focused in a general direction, such as generally in front of the heater, but diffused over a range in that direction to provide heat over a large area.
Accordingly, it is desirable to provide a radiative heater that can promote diffusion of heat through a broad region generally centered on the front of the heater.
SUMMARY OF THE INVENTION
The foregoing needs are met, to a great extent, by the present invention, wherein in one aspect an apparatus is provided that in some embodiments provides a radiative heater that can promote diffusion of heat through a broad region, which region may in some embodiments be substantially centered on the front of the heater.
In accordance with one embodiment of the present invention, a radiant heater is provided. The heater comprises a heating element configured to radiate heat, and a reflector located proximate to the heating element. The reflector has a generally parabolic shape with the exception of having a generally middle portion of the reflector displaced, while a first edge and a second edge of the reflector remain approximately in positions associated with the generally parabolic shape.
In accordance with another embodiment of the present invention, a radiant heater is provided. The heater comprises means for radiating heat, and means for reflecting heat in a direction. The reflecting means has a generally parabolic shape, with the exception of having a middle portion of the reflecting means displaced, while a first and a second edge of the reflecting means remain approximately in positions associated with the generally parabolic shape.
In accordance with yet another embodiment of the present invention, a method for applying radiant heat is provided. The method comprises the steps of configuring a radiant heat generating device for connection to an electrical power source, displacing a middle portion of a radiant heat reflector configuration from a substantially parabolic shape while leaving a first extent and a second extent of the radiant heat reflector configuration substantially undisplaced, enclosing an electrical power circuit, guarding the radiant heat generating device from physical intrusion, and providing electrical connectivity from the radiant heat generating device to an electrical terminal apparatus configured as a component of the radiant heat applying method.
There have thus been outlined, rather broadly, certain embodiments of the invention, in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a first perspective view illustrating a heater according to an embodiment of the invention.
FIG. 2 is a section view comparing the reflector shape profiles for a generally parabolic reflector and the reflector according to an embodiment of the invention.
FIG. 3 is a graph showing the relative heat profiles of a heater having a generally parabolic reflector and a heater according to an embodiment of the invention.
FIG. 4 is an isometric cutaway view of a heater reflector and associated elements according to an embodiment of the invention.
FIG. 5 is a second perspective view illustrating the louvers and feet of an embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention will now be described with reference to the drawing figures, in which like reference numerals refer to like parts throughout. An embodiment in accordance with the present invention provides a radiant heater with infrared reflectors for one or more heating elements generally configured for broad heat diffusion in a generally forward direction.
FIG. 1 is a perspective view that shows an embodiment in accordance with the present invention. Shown is a heater 10 with a housing 12 , and a grille 14 that generally prevents direct access to a heating element 16 . FIG. 1 also shows additional features of a heater, such as a base 18 , feet 20 , an electrical cord 22 with a plug 24 , a handle 26 , a power switch 28 , a tip switch (internal), a thermostat 30 , an indicator light 32 , and a thermal overload 34 . FIG. 1 further shows the fittings 36 , 38 , and 40 used to attach the defocused reflector 42 to the visible side of the housing 12 and to maintain the broad diffusion capability of the reflector 42 .
A housing 12 of the type shown is generally suitable for containing and preventing inadvertent contact with electrical components and for providing a rigid mechanical framework in which heating element 16 and the defocused reflector 42 may be mounted and held in comparatively immovable relationship to the other components therein. A housing 12 may be made of metal, suitable nonmetals, or a combination thereof, and may be formed of one or more pieces by a variety of manufacturing methods such as punching and pressing metal parts, molding plastics, and the like. Component parts may be given corrosion-resistant finishes where appropriate. Parts may be joined to form an integral whole using fastenings such as screws, rivets, and clips, integral attachment fittings such as self-hinges, barbs, and receptacles, and assembly materials and processes such as welds, solders, and glues if needed.
The grille 14 shown is one of a variety of suitable embodiments. Grilles 14 of comparable function may be welded or otherwise bonded from suitable materials, or may be punched and pressed, cast, or formed by other processes suitable to the materials chosen. A typical grille 14 may be mounted substantially permanently to the housing 12 , for example with clips, screws, barb fittings, spring tension, and the like.
FIG. 1 shows a heating element 16 , one of many common types of heating elements that may be suitable for the instant invention. Suitable types include resistive ribbon, a heating element sold under the trademark CALROD® (a substantialy continuous, commonly metallic sheath surrounding a nickel chromium or similar resistance wire, with thermally conductive, electrically insulating material between; CALROD is a registered tradename of the General Electric Corporation), a resistance wire wound on an insulating core, and a fused-quartz-jacketed heating element, as well as other types. Any heating element type, when applied to the instant invention, may have a generally linear configuration and generally uniform radial distribution of radiant energy about a longitudinal axis. Typical materials for a resistive heating element include nickel-chromium-iron alloys.
A base 18 is shown in FIG. 1 . The base 18 shown separates potentially warm regions of the housing 12 from a surface on which it would otherwise rest, and is one of various embodiments capable of performing this function. While many portable heaters incorporating the inventive apparatus may have bases, heaters intended for mounting to a wall or overhead support, for example, may not include bases on which they can stand. Still other heaters may have separate bases or stands to which they may be permanently, adjustably, or removably attached.
Feet 20 are shown beneath the base 18 . Where used, feet 20 may be of any suitable shape, and may be variously insulating, skid-resistant, and/or made from thermosetting (non-melting) material as appropriate. The use of feet 20 may in some embodiments enhance airflow beneath the base 18 bottom surface. This is addressed further under FIG. 5 , below. The number of feet 20 used may be as few as one for some embodiments, while other embodiments may use any number, although it may be anticipated that many embodiments use three or four feet 20 .
A flexible power cord 22 terminated in a 3-wire plug 24 is shown. A typical cord 22 may also be terminated in a 2-wire plug 24 . A flexible or semirigid cord 22 , substantially permanently attached to the housing 12 , may provide utility to a space heater without imposing a requirement on a user to manage a separate electrical wiring arrangement. Notwithstanding the desirability of a built-in cord 22 for some applications, a cord 22 that can plug into a socket on the heater may also be used. Similarly, for other applications, electrical contacts at fixed locations such as terminals or free-hanging wires within the housing 12 may be provided so that a user can make electrical connections, which connections may use conduit, premises wiring materials, electrical cord, or the like. In such applications, cover plates may allow electrical connections made by the user to be guarded against intrusion or disruption.
A handle 26 is an optional feature of a portable heating device 10 . If present, a handle 26 may, for example, be insulating and/or made from thermosetting (non-melting) material. A handle 26 may instead be predominantly metallic, where a metallic handle may in some embodiments be attached to the housing 12 using insulating standoffs or clips. A handle 26 may also be an integral part of the housing 12 , for example.
A power switch 28 is shown in FIG. 1 . This may be a basic on-off switch 28 or may additionally function to allow selection between multiple power settings. For example, a three-position switch 28 can have high and low output positions and an off position, while other switch 28 styles may allow one or more intermediate output settings as well. For some embodiments, there may be no power switch 28 , such as for permanently-mounted heaters 10 operated from fixed remote controls.
The use of multiple output settings may include two or more output levels and multiple output functions. The number of output power levels available may be determined by details of implementation. For example, a heater with a single element 16 and an on-off switch 28 may have a single output level. A heater with two unequal heating elements 16 can power the lower alone, the higher alone, or both in parallel to get three output levels, which requires a four-position switch 28 (off-low-medium-high) and appropriate internal wiring. Alternate embodiments may, for example, omit one of the three “on” positions to provide a two-level heater, may reduce power by configuring elements in series rather than in parallel, or may remove power to elements in series (to increase) or parallel (to reduce) power output.
The embodiment shown in FIG. 1 combines forced-air and radiant heating by adding a fan internal to the heater 10 , which fan runs at some switch 28 settings in conjunction with heating element 16 and with a second heating element substantially concealed behind the visible reflector 42 . The second heating element is positioned between a second reflector (not shown) and the visible reflector 42 , which two reflectors create an air slot through which fan-forced air passes at some switch 28 settings. Inlet air in support of this operating mode is admitted in the embodiment of FIG. 1 through louvers in the base and rear of the enclosure 12 , as discussed below under FIG. 5 .
FIG. 1 further shows an optional built-in thermostat 30 . A thermostat 30 allows a self-contained portable heater 10 to be self-regulating, switching itself on when an ambient temperature drops below a minimum and switching itself off when the ambient temperature exceeds a maximum. A thermostat 30 may have hysteresis to permit power cycling to occur at moderate intervals. Since the heater 10 itself may need to cool after cycling off before it can sense the ambient temperature, a thermostat 30 may need greater hysteresis than would be required if, as in an alternate embodiment, the thermostat 30 were installed in the heated space but remote from the heater 10 .
FIG. 1 further illustrates an optional indicator light 32 . An indicator light 32 can be configured to indicate when power is applied to the heater 10 or when heat is being emitted by the heater 10 . Alternative embodiments could indicate both of those functions, or could have contact closures to permit remote detection of the mode of the heater 10 .
FIG. 1 further shows a thermal overload circuit interrupter 34 . A thermal overload interrupter 34 may be used to automatically shut down the heater 10 in event of an overtemperature or overcurrent event. The externally visible element of the thermal overload interruptor 34 in FIG. 1 is a reset button. Thermal overload interrupters 32 may be resettable or nonresettable. Resettable types may be reset using, for example, a push or a pull element, a toggle, or an automatic cycling device with no actuator. Fuses may be used as interrupters.
A tip switch (entirely enclosed within the housing in the embodiment shown and thus not visible in the figures shown) is a device to immediately remove power from a heater 10 if the heater 10 is tilted outside an allowed range or is knocked over. In some embodiments a tip switch may also detect if a heater is picked up. Fixedly mounted heaters may not use a tip switch. Some styles of tip switch may be integral with the power switch 28 , the thermostat 39 , or the overload circuit interrupter 34 .
FIG. 2 is a section view that shows both a substantially parabolic reflector configuration 50 that approximates a shape known as a parabolic cylinder, and the generally nonparabolic reflector profile 52 of the inventive apparatus. It may be observed that the bulk of the radiant energy reflected by a generally parabolic shape 50 of the type shown, with a heater element 54 located proximal to its focus, travels along a roughly parallel path. The defocused reflector shape 52 of the inventive apparatus, by contrast, may have its heater element 56 located away from any focal point of the reflector 52 . This may result in increased scattering of the reflected heat, so that there is a less intense, more distributed zone of highest heat proximal to the grille 14 of FIG. 1 .
Formation of the nonparabolic, defocused reflector 52 of the inventive apparatus may be realized by bending a self-supporting parabolic reflector 50 into the generally nonparabolic profile shown and stabilizing the defocused reflector 52 so formed using deflection fittings such as screws, rivets, clips, tabs, or brackets. The defocused reflector 52 profile of FIG. 2 may also be formed by pressing the reflector material directly into the preferred shape using a die, fitting the material into a groove, slot, guide, series of retention fittings, or the like that are integral with or retained by the housing 12 of FIG. 1 , curving the reflector material around a forming profile, or otherwise shaping the reflector material to achieve the properties herein described.
FIG. 3 is a graph comparing the heat distribution intensities of a parabolic reflector and the inventive reflector. Curve 60 represents the heat distribution characteristic of a parabolic reflector, while curve 62 represents the heat distribution characteristic of an embodiment of a reflector in accordance with the present invention. Evident in the graph is that the peak energy in the region of highest radiative intensity for the paraboloid reflector may be appreciably greater than the corresponding region for the inventive apparatus.
FIG. 4 is a view of a defocused reflector 42 with first, second, third, and fourth attachment apparatuses 36 , 72 , 40 , and 76 , where each of the mounting apparatuses 36 , 72 , 40 , and 76 supports a corner of the defocused reflector 42 . The defocused reflector 42 further employs first and second deflection fittings 38 and 74 that maintain the attached reflector 42 in a defocused orientation. The first and second attachment apparatuses 36 and 72 may in some embodiments take the form of a single rod around which an upper edge 78 of the reflector 42 is formed. In some embodiments, a bottom edge 80 of the reflector 42 may likewise be formed around a rod serving as the third and fourth attachment apparatuses 40 and 76 . Such rods may penetrate the housing 12 and be attached thereto by fastenings 82 , or may be attached by other suitable methods. In other embodiments, the first, second, third, and fourth attachment apparatuses 36 , 72 , 40 , and 76 may be realized in the form of tabs or equivalent fittings integral with or attached to the reflector 42 . Such tabs may be inserted into slots, screwed or riveted, or welded to the housing 12 , or may be integral with the housing 12 .
Deflection fittings 38 and 74 are shown in FIG. 4 . The fittings assist in establishing the shape of the reflector 42 and in stabilizing the curve thereof. Such fittings may be fastening hardware of various styles, such as screws, as shown in FIG. 4 , or rivets, or may, for example, be established as tabs attached to or formed out of the housing 12 material. In some embodiments, fastening hardware may be secured to an inner housing wall and thus not visible outside the housing 12 .
FIG. 4 further shows mounting brackets 84 and 86 that carry a heating element 16 . As shown, the reflector 42 provides support for the brackets 84 and 86 . This arrangement couples the shape of the reflector 42 to the position of the heating element 16 . Other arrangements, such as one in which the heating element brackets are attached to the housing 12 , may permit the reflector 42 shape and heating element 16 position to be varied independently. Electrical wires 90 provide power to the heating element 16 .
Alternative reflector 16 shapes may also provide effective defocusing, such as a vee shape or a “washboard” shape in place of the approximate paraboloid of a focused reflector. Similarly, placing the heating element 16 away from any functional axis of focus of a reflector of any configuration may further reduce and distribute heat concentration.
FIG. 5 shows an oblique view from below. Here, the feet 20 may be seen to be able to position the base 18 off a floor. Since air flow into the heater 10 by back louvers 92 and bottom louvers 94 can promote the forced-air modes of operation described above for the embodiment shown, the use of feet 20 as indicated may be desirable. Alternative embodiments can provide for air flow into the heater 10 without bottom louvers 94 , in which embodiments inclusion of feet 20 may nonetheless be desirable.
Although an example of the defocused radiative heater 10 is shown with insulating feet 20 to rest on a floor, it will be appreciated that the heater 10 can be used attached to a vertical surface such as a wall or hung from a ceiling using a suitable support mount. Also, although the heater 10 is useful for space heating in spaces intended for human occupancy, it can also be used both for warming other habitable spaces, such as barns and kennels, and for performing such functions as maintaining air temperatures above freezing in manufacturing and storage facilities, machinery rooms, and the like.
The many features and advantages of the invention are apparent from the detailed specification, and, thus, it is intended by the appended claims to cover all such features and advantages of the invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to that fall within the scope of the invention. | A radiant heater includes a radiant heat source and a reflector to direct the bulk of the heat generated by the radiant source in one direction. The shape of the reflector determines the radiant pattern of the heater, and generally defocuses the output to provide a diffuse heat pattern that is substantially free of hot spots. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention herein pertains to high production commercial embroidering as is used to place logos or names on shirts as required by businesses and particularly to the continuous hoop framing of such garments before they are loaded on an embroidering machine.
2. Description of the Prior Art and Objectives of the Invention
In recent years the demand for garments having first quality, logos, trademarks and the like has increased as more and more businesses realize the benefits of supplying workers with shirts, jackets and other garments employing company identification. Also, sports fans have become increasingly enthusiastic about purchasing apparel which identifies their team. While printing of identifying markings on various items has not been totally replaced, the demand for sewn or embroidered goods has rapidly multiplied and shop owners which use multiple-head embroidering machines (which may embroider twelve to fifteen garments at a time), which are computer controlled, are now running two to three shifts a day to keep up with demand. Hoop framing, as is conventionally performed in the trade, utilizes a relatively large exterior embroidery hoop which may be placed, for example, inside a t-shirt to provide a selected area upon which the logo or emblem is later embroidered. Once the exterior hoop is so placed, an interior embroidery hoop is then urged from outside the shirt into the exterior hoop, thereby sandwiching a tight circle of cloth therebetween. The so "hooped-framed" garment is then positioned in a hoop holder on an embroidering machine and the logo or emblem is then sewed within the framed circle. After sewing, the framed garment is removed from the machine, the hoops disengaged, and another framed garment is placed on the embroidering machine and the cycle repeated. For multi-head embroidering machines, twelve to fifteen framed garments are simultaneously loaded and embroidered.
While the sewing (or embroidering) is usually completed in rapid fashion and the loading and off-loading of the hoop-framed garments can be quickly, manually carried out, the steps of hoop framing the garment are generally slow and create bottlenecks in the embroidering process. While some mechanical framed presses have been utilized to increase the hoop framing speed, such mechanical devices are lacking in versatility and cannot be easily and quickly varied for different garment sizes.
Thus with the disadvantages and shortcomings of prior hoop framing methods, the present invention was conceived and one of its objectives is to provide a jig and method for embroidery hoop framing which will allow a high volume of particularly sized garments to be rapidly, accurately and consistently hoop-framed.
It is another objective of the present invention to provide an apparatus and a method for hoop framing garments such as shirts which will allow the jig employed to be quickly changed for use from one size garment to another.
It is still another objective of the present invention to provide an embroidery hoop framing jig having an insert which will accommodate various positionings of logos or emblems on a garment and which will accommodate many sizes of embroidery hoops to suit the needs of the user.
It is also another objective of the present invention to provide an embroidery hoop framing jig which is positioned on a stand to provide convenience for the user.
Various other objectives and advantages of the present invention become apparent to skilled in the art as a more detailed description is set forth below.
SUMMARY OF THE INVENTION
The aforesaid and other objectives are realized by providing an embroidery hoop framing jig and method which will allow accurate, consistent hoop framing of garments or other items for embroidering purposes. The framing jig includes a curved stand which is attached to the back of the jig to position it at an approximately eighty degree (80°) angle for stability and convenience to the user. The hoop framing jig includes a base mounted stand and a base insert which can be turned to any of a variety of positions for placement in the base to suit the user's needs. The insert may include a plurality of hoop apertures for various size embroidery hoops and, in addition to being turned, the insert can be reversed for additional versatility during positioning in the base. The apertures in the base are configured to accept conventional exterior embroidery hoops and may, for example, accommodate four different hoop sizes. A tension member on the insert allows a properly sized exterior embroidery hoop to "snap" into the insert and be tightly held in place as the garment is positioned over the jig and the interior embroidery hoop pressed into engagement therewith. Side and top base extensions attached to the base allow the jig to increase in size for larger garments and a collar slide helps insure proper garment positioning. Knobbed threaded members are tightenable to insure that the side and top base extensions are secured in place and can be loosened for quick adjustment of the side and top base extensions. The collar slide likewise has knobs for tightening the slide at a chosen lateral position.
The method utilizing the embroidery hoop framing jig includes positioning the insert in the base with the selected aperture at the desired location. An exterior embroidery hoop is then manually urged into the selected aperture. Next a garment or other item of required size is placed over the hoop framing jig and the top and side base extensions are adjusted to snugly fit within the garment. The collar slide is then adjusted as necessary and lastly, an interior embroidery hoop is urged into the prepositioned exterior embroidery hoop to tightly sandwich a circle of garment material therebetween. The garment is then removed from the hoop framing jig with the embroidery hoop attached and positioned on an embroidering machine for embroidering purposes. Another garment of the same size or dimensions can then be placed on the hoop framing jig without modification to the jig and subsequent garments can be rapidly "hoop framed" and embroidered.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a front view of an embroidery hoop framing jig of the invention with the left side, right side and top base extensions slightly spaced from the base;
FIG. 2 demonstrates a view of the framing jig as shown in FIG. 1 with a shirt positioned thereon which has been hoop framed for embroidering purposes;
FIG. 3 illustrates a side elevational view of the hoop framing jig as shown in FIG. 1;
FIG. 4 shows a view of the base insert as shown in FIG. 1 which has been rotated ninety degrees (90°);
FIG. 5 depicts the hoop framing jig as shown in FIG. 1 from a rear elevational view;
FIG. 6 pictures a cross-sectional view along lines 6--6 of FIG. 5; and
FIG. 7 demonstrates a top plan view of the collar slide along line 7--7 of FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred form of the apparatus of the invention is presented in FIGS. 1-7 whereby a hoop framing jig is seen having a substantially rectangular base with a depression or cavity for accommodating an insert. The insert is receivable within the base depression in any of four ninety degree (90°) turned positions and can also be reversed (front to back) to increase its positioning versatility. The insert includes tension members along spaced apertures and, in the insert preferred form, four different apertures of various sizes are utilized for maximum convenience. A left side base extension, right side extension and a top base extension are slidably joined to the base to adjust the base for snugly fitting within a selected size garment. Threaded members are tightenable to a back plate to insure that the base extensions stay in the desired position during consecutive garment hoop framing. A collar slide is laterally adjustably tightenable along the upper surface of the top slide. A stand attached to the back plate of the base causes the hoop framing jig to realize an approximately seventy-five degree (75°) angle from the horizon for convenience in use.
The preferred method of the invention comprises positioning the insert in the base with a desired aperture at the required position. An exterior framing hoop is then placed in said desired aperture and a particular size garment is selected and drawn over the hoop framing jig. Next, the left and right base extensions are adjusted along with the top base extension to provide a snug garment fit with the exterior embroidery hoop centered around the area of the garment which is to be embroidered. Next, an interior embroidery hoop is urged with garment fabric into the prepositioned exterior embroidery hoop whereby a circle of fabric is held tightly between the exterior and interior hoops. The garment is next removed from the hoop framing jig with the embroidery hoops attached and the garment is subsequently positioned on an embroidering machine for stitching purposes. Thereafter, another exterior embroidery hoop is positioned in the desired aperture and another garment of the same size is positioned over the hoop framing jig without any modifications or adjustments required. An interior embroidery hoop is then urged with the garment fabric into the prepositioned exterior hoop and the garment is then removed for subsequent embroidering. This process is repeated over and over for as many garments of the same size as is required without adjustment to the jig. Thereafter, the embroidery frame hoop jig can be again adjusted for a different size garment and the process repeated as often as necessary.
DETAILED DESCRIPTION OF THE DRAWINGS AND OPERATION OF THE INVENTION
For a more complete understanding of the invention and its method of operation, turning now to the drawings, FIG. 1 shows a front view of an embroidery hoop framing jig 10 positioned on stand 11 which includes a substantially rectangular base 12 with insert 13 positioned therein. As seen in FIG. 4, base insert 13 is likewise somewhat rectangularly shaped and includes a plurality of apertures 14, 15, 16 and 17, each for receiving an exterior embroidering hoop. Apertures 14, 15, 16 and 17 are shown with various diameters for accepting and surrounding various size embroidery hoops although such apertures may be the same size if desired, or all different sizes.
Base insert 13 is formed from a one-half inch composite material to provide a light yet durable insert. Base 12 may be aproximately one inch (1") (2.54 cm) thick with a one-half inch (0.5") (1.27 cm) depression 22. Tension members 18, 19, 20 and 21 provide tension for an exterior embroidery hoop of a hoop set as may be positioned within respectively apertures 14-17. Insert 13 as seen in FIG. 4 can be rotated to four ninety degree (90°) positions to accommodate a particular hoop size and placement. As shown, insert 13 has four hoop apertures therein but any number and positioning of apertures may be utilized.
In FIG. 2, shirt 23 is in position on hoop framing jig 10 with interior embroidery hoop 24 in place. Interior hoop 24, as understood by those skilled in the art defines an area on the front of a shirt which is "framed" by a circular section of garment cloth between an exterior embroidery hoop (not seen) (inside shirt 23) and interior embroidery hoop 24.
As further illustrated in FIG. 1, hoop framing jig 10 includes left side base extension 25 and a right side base extension 26 slidably joined to base 12 to adjust to the particular width of a selected t-shirt or other garment to hold the garment is a relatively tight posture as seen in FIG. 2. Top base extension 27 is also shown in FIG. 1 which will provide additional height in the event a shirt is used which is longer than base 12. Top base extension 27, right side base extension 26 and left side base extension 25 are secured in place by threaded members 31, 29 and 30 respectively as seen in FIG. 5. FIG. 6 demonstrates a close-up view along lines 6--6 of FIG. 5 of left side base extension plate 32 which is slidably positioned between back plate 33 and hoop framing base 12. As shown, threaded member 30 is tightable into nut 34 (within base 12) and when threaded member 30 is tightened, prevents left side base extension 25 from moving. The same type of means is used for right side extension 26 and top base extension 27. In FIG. 7 a top view of collar slide 35 is shown with threaded members 38, 39 positioned in slots 40, 41 respectively. Collar slide 35 is moved laterally as needed depending on the particular shirt and/or mounting desired on jig 10.
As shown in FIG. 3, stand 11 allows jig 10 to be positioned at an approximately seventy-five degree (75°) angle and includes a stiffening brace 50. Brace 50 may be made of one inch (1") angle iron to provide rigidity and durability for stand 11.
The method of hoop framing employing jig 10 as shown in FIGS. 1-7 includes selectively positioning base insert 13 into depression 22 within base 12. Base insert 13 is so placed to provide the proper size and position of one or more apertures 14, 15, 16 or 17 as hereinbefore described. With base insert 13 so positioned, exterior framing hoop 36 as shown in FIG. 1 is positioned within aperture 15. Next, a shirt such as 23 shown in FIG. 2 is positioned over collar slide 35 and is urged downwardly along its full length to cover base insert 13. Next, right side base extension 26 and left side base extension 25 are released by threaded members 29, 30 respectively and are tightened as is top base extension 27 whereby shirt 23 is taut on jig 10. Next, an interior embroidery hoop such as 24 as shown in FIG. 2 is then pressed into exterior framing hoop 36 with fabric therebetween. Once shirt 23 is so framed, shirt 23 is then pulled upwardly from jig 10 with the interior and exterior framing hoops in place. The hoop-framed shirt can then be positioned on an embroidering machine and the stitching completed. In the meantime, during the embroidering process, another exterior embroidery hoop can be positioned in aperture 15, and another shirt of the same size positioned on jig 10 without adjusting the side or top base extensions and another interior framing hoop inserted to form a tight fabric circle whereupon the process can be repeated over and over without having to make adjustments for the overall jig size. As smaller or larger shirts are thereafter required, the proper positioning of insert 13 can be established, top base extension 27 and side base extensions 25, 26 adjusted and the hoop-framing process repeated. As shown, once jig 10 is properly adjusted, shirts of the same size can be hoop-framed continuously with minimal effort.
As would be understood, shirts are used herein for explanatory purposes and various other garments and items can be employed utilizing jig 10 to save time and effort in the hoop framing process. Also, greater consistency and accuracy is provided and precise, easy changes can be made depending on the size of the garments and the location of the embroidering as needed. | A framing jig is provided to insure accurate., consistent hoop framing of garments such as t-shirts, jackets, pants or other items for subsequent embroidering. The framing jig is especially useful in high production shops which require rapid hoop framing of a large number of similarly sized items. The framing jig includes a removable insert having a plurality of apertures for receiving variously sized exterior embroidery hoops and also includes adjustable side and top base extensions for quick changes to accommodate different size garments. The insert can be removed, rotated and replaced in a matter of seconds in the base for the most accurate and desired framing area possible. In addition, an adjustable collar slide permits the easy centering of the garment on the jig. | 3 |
BACKGROUND OF INVENTION
This invention relates to a microphone circuit used for a mobile telephone or the like and more particularly, to a microphone circuit having a control switch for changing the communication mode of the telephone.
This kind of microphone circuit is, for example, employed for a mobile telephone designed to accommodate a hands-free mode in which a loudspeaker and microphone are used with subscriber's hands free and a press-to-talk mode in which the loudspeaker and microphone are used alternatively. In the hands-free mode, howling or singing may occur due to crosstalk either in a transformer of a telephone switching office or between the loudspeaker and microphone or both. In order to avoid the singing, the microphone circuit includes a control switch which is manually actuated when the singing occurs, to provide a mode switching signal for changing the hands-free mode in to the press-to-talk mode.
In the conventional microphone circuit, the control switch connects a parallel resistor to or disconnects it from the output of a microphone unit. If the control switch is turned on, the DC bias voltage for the microphone unit decreases by the virtue of the resistor. This decrease of bias voltage is detected by a voltage comparator. The detected output is used as a control signal of mode switching.
Upon turning on the control switch, however, the load impedance of the microphone unit of the conventional microphone circuit decreases due to the resistor, so that not only the bias voltage but also the output signal voltage of the microphone unit decreases. In order to solve this problem, it may be possible to amplify the decreased output of the microphone unit using an amplifier connected to the output terminal of the microphone circuit. This solution increases the circuit size. Moreover, since this solution causes the amplification of the bias voltage in addition to the output signal, the predetermined bias voltage must be again modified. This modification further causes the change of the load impedance of the microphone unit and, therefore, the amplification factor must be modified again. Consequently, it is difficult to adjust the bias voltage and the amplification factor properly.
Another solution of the above problem is to provide a detection signal line for indicating the on/off status of the control switch. However, it means that another signal wire lead must be added to the two-wire lead microphone unit, with the result that the advantage of the two-wire lead microphone unit disappears.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a microphone circuit, wherein the status of the control switch for controlling the output of the control signal can be detected without a decrease in the output level of the microphone unit of two-wire leads.
Another object of the present invention is to provide a microphone circuit for both the hands-free mode and the press-to-talk mode of the mobile telephone.
In a device including a microphone circuit, the microphone circuit comprises microphone unit means operated by a DC bias voltage for providing a microphone output signal superposed on the DC bias voltage. A constant current source means is connectable in parallel with the microphone unit. First control switch means controls the parallel connection of the constant current source means to change the DC bias voltage. A voltage comparator means is connected in parallel with the microphone unit means for comparing the bias voltage with a predetermined reference voltage to detect the status of the control switch means and to provide a control signal.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the invention will be obtained from the detailed description below, with reference to the accompanying drawings, in which:
FIG. 1 is a block diagram of the mobile telephone system, to which, the microphone circuits of the present invention and the prior art are applicable;
FIG. 2 is a schematic diagram of a microphone circuit according to a preferred embodiment of the present invention;
FIG. 3 is a detailed schematic diagram of the circuit shown in FIG. 2;
FIG. 4 is a graphical diagram for showing the voltage outputs of a microphone unit and a voltage comparator shown in FIG. 2;
FIGS. 5A and 5B show the voltage waveforms of the outputs of the microphone units according to the prior art and the preferred embodiment of the invention, respectively;
FIG. 6 is a schematic diagram of a microphone circuit according to the prior art; and
FIG. 7 graphically shows the relationship between the load impedance of the microphone unit shown in FIG. 6 and its output voltage.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a transmission/reception antenna 1 is connected to a tranceiver (Tx Rx) 2, which in turn is connected to switches 3 and 4. The switches 3 and 4 connect the tranceiver 2 to either a handset unit 8 or a loudspeaker circuit 20 under the control of a control switch unit 5. The communication or conversation using the loudspeaker circuit 20 includes the aforementioned hands-free mode and press-to-talk mode. Since the communication using the handset unit 8 is usual in the mobile telephone system and is well-known in the art, the explanation thereof will be omitted.
The communication using the loudspeaker circuit 20 is performed in the following way. Suppose that the tranceiver 2 is connected to the loudspeaker circuit 20, as is shown in FIG. 1. A reception signal from the antenna 1 is fed sequentially to the tranceiver 2, switch 3, a loss insertion circuit 10, such as an attenuator, a switch 13, and finally a loudspeaker 14 from which the reception signal is output as a reception speech signal. On the other hand, a transmission speech signal from a microphone unit in a microphone circuit 15 is fed from a terminal 17 to a loss insertion circuit 12, and then transmitted, via switches 6 and 4 and the tranceiver 2, from the antenna 1 to a base station (not shown). Here, a loss control unit 11 controls the insertion loss given by the loss insertion circuits 10 and 12, to prevent the crosstalk between the speaker and the microphone. In the above explanation, it is assumed that both switches 6 and 13 are closed.
Now, it is assumed that the howling or singing occurs in the hands-free mode, due for example, to crosstalk in either a transformer in a telephone exchange office (not shown) or between the speaker 14 and the microphone circuit 15 or both. On this occasion, the subscriber manually closes a control switch contained in the microphone circuit for controlling the communication mode. The closed status of the control switch is applied from a terminal 16 to the switches 6 and 13. Consequently, the switches 6 and 13 are switched to operate in the press-to-talk mode. In other words, they are alternatively switched by the subscriber to operate in the press-to-talk mode communication.
In order to fully understand the present invention, the prior art microphone circuit will first be explained with reference to FIG. 6. In FIG. 6, a microphone unit 27 is a two-wire lead electret capacitor microphone, which is composed of a transistor 44, resistors 45 and 47, and a parallel plate capacitor 46 formed by a microphone vibrator plate. In response to a speech signal acting upon the vibrator plate 46, the microphone output is taken out from a terminal 17, to which a bias and load resistor 23 is connected. A serial connection of a resistor 51 and a control switch 25 is connected to the output of the microphone unit 17. When the control switch 25 is closed, the resistor 51 is inserted in parallel with the microphone unit 27, so that the DC bias voltage of the microphone unit 27 is reduced. This reduction is detected by a voltage comparator 24, output of which is taken out from a terminal 16 as a mode switching signal. The mode switching signal is used for switching from a hands-free mode to a press-to-talk mode in the system as is shown in FIG. 1.
This conventional microphone circuit has the following disadvantages. The output of the microphone unit 27 is taken from one end of bias and load resistor 23, that is, the terminal 17. Since this output is provided from the collector of the transistor 44 in the microphone unit 27, the load of the transistor 44, that is, the load of the unit 27 is affected by the insertion of the resistor 51, which occurs upon the closure of the control switch 25. Therefore, not only the DC bias voltage for the microphone unit 27, but also the microphone output signal at terminal 17, change due to the insertion of the resistor 51.
In FIG. 7, the relationship between the load impedance of the microphone unit and its output voltage is shown. As can been seen from FIG. 7, the output voltage of the microphone unit varies with the load impedance which, in the prior art circuit of FIG. 6, changes in response to the closure of the control switch 25. As a result, the output voltage of the microphone unit 27 has a waveform as is shown in FIG. 5A. In FIG. 5A, when the control switch 25 (FIG. 6) is closed at time t 1 , the output voltage of the microphone unit decreases. If this conventional microphone circuit is used in, for example, a mobile telephone, the transmission speech signal level decreases by closing the control switch 25 to switch the mode from hands-free to press-to-talk upon detection of the howling or singing.
In order to overcome this problem, it may be possible to amplify the decreased output voltage. However, this solution causes additional problems, such that the size of the circuit inevitably becomes large, as is mentioned above, and the adjustment of the bias voltage becomes complex. Also, another solution utilizes the detection wire lead for detecting the closure of the control switch but this solution, eliminates the advantage of the two-wire lead microphone unit.
An object of the present invention is to overcome the above-mentioned disadvantages. FIG. 2 shows a microphone circuit according to a preferred embodiment of the present invention.
A bias voltage V 1 for a microphone unit 27 is applied from a power source via resistor 23. The reference or threshold voltage V 0 of a voltage comparator 24 is less than the bias voltage V 1 given by resistor 23. When the control switch 25 is closed, current flows through a constant current source 26 from the power source via resistor 23. The bias voltage of the microphone unit 27 decreases to a voltage V 2 , which is lower than V 1 by the amount of the voltage drop of resistor 23. If the threshold voltage V 0 is higher than voltage V 2 , the voltage comparator 24 provides a detected output at a terminal 22 upon closure of the control switch 25.
Since the internal impedance of the constant current source 26 is infinite, the load impedance of the microphone unit 27 does not change even with the closing of the control switch 25, with the result that the output level of the unit 27 does not change. Thus, the level reduction problem can be overcome.
FIG. 3 shows the detailed schematic diagram of the circuit shown in FIG. 2. The construction of the microphone unit 27 is the same as the conventional unit shown in FIG. 6. The voltage comparator 24 is composed of an operational amplifier 35, a low-pass filter constituted by a resistor 34 and a capacitor 37, and a voltage divider constituted by resistors 33 and 36 to provide a reference voltage to the amplifier 35. The constant current source 26 is composed of capacitors 41 and 43, a transistor 39, and resistors 40 and 42. The capacitor 41 is a by-pass capacitor to absorb any noise which may be generated upon a closure of the control switch 25.
The bias voltage V 1 is supplied via resistor 23 to the microphone unit 27, the output of which is applied to the inverted terminal of the amplifier 35 by way of the low-pass filter composed of resistor 34 and capacitor 37. The reference voltage V 0 of the amplifier 35 is set by the voltage divider to be lower than the bias voltage V 1 , and is applied to the non-inverted terminal. When the control switch 25 is closed, the DC voltage is applied to the base of the transistor 39 via the low-pass filter constituted by the resistor 42 and the capacitor 43. A constant current determined by this DC voltage and the emitter resistor 40 flows through transistor 39, by which current the bias voltage V 2 for the microphone unit 27 is decided. The reference voltage V 0 is chosen to be larger than the bias voltage V 2 to detect the change of status of the switch 25.
FIG. 4 shows the voltage waveforms at microphone circuit output 21 and output terminal 22 of the voltage comparator 24 (FIG. 3). In this FIG. 4, the control switch 25 is open until time t 1 and the output voltage at microphone circuit output 21 is V 1 (the output speech signal is shown as being superposed on the bias voltage V 1 ) At time t 1 , the control switch 25 is closed. The result is that, at an instant when the voltage at terminal 21 falls below the reference or threshold V 0 , the output voltage at terminal 22 changes from a high level "H" to a low level "L". At time t 2 , the control switch is opened. The voltage at terminal 21 increases from V 2 to V 1 with the time constant determined by the capacitor 41, the resistor 23 and the output impedance of the microphone unit 27. At the instant when the voltage at terminal 21 exceeds the threshold V 0 , the voltage at terminal 22 changes from "L" to "H". Thus, the status of the control switch 25 is detected by the comparator 24. The terminals 21 and 22 of FIG. 4 correspond to the terminals 17 and 16 of FIG. 1, respectively.
Since the output impedance of the constant current source is theoretically infinite in comparison with the impedance of the microphone unit, the load impedance of the microphone unit 27 does not change even when the DC bias voltage of the unit 27 changes. Therefore, the output of the microphone at terminal 21 is not affected by the on/off status of the control switch 25.
FIGS. 5A and 5B show the voltage waveforms of the microphone circuits of the prior arr and of a preferred embodiment of the present invention, respectively. It is to be noted in FIGS. 5A and 5B that the DC voltage is omitted for brevity's sake. As shown in FIG. 5A, if the control switch 25 is closed at time t 1 , the output voltage of the prior art microphone circuit decreases as mentioned earlier, while it does not change in the circuit according to the preferred embodiment of the present invention as shown in FIG. 5B.
In case the preferred embodiment is used for the system shown in FIG. 1, the output voltage of the microphone circuit is not affected by the status of the control switch 25 on the press-to-talk mode.
In summary, the microphone circuit according to the present invention can detect the status of the control switch without a changing of the output voltage of the microphone circuit using two-wire lead microphone unit. | A microphone circuit for a mobile telephone is capable of operations in either of two modes, i.e. in a hands-free or a push-to-talk mode. A constant current circuit is coupled in parallel with the microphone to preclude a change in a DC bias voltage responsive to switch operations, especially in a push-to-talk mode. A voltage comparator compares the bias voltage with a reference to detect control signals and selects a preferred mode of operation. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of collaborative computing and more particularly to element identification in a collaborative computing environment.
2. Description of the Related Art
In a collaborative computing environment, elements including documents, roles, folders and attachments can be identified by name and stored by name or by a hierarchy of names in a central server. Identifying a collaborative computing element by name or a hierarchy of names can require a structured, unique method of storing and retrieving data, for example a file system or content repository. As such, in a collaborative computing environment, oftentimes the element identification structure can be presented to end users in the form of named folders, named documents and named files.
The identification of an element in a collaborative computing environment according to a name or hierarchy of names can result in several known problems. In particular, problems can arise in identifying an element according to name or a hierarchy of names when supporting computing systems that lack a central data store and where the data is distributed among multiple systems, or where the data is replicated across host platforms, or where a computing system provides collaborative services without connection to a central server. Additionally, in a collaborative computing environment utilizing names and hierarchy of names to identify elements, the alphanumeric characters for names to be used in naming elements can be limited in the circumstance that the data store for the collaborative computing environment is a file system. In particular, many symbolic characters are not permitted in naming files for most file systems.
In order to support the identification of elements using names and hierarchies of names, collaborative environments have limited element storage to a centralized data store. However, the use of a centralized data store can be limiting, particularly in respect to offline computing and performance when multiple clients access the centralized data store. Other systems provide for distributed collaborative environments, including offline, disconnected environments with the condition to allow “read” requests on all the data stores for the distributed systems, but to limit write operations to a single host system. Accordingly, slow performance can result on “write” requests because the single host can be geographically located in a different continent of the globe. Furthermore, the single host can be susceptible to failure in which case no write permissions can be allowed.
In the former circumstance, write requests can be marshaled in distributed platforms and applied at a later time to the centralized data store, yet at some point the prolonged failure of the single host can defeat the marshaled write operations. In the latter circumstance, write operations can be applied at each remote server in cluster a distributed manner and replicated at a later time to harmonize the different data stores in the cluster. Still, the replication process can give rise to replication conflicts where two elements with the same name or record number are created, modified or deleted. Furthermore, merging data amongst data stores in a cluster can be complicated by modifying same names for different elements from different hosts in the cluster during replication so as to result in one element being overwrite by another. This limits the user experience due to suddenly changed names or incorrect merging which requires manual administrative intervention to restore the intended data.
BRIEF SUMMARY OF THE INVENTION
Embodiments of the present invention address deficiencies of the art in respect to element identification for elements in a collaborative computing environment and provide a novel and non-obvious method, system and computer program product for identifying unstructured elements of a collaborative place in a hierarchically structured manner. As used herein, a collaborative place can include a collaborative workspace, for instance a Wiki, blog, or document library. In one embodiment of the invention, a method for locating an unstructured element in a collaborative computing environment can be provided. The method can include receiving a request for an unstructured element in the collaborative environment, extracting a hierarchy of unique identifiers from the request, locating a last folder or other hierarchical structure referenced by the hierarchy of unique identifiers, and returning a reference to the folder or other hierarchical structure as a location of the unstructured element.
In one aspect of the embodiment, extracting a hierarchy of unique identifiers from the request can include extracting a hierarchy of unique identifiers from the request, each of the unique identifiers comprising an attribute type for an attribute of the unstructured element and a name for the attribute. For example, the attribute type for an attribute of the unstructured element can include an attribute type selected from the group consisting of a collaborative place, room, folder, document and attachment. Other attribute types can include comments, versions and the like. In another aspect of the embodiment, returning a reference to the folder or other hierarchical structure as a location of the unstructured element can include additionally extracting a name hierarchy for the unstructured element, resolving a folder as a child of the folder referenced by the hierarchy of unique identifiers based upon the name hierarchy, and returning a reference to the resolved folder as a location of the unstructured element.
In another embodiment of the invention, a collaborative computing data processing system can be configured for locating an unstructured element such as a memo, calendar item, document, and task. The system can include at least one collaborative server communicatively coupled to multiple different collaborative clients. The system also can include element naming logic coupled to each of the collaborative clients. The element naming logic can include program code enabled to receive a request for an unstructured element in the collaborative environment, extract a hierarchy of unique identifiers from the request, locate a last folder referenced by the hierarchy of unique identifiers, and return a reference to the folder as a location of the unstructured element. For example, each of the unique identifiers can include an attribute type for an attribute of the unstructured element and a name for the attribute. For instance, the attribute type can include by way of example a collaborative place, room, folder, document and attachment.
Additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The aspects of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention. The embodiments illustrated herein are presently preferred, it being understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown, wherein:
FIG. 1 is a block diagram illustrating a syntax for hierarchically identifying unstructured elements in a collaborative environment;
FIG. 2 is a schematic illustration of a collaborative data processing system configured for hierarchically identifying unstructured elements; and,
FIG. 3 is a flow chart illustrating a process for hierarchically identifying unstructured elements in a collaborative environment.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention provide a method, system and computer program product for hierarchically identifying unstructured elements in a collaborative environment. In accordance with an embodiment of the present invention, an unstructured collaborative element such as a memo, calendar item, document, task and the like can be identified according to a hierarchy of unique identifiers. Each unique identifier can be defined by a combination of an attribute type and attribute name, the attribute type including by way of example, a collaborative place, room, folder, document or attachment. Optionally, the hierarchy of unique identifiers for an element can be combined with a named identification of the element in order to support a hierarchical representation of the element in a collaborative environment where different collaborative platforms represent the element differently according to different data structures.
In illustration, FIG. 1 depicts a syntax for hierarchically identifying unstructured elements in a collaborative environment. The syntax 100 can include one or more unique identifiers 160 . Each of the unique identifiers 160 can include a hierarchical delimiter 110 followed by a type delimiter 120 followed by a name 130 . For example, the type delimiter 120 can indicate a collaborative place, a collaborative room within a place, a collaborative folder within a room, a document within a folder, or an attachment to a document so that the syntax, “@Pmyplace/@Rmyroom/@Fmyfolder/@D1234” is a unique identifier indicating a document having the system generated string identifier “1234” stored within the folder myfolder in the room myroom in the place myplace.
Optionally, the syntax 100 further can include a name identifier 170 combined with one or more of the unique identifiers 160 . Each of the name identifiers 170 can include a hierarchical name reference to a document in a folder within a file system location. For example, the hierarchical name reference
“Folder/Subfolder/Document.doc” can refer to the document entitled Document.doc stored within the subfolder of the folder Folder. Combining both the unique identifiers 160 and the name identifiers 170 , a syntax for an element within a collaborative environment can include @Pmyplace/@Rmyroom/myfolder/1234.doc in which case the unique identifier can resolve to the collaborative place myplace and the room myroom within the place irrespective of how the room and place are represented within the file system. Thereafter, the file system can be consulted to determine whether or not the folder myfolder is unique for the room and whether to create or merely locate the folder myfolder in the file system before resolving the document 1234.doc.
Notably, the syntax 100 can be applied in a collaborative data processing system in the management of unstructured elements, such as memos, documents, calendar appointments meetings, tasks and the like. In illustration, FIG. 2 schematically depicts a collaborative data processing system configured for hierarchically identifying unstructured elements. The system can include one or more host computing platforms 210 configured for communicatively coupling to one or more client computing platforms 230 over computer communications network 220 . Each of the host computing platforms 210 can support the operation of a collaborative server 260 , for instance, a Domino™ or Workplace™ brand collaborative server manufactured by International Business Machines Corporation of Armonk, N.Y.
Each of the client computing platforms 230 , by comparison, can include an operating system 240 hosting a respective operating system 240 . Each operating system 240 , in turn, can support the operation of a collaborative client 250 such as the Lotus™ Notes™ collaborative client manufactured by International Business Machine Corporation of Armonk, N.Y. In particular, each collaborative client 250 can be configured to communicate with a corresponding one of the collaborative servers 260 over computer communications network 220 . Finally, element naming logic 300 can be coupled to one or more of the collaborative servers 260 .
The element naming logic 300 can include program code enabled to locate an unstructured element in the collaborative servers 260 according to a hierarchy of unique identifiers optionally combined with a naming hierarchy for the element. In this regard, one or more attribute types for attributes of the element can be specified in hierarchical order irrespective of an underlying file system data structure storing the element. For example, a hierarchy of place, room, folder, document and attribute can be specified wholly or partially in order to uniquely identify the element without regard to the underlying file system structure storing the element. Further, a naming hierarchy reflective of the file system data structure storing the element can be combined with the hierarchy of unique identifiers for the element such as folder-subfolder-file.
In further illustration of the operation of the element naming logic 300 , FIG. 3 is a flow chart illustrating a process for hierarchically identifying unstructured elements in a collaborative environment. The process can begin in block 310 with a request to locate an unstructured element in the collaborative environment. In block 320 , a unique identifier or combination of unique identifiers arranged in hierarchical form can be extracted for the element in order to locate the element. In decision block 330 , a last folder or other hierarchical structure specified by the hierarchy of unique identifiers can be determined. If none can be located, in block 340 an error can be returned. Otherwise, the process can continue through block 350 .
In decision block 330 , if a last folder or other hierarchical structure can be located for the hierarchy of unique identifiers, in decision block 350 it can be determined whether a named hierarchy for the element has been combined with the hierarchy of unique identifiers. If not, a reference to the last folder or other hierarchical structure can be returned as the location of the element in block 360 . However, if a named hierarchy has been provided, in block 370 the folder-subfolder-file hierarchy specified by the named hierarchy can be located relative to the last folder or other hierarchical structure.
In decision block 380 , if the folder-subfolder-file hierarchy exists in the collaborative environment, in block 390 , the folder resolving for the folder-subfolder-file hierarchy can be resolved relative to the last folder or other hierarchical structure referenced by the hierarchy of unique identifiers. Otherwise, in block 400 , a folder-subfolder-file hierarchy and resulting folder can be created relative to the last folder or other hierarchical structure referenced by the folder-subfolder-file hierarchy. In either case, in block 360 the final reference to the folder or other hierarchical structure can be returned as the location of the element for processing in the collaborative environment.
Embodiments of the invention can take the form of an entirely hardware embodiment, an entirely software embodiment or an embodiment containing both hardware and software elements. In a preferred embodiment, the invention is implemented in software, which includes but is not limited to firmware, resident software, microcode, and the like. Furthermore, the invention can take the form of a computer program product accessible from a computer-usable or computer-readable medium providing program code for use by or in connection with a computer or any instruction execution system.
For the purposes of this description, a computer-usable or computer readable medium can be any apparatus that can contain, store, communicate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. The medium can be an electronic, magnetic, optical, electromagnetic, or semiconductor system (or apparatus or device). Examples of a computer-readable medium include a semiconductor or solid state memory, magnetic tape, a removable computer diskette, a random access memory (RAM), a read-only memory (ROM), a rigid magnetic disk and an optical disk. Current examples of optical disks include compact disk-read only memory (CD-ROM), compact disk-read/write (CD-R/W) and DVD.
A data processing system suitable for storing and/or executing program code will include at least one processor coupled directly or indirectly to memory elements through a system bus. The memory elements can include local memory employed during actual execution of the program code, bulk storage, and cache memories which provide temporary storage of at least some program code in order to reduce the number of times code must be retrieved from bulk storage during execution. Input/output or I/O devices (including but not limited to keyboards, displays, pointing devices, etc.) can be coupled to the system either directly or through intervening I/O controllers. Network adapters may also be coupled to the system to enable the data processing system to become coupled to other data processing systems or remote printers or storage devices through intervening private or public networks. Modems, cable modem and Ethernet cards are just a few of the currently available types of network adapters. | Embodiments of the present invention address deficiencies of the art in respect to element identification for elements in a collaborative computing environment and provide a method, system and computer program product for identifying unstructured elements of a collaborative place in a hierarchically structured manner. In one embodiment of the invention, a method for locating an unstructured element in a collaborative computing environment can be provided. The method can include receiving a request for an unstructured element in the collaborative environment, extracting a hierarchy of unique identifiers from the request, locating a last folder referenced by the hierarchy of unique identifiers, and returning a reference to the folder as a location of the unstructured element. | 6 |
This application is a continuation of application Ser. No. 08/017,318 filed Feb. 11, 1993, now abandoned which is a continuation of prior Ser. No. 07/610,812 filed Nov. 8, 1990, now abandoned which is a continuation of prior Ser. No. 07/396,542. filed Aug. 21. 1989 which is now U.S. Pat. No. 5,033,957, issued on Jul. 23, 1991.
BACKGROUND OF THE INVENTION
This invention relates to burners which utilize a pressurized supply of fuel and which vaporize the fuel prior to combustion.
Liquid-fueled burners that do not require any external source of power are in common use as portable heat sources for applications such as campstoves and military field kitchens. Generally such burners store the fuel in a pressurized fuel tank and vaporize the liquid fuel prior to combustion in order to provide for complete mixing with combustion air and in order to provide a pressurized gas stream to propel the mixture to the burner head. In the past, most such burners utilized highly volatile fuels such as gasoline or kerosine, since these fuels vaporize at a low temperature, making it easy to heat the vaporizer and maintain the fuel in the vapor state. Operation with less volatile fuels, such as diesel fuel, is far more difficult, since diesel fuel vaporizes at a relatively high temperature, on the order of 600-700 degrees Fahrenheit, making it far more difficult to heat the vaporizer and to deliver the fuel to the burner as a vapor. Moreover, at elevated temperatures liquid fuels tend to decompose, resulting in the formation of carbon and tars which foul the vapor passages. Nonetheless, it is highly desirable to use diesel fuel, since it is much safer than gasoline and is readily available in the military, which uses it as a universal automotive fuel.
Prior-art burners exist that are capable of burning liquid-fuels without an external source of power. The vaporized fuel is generally accelerated under pressure in a nozzle, and the resulting fuel vapor jet entrains some or all of the air required for combustion. A common example of this class of burners is the "Coleman Stove", which utilizes a closed fuel tank which is pressurized by pumping air into the fuel tank. The fuel is forced out of the tank by action of the tank pressure and flows through a "generator" in which the fuel is vaporized. The heat necessary for vaporization is provided by a "pre-heat burner" during start-up, and following the pre-heat period, by heat from the main burner. The generator may take many forms, but commonly takes the form of a tube heated on the outside by a preheat burner, and once the main burner is ignited, by the main burner flame. From the generator, the now-vaporized fuel flows through a nozzle in which it accelerates to a high velocity, and then mixes with and entrains air for combustion. The air/fuel mixture then flows to a burner head, which anchors the flame. A fuel valve is generally provided to modulate and/or shut-off the flow of fuel. The fuel valve may control either the liquid fuel or the vaporized fuel.
Other examples of prior-art, non-powered, vaporizing, liquid-fueled burners include:
MSR X/GK campstove (gasoline, kerosine or diesel fuel)
Optimus 199 Ranger (alcohol, gasoline, kerosine)
Coleman Peak 1 (gasoline or kerosine)
Optimus III Hiker (gasoline or kerosine)
U.S. Army M-2 Gasoline Burner Unit (gasoline)
Haas +Sohn V75/1 Type Multicombustible Burner (gasoline, kerosine, diesel fuel)
Karcher Field Kitchen Burner (Gasoline, kerosine, diesel fuel)
The first four prior-art citations are examples of small campstoves, typically under 10,000 BTU/hr output, that may be carried in a back-pack for individual use. The latter three citations are examples of field-kitchen burners having capacities on the order of 60,000 BTU/hr. It is somewhat easier to burn low-volatility fuels in the smaller burners since the entire burner and fuel delivery system may be heated by conduction from the burner head. On account of their larger size, it is more difficult to conduct sufficient heat throughout the larger burners to prevent fuel vapor from condensing in the passages leading from the vaporizer to the burner. The present invention is directed towards solving this problem in larger burners.
Prior-art burners suffer from a number of additional deficiencies which the present invention is intended to overcome. These include:
Slow Start-Up
Many burners, particularly those of larger capacity, are slow-to-start because of the large mass of their vaporizers.
Large Size and Weight
Some burners are heavy and bulky, which is a disadvantage in a burner intended for field use.
Complex and Expensive
Some burners use complex and expensive mechanisms.
Unsafe Operation
Some burners may allow unsafe operation by overheating the fuel tank or burner parts, allowing fuel to drip from the burner, or storing a large volume of vaporized, pressurized fuel.
Unstable Operation
Some burners may operate in a pulsating mode or may be subject to flooding during start-up.
High Maintenance
Most vaporizing burners are subject to fouling of the vapor passages by tars formed by the fuel. This problem is particularly acute in small vapor passages.
Noisy, Dirty Combustion
Many burners produce smoky flames as a result of insufficient combustion air or poor mixing with air or require high air pressure to provide sufficient combustion air, which results in a noisy burner.
DISCLOSURE OF THE INVENTION
In accordance with the present invention, liquid fuel is vaporized and then burned on a flame holder of a burner. A vapor generator comprises at least one vertical tube having fins exposed to a flame on the flame holder. Liquid is vaporized within the vertical tube. A vapor flow control valve is positioned between the vapor generator and the flameholder. Preferably, a liquid flow restrictor is provided between a liquid fuel tank and the vapor generator.
Preferably, the flame holder is a cylindrical screen mounted on a vertically oriented fuel and air mixer over a fuel nozzle. A cup is formed about the nozzle to collect any condensed fuel from the mixer. The mixer is preferably of high thermal conductivity material and is heated by the flame to minimize condensation. A flame deflector surrounds the flame holder and directs the flame upward. The deflector also serves to collect any fuel which condenses at the flame holder during start-up.
A superheater tube carries fuel vapor from the vapor generator past the flame to the fuel nozzle. Preferably, the superheater connects into a strainer and is easily disconnected for cleaning.
By means of the present invention, a burner is capable of burning less volatile liquid fuels without any external source of power. The burner can ignite rapidly from a cold initial state and is ready to operate in a short time. It is compact, lightweight, simple and of inexpensive construction. It is safe and operates in a stable manner under all conditions. Further, it requires little maintenance and operates cleanly and quietly with a low pressure fuel supply.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic illustration of a vaporizing burner embodying the present invention.
FIG. 2 is a more detailed schematic illustration of the mixer/aspirator of the burner of FIG. 1.
FIG. 3 is a detailed cross-sectional schematic view of the vapor generator of the burner of FIG. 1.
FIG. 4 is a side view of the vapor generator of FIG. 1.
FIG. 5 is a longitudinal-sectional view of a safety valve in the burner of FIG. 1.
FIG. 6a and 6b are cross-sectional and longitudinal-sectional views of the flame control valve of the burner of FIG. 1.
FIG. 7 is a side view of the mixer, flame holder and vapor generator of the system of FIG. 1.
DESCRIPTION OF THE INVENTION
The principal features of the invention are described in the following figures.
FIG. 1 shows a schematic of the burner system. Fuel storage tank 10 contains dip-tube 12 which draws fuel from the bottom of the tank into preheat torch 18 through conduit 14 and shut-off valve 16. Compressed air is drawn from the top space 20 of fuel tank 10 through conduit 22 to mix with the liquid fuel in torch 18. The flame 24 of the preheat torch 18 heats vapor generator 40 to start the main burner 100. Once the vapor generator 40 has been heated to a sufficient temperature, on the order of 700 degrees Fahrenheit, fuel safety valve 200 is opened, admitting liquid fuel to vapor generator 40. Liquid fuel flows from tank 10 through dip tube 30, through conduit 32 and fuel metering orifice 34 to the fuel safety valve 200. Fuel metering orifice 34 limits the rate of fuel flow so that vapor generator 40 will not become flooded with unvaporized fuel. By thus limiting the rate of liquid flow, fuel can be vaporized at a sufficient rate within vaporizer 40 to build a back-pressure which prevents excessive in-flow.
After the fuel safety valve 200 has been opened, vapor flow control valve 300 is opened. This permits fuel vapor to flow from vapor generator 40 through superheater 60 and conduit 70, through vapor flow control valve 300, and into fuel vapor nozzle 320. The vapor issues from vapor nozzle 320 as a high-velocity jet, entraining primary air into mixer/aspirator 340, which delivers the fuel/air mixture to burner head 100. Once ignited by the preheat burner flame 24, the burner flame 110 heats the vapor generator 40 and superheater 60, which in turn heats the fuel vapor flowing within it to a temperature on the order of 1000 degrees Fahrenheit. This superheating compensates for heat loss by the fuel vapor as it flows through conduit 70, vapor valve 300, and nozzle 320.
In one embodiment, fuel safety valve 200 may be a normally-closed electric solenoid valve powered by a thermocouple 250. To admit fuel to the vapor generator 40, valve 200 is manually kept open until flame 110 or 24 heats thermocouple 250 sufficiently to generate enough power to hold valve 200 in the open position. In the event of a loss of flame for any reason, thermocouple 250 would cool and allow valve 200 to close, thereby shutting-off the fuel flow. This arrangement also permits thermal fuses or thermostatic switches to be placed in series with the thermocouple leads 252 to open the circuit if an unsafe temperature is reached.
FIG. 2 shows the arrangement of burner 100 and mixer/aspirator 340. Burner head 100 comprises burner screen 110 fitted between top cap 114 and bottom cap 116, and flame deflector 120. Burner screen 110 comprises a cylinder of heat resistant sheet-metal such as stainless steel that is perforated with numerous holes or slots, each having a minor dimension of not more than 0.03 inches and representing an open area of 10% to 20% of the total surface area of the cylinder. Top cap 114 is preferably made of a thin heat-resistant sheet-metal such as stainless steel, and may optionally contain additional burner ports. Bottom cap 116 is preferably constructed of a highly conductive metal such as copper which has been plated with nickel to minimize oxidation. Bottom cap 116 is bonded to mixer tube 346, which preferably is similarly constructed of nickel-plated copper.
In the preferred embodiment, heat from the burner flame is conducted by bottom cap 116 and mixer tube 346 down to the inlet 356 of the mixer/aspirator 340. Flame deflector 120 serves to impose a vertically upward component to the primarily radial flow direction of the flame leaving burner screen 110. It also serves to collect any condensation of fuel during startup for subsequent evaporation and burning. Preferably deflector 120 is constructed of heat-resistant sheet-metal such as stainless steel.
Mixer/aspirator 340 comprises mixer tube 346 connected to mixer inlet 356 and fuel vapor nozzle 320. Mixer inlet 356 has an open bellmouth end connected to mixer tube 346 and an opposite flat base 366. The sides of inlet 356 contain openings 370 which admit combustion air to the mixer/aspirator 340. Preferably, openings 370 may be adjusted by a sliding or rotary shutter (not shown). Fuel nozzle 320 is fitted and bonded to a hole centered in base 366 to direct the fuel vapor jet 330 along the centerline of mixer tube 346. The vapor jet 330 entrains and induces combustion air to flow into the mixer inlet openings 370 and along mixer tube 346 into burner 100.
Since mixer/aspirator 340 is heated by conduction from burner 100, once the burner has reached a steady operating temperature fuel does not condense within the mixer/aspirator. During startup, any fuel that does condense within the burner 100 or mixer aspirator 340 is collected within the base 366 of inlet 356. During subsequent operation, that liquid evaporates.
FIG. 3 shows the form of vapor generator 40. Vapor generator 40 is placed between burner head 100 and preheat torch 18 in order that it may be heated by the flame of either. Liquid fuel enters from conduit 36 through inlet manifold 42 which is connected to one or more riser tubes 44. Riser tubes 44 have fins 46 at the top which are positioned to be heated by the flames from both the preheat torch 18 and main burner 100. Vaporized fuel exits from the top(s) of riser tube(s) 44 into outlet manifold 48, from which the fuel vapor then flows into superheater 60 (not shown).
Most of the heating of the fuel occurs within the finned section 46 of riser tube(s) 44. A liquid-vapor interface 50 will normally exist within the finned section 46. Below the liquid-vapor interface 50 liquid fuel is heated to its saturation temperature and caused to vaporize and bubble. Above the interface 50 the fuel is mostly in the vapor state, and as a result of the significantly lower coefficient of heat transfer to the vapor in comparison to the liquid, relatively little heating of the fuel occurs above interface 50.
The elevation of interface 50 within riser 44 is established by a balance between the rate of vaporization and the flow of vapor out of nozzle 320 (not shown, see FIG. 1). If interface 50 is below its equilibrium elevation, less of the interior surface of riser 44 is exposed to liquid, resulting in lower heat input and a correspondingly lower rate of evaporation of fuel. This in turn causes a lower rate of flow through nozzle 320 and vapor valve 300, which results in a lower back-pressure. If the back-pressure is less than the supply pressure established by the pressure in fuel tank 10 (not shown), less any pressure drop caused by flow resistance and elevation change, the flow of liquid fuel into riser 44 will increase, causing interface 50 to rise. This in-turn will increase the surface of liquid being heated, thus increasing the evaporation rate and reestablishing equilibrium.
The rate at which interface 50 will rise or fall in response to a perturbation from equilibrium is governed in part by the resistance of orifice 34 (See FIG. 1). It has been found that a flow resistance sufficient to limit fuel flow to between twice to six times the normal rate of evaporation in the vapor generator 40 will prevent flooding or flow oscillation while permitting good modulation of the burner. Moreover, by limiting the maximum diameter of orifice 34 to 0.020 inches, it acts as a flame arrestor, preventing a flashback of flame from entering the fuel tank.
The use of the vertical vapor generator in combination with the flow-limiting liquid orifice eliminates the problems of flooding and flow oscillations common with other non-powered burners, resulting in a safer, easier-to-operate burner.
Some prior-art generators have sought to solve the problem of flow oscillation by using a small diameter/volume vapor generator (e.g., 1/4 inch internal diameter), which causes the frequency of flow oscillation to increase to a point at which the oscillation may not be objectionable. However, such vapor generators are highly susceptible to fouling by the tars which remain after the lighter fuel fractions have evaporated. Riser(s) 44 preferably have an internal diameter between one-half inch to one inch. Diameters smaller than one-half inch may result in premature failure due to the build-up of tar or carbon, which may block the flow within the vapor generator. Larger diameters result in a larger thermal mass, requiring longer time to preheat the vapor generator.
FIG. 4 shows a preferred embodiment of vapor generator 40. Liquid fuel supply tube 36 is joined to inlet manifold tee 442 by soldering, brazing, welding or similar bonding method. Inlet tubes 410 and 412 are also bonded to manifold 442 and extend into riser tubes 444 through compression fittings 420 and 430. Compression fittings 420 are fitted to inlet tubes 410 and 412 and are joined to compression fittings 430, which are fitted to riser tubes 444. Riser tubes 444 are joined to finned tubes 450 having fins 446 by a suitable high-temperature method of bonding, such as "nicro-brazing" or welding. Fins 446 may be machined in tubes 450 or may be stamped out of sheet-metal and brazed to tubes 450. Outlet header 448 may be made out of a closed rectangular tube that is brazed to the top of finned tubes 450 and brazed or welded to the inlet 460 of superheater 60.
This preferred embodiment provides an economical construction which facilitates cleaning of the interior of the vapor generator by unscrewing the compression fittings 420 and 430. Tubing 36, 410 and 412, and fittings 442 and 420 may be constructed of inexpensive low-temperature materials, such as copper or brass, since they are not exposed to high temperature. The remainder of the assembly should be constructed of temperature-resistant materials, such as stainless steel.
FIG. 5 shows a cross-sectional view of fuel safety valve 200. Fuel enters through inlet fitting 210 to inlet plenum 220 within housing 230. Valve plug 240 is fitted to shaft 242 which is surrounded by solenoid winding 244. Spring 246 positioned between solenoid winding 244 and plug 240 forces "O" ring 248 contained in plug 240 against valve seat 232 when the solenoid is deenergized, sealing inlet plenum 230 outlet plenum 260 and outlet fitting 262. Valve plunger 270 is used to manually open valve 200 by pushing on push-button against return spring 274. Plunger "O" ring 276 prevents leakage of fuel between plunger 270 and housing 230. Thermocouple 250 is connected through thermocouple lead 252 and connector 254 and feedthrough 256 to solenoid winding 244. Optional series connector 258 has external terminals 259 which provide connection to an external series loop which may contain thermostatically activated fuses or switches to interrupt the circuit between thermocouple 250 and solenoid winding 244.
In operation, after vapor generator 40 has has been heated sufficiently by preheat torch 18, push-button 272 is depressed and held in the depressed position, pushing valve plug 240 away from seat 232 until thermocouple 250 is heated sufficiently by the main burner so that solenoid 244 captures shaft 242 and button 272 may be released. In the event of a flameout, thermocouple 250 will cool, thereby reducing its electrical output, deenergizing solenoid 244 and allowing spring 246 to close plug 240. If any optional thermal switches or fuses are used in combination with optional connector 258, any event which causes them to open will also result in closing of the safety valve.
FIGS. 6A and 6B show one form of a combination vapor flow control valve 300 and fuel vapor nozzle 320. Vaporized fuel enters from superheater outlet conduit 70 through valve inlet 310. Valve stem 350 has male threads 352 which engage female threads 302 in valve body 300 to enable valve tip 340 to seal against valve seat 330 in body 300. Valve stem 350 is sealed in body 300 by packing 354 and packing nut 356. Outlet plenum 370 communicates with chamber 372 into which is screwed vapor nozzle 320, sealed with nozzle gasket 322. Pinion gear 360 is located on valve stem 350 between threads 352 and valve tip 340. Gear 360 engages rack 362 which contains cleanout pin 364. When valve stem 350 is rotated to draw valve tip 340 away from seat 330, gear 360 causes rack 362 to rise. Further opening of the valve causes the cleanout pin 364 in rack 362 to pass through the orifice in vapor nozzle 320, thereby clearing away any debris that may have collected at the orifice.
In a preferred embodiment, cleanout pin 364 may be a twist drill shortened to an appropriate length. The flutes in the twist drill permit vapor to flow through the orifice while the nozzle is being cleaned, thereby permitting the nozzle to be cleaned without extinguishing the main burner.
Additionally, the cleanout pin 364 may be used as a modulating valve, using the nozzle 320 as a secondary valve seat. This can be advantageous when operating the burner at its minimum firing rate, since this causes the nozzle to operate as a variable-area nozzle, maintaining a high vapor velocity through a reduced nozzle cross-sectional area. This results in greater entrainment of air at a given vapor flow rate than if the vapor were throttled by the main vapor flow control valve at seat 330.
FIG. 7 shows an assembly of the vapor generator, vapor flow control valve and burner/mixer. Vapor generator 40 is attached by clamp 140 to bracket 130 which is bonded to deflector 120 of burner head 100. Fins 46 are positioned to be opposite burner screen 110, and tubular superheater 60 is connected to outlet header 48 and coils about burner screen 110 for approximately 180 degrees before bending downward to the vapor flow control valve 300. The body of valve 300 is fitted and bonded to a hole in the base 366 of mixer inlet 356, securely aligning the nozzle 320 with the centerline of mixer tube 346.
In a preferred embodiment, vapor strainer 72 is positioned between superheater 60 and valve 300 to trap any carbon particles that may have been formed in the vapor generator or superheater and which may clog the vapor valve or vapor nozzle. Superheater tube 60 is readily disconnected from strainer 72 for ease of cleaning. Mixer inlet 356 may also be separably attached to mixer tube 346 and fastened by hose clamp 380. Cable 376 attached to tab 374 on rotary shutter 372 may be used to adjust the position of shutter 372 over air slots 370 to alter the ratio of air to fuel. | Diesel fuel is vaporized and then burned on a cylindrical screen flame holder. The fuel is vaporized in a finned, vertical tube vapor generator and directed through a superheater tube past the flame to a flow control valve and nozzle. A flow restriction is provided between a liquid fuel supply and the vapor generator. The flame holder is vertically supported over a mixer and the nozzle. A flame deflector about the flame holder and a reservoir about the nozzle collect fuel condensate during start-up. | 5 |
BACKGROUND OF THE INVENTION
[0001] (a) Field of the Invention
[0002] The present invention relates to a manufacturing method of an organic zinc catalyst having more uniform and finer particle size and showing a more improved activity in a polymerization process for manufacturing a polyalkylene carbonate resin, and a manufacturing method of the polyalkylene carbonate resin using the organic zinc catalyst obtained by the manufacturing method of the organic zinc catalyst.
[0003] (b) Description of the Related Art
[0004] Since the industrial revolution, modern society has been built by consuming a large amount of fossil fuels, but on the other hand, carbon dioxide concentration in the atmosphere has increased, and further, this increase has been more accelerated by environmental destruction such as disforestation, etc. Global warming is caused by an increase of greenhouse gases such as carbon dioxide, freon, and methane in the atmosphere, such that it is significantly important to reduce the atmospheric concentration of carbon dioxide highly contributing to global warming, and several studies into emission regulation, immobilization, etc., have been conducted on a global scale.
[0005] Among the studies, a copolymerization of carbon dioxide and epoxide developed by Inoue, et al., is expected as a reaction for solving the problems of global warming, and has been actively researched in view of immobilization of chemical carbon dioxide and in view of the use of carbon dioxide as a carbon resource. Particularly, a polyalkylene carbonate resin obtained by the polymerization of carbon dioxide and epoxide has recently received significant attention as a kind of biodegradable resins.
[0006] Various catalysts for manufacturing the polyalkylene carbonate resin have been researched and suggested for a long time, and as representative examples thereof, zinc dicarboxylate-based catalysts such as a zinc glutarate catalyst, etc., in which zinc and dicarboxylic acid are combined to each other have been known.
[0007] Meanwhile, the zinc dicarboxylate-based catalyst, as a representative example, a zinc glutarate catalyst is formed by reacting a zinc precursor with a dicarboxylic acid such as a glutaric acid, etc., and has a shape of fine crystalline particle. The zinc dicarboxylate-based catalyst having the crystalline particle shape has a difficulty in being controlled to have a uniform and fine particle size in a manufacturing process thereof. For reference, when it is possible to control the catalyst particle size to be finer, surface area is more increased and active sites of a catalyst surface are more increased in the same amount of catalyst, which is preferred. However, it is difficult to control the catalyst particle size to be fine and uniform.
[0008] Due to the above-described reasons, the existing known zinc dicarboxylate-based catalysts have a relatively large particle size and a non-uniform particle shape in many cases, and accordingly, when a polymerization process for manufacturing the polyalkylene carbonate resin is performed by using the zinc dicarboxylate-based catalyst, a sufficient contact area between reaction materials and the catalyst is not secured, such that there is a drawback in that a polymerization activity is not sufficiently implemented. Further, there are many cases in which an activity of the existing zinc dicarboxylate-based catalyst itself is not sufficient, either.
[0009] Further, the zinc dicarboxylate-based catalyst has difficulty in dispersing and controlling the catalyst particles in a reaction solution due to non-uniformity of the particle size.
[0010] The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art.
SUMMARY OF THE INVENTION
[0011] The present invention has been made in an effort to provide a manufacturing method of an organic zinc catalyst having more uniform and finer particle size and showing a more improved activity in a polymerization process for manufacturing a polyalkylene carbonate resin, and an organic zinc catalyst obtained by the manufacturing method of the organic zinc catalyst.
[0012] In addition, the present invention has been made in an effort to provide a manufacturing method of the polyalkylene carbonate resin using the organic zinc catalyst obtained by the manufacturing method.
[0013] An exemplary embodiment of the present invention provides a manufacturing method of an organic zinc catalyst including: forming a zinc dicarboxylate-based catalyst by reacting a zinc precursor with C3-C20 dicarboxylic acid,
[0014] wherein the reaction step is performed under a condition in which the number of moles of the dicarboxylic acid is more than that of the zinc precursor in a reaction system, throughout the entire reaction steps.
[0015] Another embodiment of the present invention provides an organic zinc catalyst in a particle shape having an average particle size of 0.8 μm or less and a particle size standard deviation of 0.2 μm or less, wherein the organic zinc catalyst is a zinc dicarboxylate-based catalyst obtained by reacting a zinc precursor with C3-C20 dicarboxylic acid.
[0016] Yet another embodiment of the present invention provides a manufacturing method of a polyalkylene carbonate resin including: polymerizing an epoxide and a monomer including carbon dioxide in the presence of the organic zinc catalyst as described above.
[0017] Hereinafter, the manufacturing method of the organic zinc catalyst according to exemplary embodiments of the present invention, the organic zinc catalyst obtained by the same, and the manufacturing method of the polyalkylene carbonate resin using the organic zinc catalyst are described in detail.
[0018] According to an exemplary embodiment of the present invention, there is provided a manufacturing method of an organic zinc catalyst including: forming a zinc dicarboxylate-based catalyst by reacting a zinc precursor with C3-C20 dicarboxylic acid, wherein the reaction step is performed under a condition in which the number of moles of the dicarboxylic acid is more than that of the zinc precursor in a reaction system, throughout the entire reaction steps.
[0019] Here, “a condition in which the number of moles of the dicarboxylic acid is more than that of the zinc precursor in a reaction system, throughout the entire reaction steps” means that a condition in which the number of moles of the dicarboxylic acid is always more than that of the zinc precursor in the reaction system (e.g., in a reactor) where a reaction thereof is performed, is maintained from a starting time for a reaction of the zinc precursor and the dicarboxylic acid up to an ending time for the reaction thereof, regardless of a total used amount (the number of moles) of the zinc precursor and the dicarboxylic acid required for manufacturing the organic zinc catalyst. As described below in more detail, in order to maintain the condition, the total used amount of the dicarboxylic acid may be added at the reaction time, or in the case of the zinc precursor, the total required amount may be separately added several times.
[0020] Meanwhile, as results from continuous experiments, the present inventors surprisingly confirmed that in the process of manufacturing the zinc dicarboxylate-based catalyst by reacting the zinc precursor with the dicarboxylic acid, when the reaction is performed in a state controlled so that the dicarboxylic acid is present in an excess amount (a molar excess amount) as compared to the zinc precursor during the entire reaction processes, the zinc dicarboxylate-based catalyst having a finer and more uniform particle size and showing a more improved activity than that of the existing catalysts could be manufactured.
[0021] It is considered that the reason is because when the reaction step is performed in a state in which the dicarboxylic acid is present in an excess amount (hereinafter, referred to as a molar excess state of the dicarboxylic acid), the reaction is slowly performed in a state in which respective zinc or precursor molecules or ions thereof are surrounded by dicarboxylic acid molecules or ions having excess amounts in the reaction system, such that the zinc or the precursor components thereof which are the catalytically active components hardly agglomerate with each other, and all react with the dicarboxylic acid components, thereby forming active sites of the catalyst.
[0022] Further, due to the reaction as performed above, it is thought that a possibility in which the respective zinc dicarboxylate-based catalyst particles agglomerate with each other in the manufacturing method thereof is decreased, thereby finally forming finer and more uniform catalyst particles. In addition, due to the reaction as performed above, it is expected to form the zinc dicarboxylate-based catalyst particles showing different crystalline characteristics from those of the existing catalyst particles.
[0023] To this end, according to an exemplary embodiment of the present invention, it was consequently confirmed that the zinc dicarboxylate-based organic zinc catalyst showing a more excellent activity could be obtained in the catalyst particle shape having the finer and more uniform particle size. In addition, due to the finer and uniform particle size of the catalyst particles, dispersing and controlling the catalyst particles in the reaction solution may be easily performed. Accordingly, the organic zinc catalyst may be preferably applied to the manufacturing of the polyalkylene carbonate resin by the reaction of carbon dioxide with epoxide.
[0024] On the other hand, it was confirmed that even though the total used amount of the dicarboxylic acid for manufacturing the organic zinc catalyst is larger than that of the zinc precursor, when the above-described condition, that is, the condition in which the dicarboxylic acid is present in the molar excess amount throughout the entire reaction steps, is not satisfied (for example, a case in which the dicarboxylic acid is slowly added and reacted with the zinc precursor such as Comparative Example to be described below, etc.,—since only a portion of the dicarboxylic acid is added to the reaction system at least at the reaction time, the molar excess amount of the dicarboxylic acid may not be maintained), the organic zinc catalyst having an agglomerated particle size as compared to the organic zinc catalyst obtained by the exemplary embodiment may be merely manufactured, which had a relatively poor activity.
[0025] Meanwhile, in the manufacturing method of the exemplary embodiment, several ways may be applied so that the condition in the reaction system is maintained as the state in which the dicarboxylic acid is present in the molar excess amount, throughout the entire reaction steps.
[0026] First, as a first way, the dicarboxylic acid may be used in a sufficient molar excess amount relative to the total used amount as compared to the zinc precursor, and in addition, the above-described molar excess amount condition of the dicarboxylic acid may be maintained throughout the entire reaction steps by adding the total used amount of the dicarboxylic acid at the reaction time. More specifically, the dicarboxylic acid may be used at a molar ratio of about 1.05 to 1.5, or about 1.1 to 1.3 relative to 1 mol of the zinc precursor, and in addition, the total used amount of the dicarboxylic acid may be added at the reaction time. By controlling the total used amount as described above, the reaction step is performed while maintaining the molar excess state of the dicarboxylic acid, thereby manufacturing the organic zinc catalyst in the zinc dicarboxylate-based catalyst shape having a more uniform and finer particle size and showing an improved activity.
[0027] Further, as a second way, the reaction step is performed in a liquid medium in which reaction materials including the zinc precursor and the dicarboxylic acid are present (for example, in a solution or a dispersion liquid in which the reaction materials are dissolved or dispersed), wherein the reaction step may be performed by separately adding the solution or the dispersion liquid containing the zinc precursor to the solution or the dispersion liquid containing the dicarboxylic acid two or more times. That is, some amount of the solution or the dispersion liquid containing the zinc precursor may be firstly added to perform the reaction, and then the remaining amount of the solution or the dispersion liquid containing the zinc precursor may be separately added later to perform the remaining reaction, such that the entire reaction steps may be performed while maintaining the molar excess state of the dicarboxylic acid in the reaction system, thereby manufacturing the organic zinc catalyst in the zinc dicarboxylate-based catalyst shape having a more uniform and finer particle size and showing an improved activity.
[0028] Here, the step of separately adding the solution or the dispersion liquid containing the zinc precursor two or more times is not particularly limited, and may be performed by several methods.
[0029] First, in an example, the total used amount of the zinc precursor may be separated into two to ten parts, and each of the obtained solutions or the obtained dispersion liquids containing the zinc precursor may be added to the solution or the dispersion liquid containing the dicarboxylic acid two to ten times at an equal time interval during the reaction. Here, preferably, each of the solutions or the dispersion liquids may be obtained by separating the total used amount of the zinc precursor into two to five parts, and may be separately added two to five times. Accordingly, it is possible to manufacture the organic zinc catalyst showing a more improved activity, etc., by effectively maintaining the molar excess condition of the dicarboxylic acid in the reaction system while more increasing productivity of the catalyst manufacturing process.
[0030] In another example, the entire reaction step may be performed by uniformly dropping the solutions or the dispersion liquids containing the zinc precursor in droplet forms onto the solution or the dispersion liquid containing the dicarboxylic acid.
[0031] Meanwhile, by applying the above-described first method (controlling of the total used amount) and the above-described second method (separate addition of the zinc precursor) together, the condition in which the molar excess condition of the dicarboxylic acid is always maintained throughout the entire reaction steps may be more appropriately achieved.
[0032] Meanwhile, in the manufacturing method of the organic zinc catalyst according to the exemplary embodiment as described above, the zinc precursor may be any zinc precursor used for manufacturing zinc dicarboxylate-based catalysts in the art without particular limitation. Specific examples of the zinc precursor may include zinc oxide, zinc sulfate (ZnSO 4 ), zinc chlorate (Zn(ClO 3 ) 2 ), zinc nitrate (Zn(NO 3 ) 2 ), zinc acetate (Zn(OAc) 2 , zinc hydroxide, etc.
[0033] Further, as the dicarboxylic acid reacting with the zinc precursor, any C3-C20 dicarboxylic acid may be used. More specifically, an aliphatic dicarboxylic acid selected from the group consisting of a malonic acid, a glutaric acid, a succinic acid, and an adipic acid, or an aromatic dicarboxylic acid selected from the group consisting of a terephthalic acid, an isophthalic acid, a homophthalic acid, and a phenylglutaric acid may be used, and various C3-C20 aliphatic or aromatic dicarboxylic acids may be used in addition thereto. However, in view of an activity, etc., of the organic zinc catalyst, the dicarboxylic acid is preferably the glutaric acid and the zinc dicarboxylate-based organic zinc catalyst is preferably the zinc glutarate-based catalyst.
[0034] In addition, when the reaction step of the zinc precursor and the dicarboxylic acid is performed in a liquid medium, any organic or aqueous solvent that is known to be capable of uniformly dissolving or dispersing the zinc precursor and/or the dicarboxylic acid may be used as the liquid medium. Specific examples of the organic solvents may include at least one solvent selected from the group consisting of toluene, hexane, DMF, ethanol and water.
[0035] In addition, the reaction step of the zinc precursor and the dicarboxylic acid may be performed at a temperature of about 50 to 130° C. for about 1 to 10 hours. In addition, as previously described, the zinc precursor is separately added at the equal time interval in the total reaction time, such that the molar excess state of the dicarboxylic acid in the reaction system may be maintained throughout the entire reaction steps. By performing the reaction step under the reaction condition, the zinc dicarboxylate-based organic zinc catalyst having more uniform and finer particle size and showing improved physical properties may be manufactured at a high yield.
[0036] The manufacturing method of the organic zinc catalyst obtained by the above-described method is optimized as described above, such that the catalyst may be manufactured in a uniform particle shape having an average particle size of about 0.8 μm or less, or about 0.5 to 0.7 μm, and a particle size standard deviation of about 0.2 μm or less, about 0.1 μm or less, or about 0.05 to 0.1 μm, as compared to the existing catalyst manufactured by the existing method and having a particle size of about 1 to 2 μm. As described above, the organic zinc catalyst has more uniform and finer particle size, such that the organic zinc catalyst may have an increased surface area of about 1.8 m 2 /g or more, or about 1.8 to 2.5 m 2 /g as compared to the existing catalyst having a surface area of about 1.1 to 1.3 m 2 /g. Accordingly, when the organic zinc catalyst is used as the catalyst at the time of manufacturing the polyalkylene carbonate resin by a copolymerization of carbon dioxide and epoxide, contact areas of catalyst particles and reaction materials may be more increased, thereby showing an improved activity.
[0037] Meanwhile, according to another exemplary embodiment of the present invention, there is provided a manufacturing method of a polyalkylene carbonate resin including: polymerizing an epoxide and a monomer including carbon dioxide in the presence of the organic zinc catalyst manufactured by the method of the above-described exemplary embodiment.
[0038] In the manufacturing method of the resin, the organic zinc catalyst may be used in a non-uniform catalyst form, and the polymerizing step may be performed in an organic solvent by solution polymerization. Accordingly, a heat of reaction may be appropriately controlled, and a molecular weight or a viscosity of the polyalkylene carbonate resin to be preferably obtained may be easily controlled.
[0039] In the solution polymerization, as the solvent, at least one selected from the group consisting of methylene chloride, ethylene dichloride, trichloroethane, tetrachloroethane, chloroform, acetonitrile, propionitrile, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, 1,4-dioxane, hexane, toluene, tetrahydrofuran, methyl ethyl ketone, methyl amine ketone, methyl isobutyl ketone, acetone, cyclohexanone, trichloroethylene, methyl acetate, vinyl acetate, ethyl acetate, propyl acetate, butyrolactone, caprolactone, nitropropane, benzene, styrene, xylene, and methyl propasol may be used. Among these examples of the solvent, when methylene chloride or ethylene dichloride is used as the solvent, the polymerization reaction may be more effectively performed.
[0040] The solvent may be used at a weight ratio of about 1:0.5 to 1:100 preferably, at a weight ratio of about 1:1 to 1:10 relative to the epoxide.
[0041] Here, when the ratio is less than about 1:0.5, which is excessively small, the solvent does not appropriately function as a reaction medium, such that it may be difficult to obtain the above-described advantages of the solution polymerization. Further, when the ratio is more than about 1:100, the concentration of epoxide, etc., is relatively decreased, such that productivity may be deteriorated, and a molecular weight of a finally formed resin may be decreased, or a side reaction may be increased.
[0042] Further, the organic zinc precursor may be added at a molar ratio of about 1:50 to 1:1000 relative to the epoxide. More preferably, the organic zinc precursor may be added at a molar ratio of about 1:70 to 1:600, or about 1:80 to 1:300 relative to the epoxide. When the molar ratio is excessively small, it is difficult to show a sufficient catalytic activity at the time of the solution polymerization. On the contrary, when the molar ratio is excessively large, since an excessive amount of the catalyst is used, the reaction is not efficiently performed, by-products may occur, or back-biting of the resin by heating in the presence of the catalyst may occur.
[0043] Meanwhile, as the epoxide, at least one selected from the group consisting of C2-C20 alkylene oxide unsubstituted or substituted with halogen or C1-C5 alkyl group; C4-C20 cycloalkylene oxide unsubstituted or substituted with halogen or C1-C5 alkyl group; and C8-C20 styrene oxide unsubstituted or substituted with halogen or C1-C5 alkyl group may be used. Representatively, as the epoxide, C2-C20 alkylene oxide unsubstituted or substituted with halogen or C1-C5 alkyl group may be used.
[0044] Specific examples of the epoxide include ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxy-7-octene, epifluorohydrine, epichlorohydrine, epibromohydrine, isopropyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide, 2,3-epoxy norbornene, limonene oxide, dieldrin, 2,3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, and the like. As the most representative example, ethylene oxide is used as the epoxide.
[0045] In addition, the above-described solution polymerization may be performed at about 50 to 100° C. and about 15 to 50 bar for about 1 to 60 hours. Further, it is more preferable to perform the solution polymerization at about 70 to 90° C. and about 20 to 40 bar for about 3 to 40 hours.
[0046] Meanwhile, since the remaining polymerization process and condition except for the above description may follow general polymerization condition, etc., for manufacturing the polyalkylene carbonate resin, additional descriptions thereof will be omitted.
[0047] According to the present invention, the catalyst manufacturing process is optimized, such that the organic zinc catalyst for manufacturing the polyalkylene carbonate resin having a more uniform and finer particle size and showing an excellent activity may be manufactured and provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] FIGS. 1 and 2 are scanning electron microscope (SEM) images of organic zinc catalysts obtained from Example 1 and Comparative Example 1, respectively.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0049] Hereinafter, preferable Examples of the present invention will be provided for better understanding of the present invention. However, the following Examples are provided only for illustration of the present invention, and should not be construed as limiting the present invention by the examples.
EXAMPLE 1
Manufacture of Organic Zinc Catalyst (Molar Ratio of ZnO and Glutaric Acid=1:1.2)
[0050] 7.93 g (0.06 mol) of a glutaric acid and 0.1 mL of acetic acid were added to 100 mL toluene in a 250 mL size round bottom flask, and dispersed under reflux. Then, the mixture was heated at a temperature of 55° C. for 30 minutes, and 4.1 g (0.05 mol) of ZnO was added to 50 mL of toluene, and dispersed. The reaction was performed by firstly adding 25 vol% of the ZnO dispersion liquid to the glutaric acid dispersion liquid, then after 1 hour, adding another 25 vol % out of 75 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid, and after 1 hour, adding the third 25 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid. Next, after 1 hour, the other 25 vol % of the ZnO dispersion liquid was lastly added to the glutaric acid dispersion liquid. The mixed solution was heated at 110° C. for 2 hours. A white solid was produced, filtered and washed with acetone/ethanol, and dried in a vacuum oven at 130° C.
[0051] According to the above-described method, the organic zinc catalyst of Example 1 was manufactured. A scanning electron microscope (SEM) image of the organic zinc catalyst of Example 1 was shown in FIG. 1 . It was confirmed from the SEM analysis that the organic zinc catalyst of Example 1 had an average particle size of about 0.5 μm and a particle size standard deviation of about 0.13 μm.
EXAMPLE 2
Manufacture of Organic Zinc Catalyst (Molar Ratio of ZnO and Glutaric Acid=1:1.5)
[0052] 9.91 g (0.075 mol) of a glutaric acid and 0.1 mL of acetic acid were added to 100 mL toluene in a 250 mL size round bottom flask, and dispersed under reflux. Then, the mixture was heated at a temperature of 55° C. for 30 minutes, and 4.1 g (0.05 mol) of ZnO was added to 50 mL of toluene, and dispersed. The reaction was performed by firstly adding 25 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid, then after 1 hour, adding another 25 vol % out of 75 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid, and after 1 hour, adding the third 25 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid. Next, after 1 hour, the other 25 vol % of the ZnO dispersion liquid was lastly added to the glutaric acid dispersion liquid. The mixed solution was heated at 110° C. for 2 hours. A white solid was produced, filtered and washed with acetone/ethanol, and dried in a vacuum oven at 130° C.
[0053] According to the above-described method, the organic zinc catalyst of Example 2 was manufactured. The organic zinc catalyst of Example 2 was confirmed by SEM analysis. As a result, it was confirmed that the organic zinc catalyst of Example 2 had an average particle size of about 0.8 μm and a particle size standard deviation of about 0.19 μm.
EXAMPLE 3
Manufacture of Organic Zinc Catalyst (Molar Ratio of ZnO and Glutaric Acid=1:1)
[0054] 6.61 g (0.05 mol) of a glutaric acid and 0.1 mL of acetic acid were added to 100 mL toluene in a 250 mL size round bottom flask, and dispersed under reflux. Then, the mixture was heated at a temperature of 55° C. for 30 minutes, and 4.1 g (0.05 mol) of ZnO was added to 50 mL of toluene, and dispersed. The reaction was performed by firstly adding 25 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid, then after 1 hour, adding another 25 vol % out of 75 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid, and after 1 hour, adding the third 25 vol % of the ZnO dispersion liquid to the glutaric acid dispersion liquid. Next, after 1 hour, the other 25 vol % of the ZnO dispersion liquid was lastly added to the glutaric acid dispersion liquid. The mixed solution was heated at 110° C. for 2 hours. A white solid was produced, filtered and washed with acetone/ethanol, and dried in a vacuum oven at 130° C.
[0055] According to the above-described method, the organic zinc catalyst of Example 3 was manufactured. The organic zinc catalyst of Example 3 was confirmed by SEM analysis. As a result, it was confirmed that the organic zinc catalyst of Example 3 had an average particle size of about 0.6 μm and a particle size standard deviation of about 0.18 μm.
EXAMPLE 4
Manufacture of Organic Zinc Catalyst (Molar Ratio of zinc Nitrate (Zn(NO 3 ) 2 ) and Glutaric Acid=1:1.2)
[0056] The organic zinc catalyst of Example 4 was manufactured by the same method as Example 1 except for using 11.36 g (0.06 mol) of Zn(NO 3 ) 2 ) instead of using ZnO, as the zinc precursor. The organic zinc catalyst of Example 4 was confirmed by SEM analysis. As a result, it was confirmed that the organic zinc catalyst of Example 4 had an average particle size of about 0.8 μm and a particle size standard deviation of about 0.20 μm.
Comparative Example 1
Manufacture of Organic Zinc Catalyst (Molar Ratio of ZnO and Glutaric Acid=1:1)
[0057] 6.61 g (0.05 mol) of a glutaric acid, 4.1 g (0.05 mol) of ZnO and 0.1 mL of acetic acid were added to 150 mL toluene in a 250 mL size round bottom flask, and dispersed under reflux. Next, the mixed solution was heated at 55° C. for 3 hours, and further heated at 110° C. for 4 hours. A white solid was produced, filtered and washed with acetone/ethanol, and dried in a vacuum oven at 130° C.
[0058] According to the above-described method, the organic zinc catalyst of Comparative Example 1 was manufactured. A scanning electron microscope (SEM) image of the organic zinc catalyst of Comparative Example 1 was shown in FIG. 2 . It was confirmed from the SEM analysis that the organic zinc catalyst of Comparative Example 1 had a particle size of about 1 to 2 μm and a particle size standard deviation of about 0.4 μm or more.
Comparative Example 2: Manufacture of Organic Zinc Catalyst (Molar Ratio of ZnO and Glutaric Acid=1:1.2)
[0059] 7.93 g (0.06 mol) of a glutaric acid and 0.1 mL of acetic acid were added to 100 mL toluene in a 250 mL size round bottom flask, and dispersed under reflux. Then, the mixture was heated at a temperature of 55° C. for 30 minutes, and 4.1 g (0.05 mol) of ZnO was added to 50 mL of toluene, and dispersed. The reaction was performed by firstly adding 25 vol % of the glutaric acid dispersion liquid to the ZnO dispersion liquid, then after 1 hour, adding another 25 vol % out of 75 vol % of the glutaric acid dispersion liquid to the ZnO dispersion liquid, and after 1 hour, adding the third 25 vol % of the glutaric acid dispersion liquid to the ZnO dispersion liquid. Next, after 1 hour, the other 25 vol % of glutaric acid dispersion liquid was lastly added to the ZnO dispersion liquid. The mixed solution was heated at 110° C. for 2 hours. A white solid was produced, filtered and washed with acetone/ethanol, and dried in a vacuum oven at 130° C.
[0060] According to the above-described method, the organic zinc catalyst of Comparative Example 2 was manufactured. The organic zinc catalyst of Comparative Example 2 was confirmed by SEM analysis. As a result, it was confirmed that the organic zinc catalyst of Comparative Example 2 had an average particle size of about 1.7 μm and a particle size standard deviation of about 0.43 μm or more.
[0061] Polymerization Example
[0062] Polyethylene carbonates were polymerized and manufactured by performing the following method and using the catalysts of Examples 1 to 4 and Comparative Examples 1 and 2.
[0063] First, 0.4 g of each catalyst and 8.52 g of dichloromethane (methylene chloride) were added to a high-pressure reactor in a glove box, and 8.9 g of ethylene oxide was added. Then, the mixture was pressed in the reactor by a pressure of 30 bar using carbon dioxide. The polymerization reaction was performed at 70° C. for 3 hours. After the reaction was completed, unreacted carbon dioxide and ethylene oxide were removed together with dichloromethane which is a solvent. In order to measure an amount of the manufactured polyethylene carbonate, the remaining solid was completely dried and quantified. Each activity and yield of the catalysts according to the polymerization results were shown in Table 1 below.
[0000]
TABLE 1
Molar ratio of
Activity of catalyst
ZnO:Glutaric
Yield
(g-polymer/g-
acid
(g)
catalyst)
Example 1
1:1.2
20.9
52.3
Example 2
1:1.5
16.5
36.2
Example 3
1:1
20.1
50.3
Example 4 a)
1:1.2
14.3
35.8
Comparative
1:1
11.9
29.8
Example 1
Comparative
1:1.2
10.2
25.5
Example 2 b)
a) Example 4: Zn(NO 3 ) 2 was used instead of using ZnO;
b) Comparative Example 2: Glutaric acid was separately added to ZnO dispersion liquid.
[0064] Referring to Table 1 above, it was confirmed that the catalysts of Examples 1 to 4 had more excellent activity than that of Comparative Examples 1 and 2. In addition, from the catalysts of Examples 1 to 4, the polyethylene carbonate could be manufactured at an excellent yield.
[0065] While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. | The present invention relates to a manufacturing method of an organic zinc catalyst having more uniform and finer particle size and showing a more improved activity in a polymerization process for manufacturing a polyalkylene carbonate resin, and a manufacturing method of the polyalkylene carbonate resin using the organic zinc catalyst obtained by the manufacturing method of the organic zinc catalyst, the manufacturing method of an organic zinc catalyst including: forming a zinc dicarboxylate-based catalyst by reacting a zinc precursor with C3-C20 dicarboxylic acid, wherein the reaction step is performed under a condition in which the number of moles of the dicarboxylic acid is more than that of the zinc precursor in a reaction system, throughout the entire reaction step. | 1 |
FIELD OF THE INVENTION
The present invention relates to rescue systems for evacuating individuals trapped in high-rise buildings in case of an emergency situation, typically fire.
More specifically the invention concerns fire escapes using chutes or tubes through which individuals glide down from the building.
BACKGROUND OF THE INVENTION
The first known attempts to tackle the problem at hand are disclosed in and by U.S. Pat. No. 908,034 (Dec. 29, 1908) and U.S. Pat. No. 1,520,440 (Dec. 23, 1924), both to Frank Pyleck and entitled “Automatic Fire-Escape”.
In the first Patent there was described a foldable chute normally stored in a box that is hingedly supported. In the standby position, the box is arrested against the outer wall of the building, at one side of a window. When needed, the box is released and allowed, under the bias of springs, to smash into and is break open the window. The chute becomes released and projects down. The ejection of the chute, as well as its support in a sloping down to ground level position, are sustained by a coil spring wound around the chute along its entire length, while the exit side is freely rested on the ground.
Further disclosed were a pair of cords passed along the chute by which the chute can be collapsed and folded back into the storage box.
In the second, later Patent, the inventor proposed to substitute the supporting coil spring by a solid track or rail permanently mounted to the building wall above the window and inclining down parallel to the path of the unfolded chute. The chute, after being deployed will be suspended from the rail by a series of wheeled hangers running along the rail.
Quite obviously, these solutions might have been of some merit at the beginning of the past century with regard to buildings of, say, four or five stories at the most, but out of the question for modern hi-rise buildings. Hence, and only quite recently, other solutions have been proposed—cf. U.S. Pat. No. 4,099,596 (1978); U.S. Pat. No. 4,240,520 (1980); U.S. Pat. No. 4,398,621 (1983), and U.S. Pat. No. 4,580,659 (1986), each one pointing in a different direction and none of them known to have gained commercially successful implementation.
It is therefore the general object of the present invention to overcome the deficiencies of the prior art chute-gliding fire-escape systems.
It is a further object of the invention to employ a tension cable as the only supporting means of the sliding sleeve.
It is a still further object of the invention to provide delimiting stretches of cables, associated with the same tension cable for forming knee-like sections along the sleeve for locally moderating the inclination angle thereof.
SUMMARY OF THE INVENTION
The invention provides a system particularly useful for the evacuation of individuals from an elevated level of a building, comprising: a flexible sleeve capable of being folded into a compact storage form, or unfolded into an extended operative form defining a tube for guiding the descent of an individual therethrough; the flexible sleeve having an entry end to be secured to the building at the elevated level, and an exit end to be secured to a stable object at a lower level in the extended operative form of the flexible sleeve.
According to one aspect of the present invention, the flexible sleeve includes a plurality of annular sections interconnected together, each section being made of strong flexible sheet material attached to and supported by a rigid ring; each of at least some of the rigid rings spaced along the length of the flexible sleeve carrying an eyelet extending upwardly from an upper portion of the respective rigid ring; a tension cable passing through the eyelets, one end of the tension cable being fixed to the rigid ring at or adjacent to the exit end of the flexible sleeve, and the opposite end of the tension cable passing through the eyelet carried by the rigid ring at or adjacent to the entry end of the flexible sleeve for securement with respect to the building; and at least one anchoring cable having one end to be secured to said tension cable at or adjacent to the exit end of the flexible sleeve in the extended operative form of the flexible sleeve, and an opposite end to be secured to the stable object at the lower level.
According to another aspect of the present invention, the flexible sleeve includes a plurality of annular sections interconnected together, each section being made of strong flexible sheet material attached to and supported by a rigid ring; each of at least some of the rigid rings carrying an eyelet extending upwardly from an upper portion of the respective rigid ring, an upper tension cable passing through the upwardly-extending eyelets, one end of the upper tension cable being fixed to the respective rigid ring at or adjacent to the exit end of the flexible sleeve, and the opposite end of the upper tension cable passing through the eyelet carried by the respective rigid ring at or adjacent to the entry end of the flexible sleeve for securement with respect to the building; a compartment for receiving the flexible sleeve when in its compact storage form; a backing plate displaceable within the compartment; and a winch in the compartment secured to said opposite end of the upper tension cable such that operation of the winch, while the flexible sleeve is in its extended operative form, draws the annular sections of the flexible sleeve into the compartment against said displaceable backing plate and folds the annular sections into the compact storage form.
According to a further aspect of the present invention, the flexible sleeve includes a plurality of annular sections interconnected together, each section being made of strong flexible sheet material attached to and supported by a rigid annular ring, and a plurality of interconnected semi-annular sections at the exit end of the flexible sleeve, each including flexible sheet material attached to and supported by a semi-annular ring; each of at least some of the rigid annular rings carrying an eyelet extending upwardly from the upper portion of the respective ring; each of at least some of the annular and semi-annular rings carrying an eyelet extending downwardly from a lower portion of the respective ring; an upper tension cable passing through the upwardly-extending eyelets; and a lower tension cable passing through the downwardly-extending eyelets, with one end of each cable being fixed to the respective ring at or adjacent to the exit end of the flexible sleeve, and the opposite end of each tension cable passing through the eyelet carried by the ring at or adjacent to the entry end of the flexible sleeve for securement with respect to the building.
Further novel features and other objects of this invention will become apparent from the following detailed description, discussion, and the appended claims taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view of the emergency rescue system in the operative position thereof;
FIG. 2 is an enlarged view of the down-stream end of the rescue sleeve;
FIG. 2 a is a side view, showing the end side of the sleeve;
FIGS. 3 a – 3 d are details of construction relating to the rings interposed between successive sections of the sleeve;
FIG. 4 a illustrates the connection between adjacent sleeve sections;
FIG. 4 b is a partial side view of FIG. 4 a;
FIG. 5 shows a knee-forming arrangement;
FIG. 6 is a detail of construction relating to the attachment of auxiliary cables;
FIG. 7 is a partly sectional side view of the sleeve-storing compartment, taken along line VII—VII of FIG. 8 ;
FIG. 8 is a view taken along line VIII—VIII of FIG. 7 ;
FIG. 9 is a view taken along line IX—IX of FIG. 7 ;
FIG. 9 a is a detail of construction relating to FIG. 9 ;
FIG. 10 is a view taken along line X—X of FIG. 7 ;
FIG. 11 is a view taken along line XI—XI of FIG. 7 ;
FIG. 12 is a view taken along line XII—XII of FIG. 8 ;
FIG. 13 is a sectional view similar to that of FIG. 7 , following the ejection of the sleeve from the standby position; and
FIG. 14 shows the system in the sleeve deployed position prior to the anchoring as depicted in FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1 there is illustrated a multiple level building 10 (residential or hotel) equipped with an evacuation system constructed in accordance with the present invention. Such an evacuation system includes a flexible sleeve 12 capable of being folded into a compact storage form ( FIG. 8 ) or unfolded into an extended operative form ( FIGS. 1 , 13 , 14 ) defining a tube for guiding the descent of an individual. The flexible sleeve 12 has an entry end secured to the building at the elevated level from which individuals are to be evacuated, and an exit end to be secured to a fixed or stable object at a lower level in the extended operative form of the flexible sleeve.
In FIG. 1 the rescue sleeve or chute 12 has been ejected as will be described in greater detail below. The exit end of the sleeve 12 is brought (e.g. by a specially trained rescue team) to a convenient evacuation point, namely one that is as far from the building as allowed by the length of the sleeve on the one hand, and by the surrounding topography (nearby buildings or other obstacles) on the other hand. As already mentioned, the sleeve is self-supported by anchoring the sleeve, e.g., by cables 14 and 15 connecting the exit end of the sleeve to any kind of stable objects such as nearby parked vehicles, trees, street lamp posts and the like, schematically represented by poles 16 and 17 . Preferably though, for the sake of better support and greater safety, a number of auxiliary anchor cables 18 should be available and used as shown and will be described further below.
It will be further noted (see FIG. 2 ) that the sleeve 12 is mostly made of tapeworm-like structure, namely a chain of annular interconnected sections 20 , which are made of strong, flexible sheet material such as nylon, canvas fabric and the like, sewn to each other and strengthened by rigid annular rings generally denoted 22 e.g., FIGS. 4 a, 4 b ).
At the exit end, however, the sleeve 12 can be constructed of semi-annular rings so as to define half-open sections 20 ′, and provided with preferably self-inflated cushions 24 , intended to brake and absorb the gliding movement o the rescued persons (shown in phantom lines) using the sleeve.
In addition there are provided a pair of tension cables 26 , 27 , running all along the sleeve 12 . Cable 16 runs at the bottom side, threaded through downwardly-extending eyelets 28 carried by lower portions of alternate rings 22 . Every eyelet is preferably pivotally connection ( FIGS. 3 a – 3 d ) via a U-shaped bracket 30 which is welded to the respective ring 22 .
One end of cable 26 is fixed to the ring 22 at the exit end of sleeve 12 .
The same arrangement exists with respect to the top running cable 27 , which is threaded through upwardly extending eyelets 28 carried by the upper portions of the remaining alternate rings 22 in a staggered fashion relative to cable 26 .
Yet another detail of construction is shown in FIGS. 4 a and 4 b. This relates to the manner the sleeve sections 20 are sewn to each other and to the rings 22 . Hence, the margins of each section are bent radially outwards, folded about themselves and fastened by stitches S 1 and S 2 , leaving an extended portion directed backwards. The ring 22 is then assembled by a circular wrapping 32 of cloth which envelops the ring and is fastened to the said extended portions by stitches S 3 and S 4 .
The brackets 30 for the eyelets 28 will of course penetrate outwards of the envelope 32 ( FIG. 4 b ).
The arrangement of FIG. 5 may be adopted in order to form locally knee-like sections that will serve to moderate the speed of the free gliding persons by constituting successive stretches of less-steep angles. When in the folded state (see below), several stretches of an additional delimiting or constraining cable 34 are tied, at certain intervals each between two spaced eyelets of the top cable 27 , restricting the distance between the respective rings at their upper points to a pre-set length. This will constrain the portion of the sleeve between the two eyelets to a predetermined curve and will thereby cause the sleeve 12 to form knee-like sections 12 a when unfolded. The number of such knee-like sections 12 a will be determined according to the overall height of the sleeve (i.e., the respective building storey) and the amount of the final desired curvature of the sleeve as a whole.
As already mentioned, auxiliary anchor cables 18 ( FIG. 1 ) may be requested. For that purpose, a second series of swivable eyelets 40 are employed ( FIG. 6 ), A pair of eyelets 40 are carried by the appropriate sides of at least one ring 22 , preferably a plurality of such rings, at or adjacent to the exit end of the sleeve and serve a anchoring elements for anchor cables 18 .
As further seen in FIG. 6 , the eyelet configuration is advantageous, allowing the auxiliary anchor cables 18 be constituted by loops, the idea being that after use, the cables can be cut and completely removed from the sleeve. This is important for facilitating a smooth folding back of the sleeve for re-use (see below), without needing to attend specially to the orderly collection of these cables.
The re-installment of the cables 18 will take place at a later stage, in the folded-back state of the sleeve, through a service opening (sliding doors 74 and 75 ), as will be described later on.
Reference shall now be made to FIGS. 7–12 . At every story of the building 10 , next to an external wall 10 a, a compartment generally denoted 50 will be installed, associated with a dedicated preferably oval opening 10 b with a funnel-like extension 10 c ( FIG. 13 ).
The rescue sleeve 12 is shown in the folded, stand-by state, after the cables 26 and 27 have been fully rewound by respective electrically powered winch systems 52 and 54 .
Cable 26 passes through a guiding tube 56 , having for that purpose a somewhat flared opening portion 56 a. The same applies with respect to tube 58 for cable 27 .
Coil springs 60 and 62 are installed, both acting against a displaceable backup plate 64 (see FIG. 9 ) defining the surface against which the sleeve 12 is folded, in an accordion-like fashion.
Compartment 50 has an entering opening 64 a, equal to or larger than the diameter of the sleeve 12 .
Since the distance between the tubes 56 and 58 is greater than the diameter of sleeve 12 , and in view of the alternate order of the eyelet 28 relative to the lower cable 26 and the upper cable 27 , the sleeve sections 20 will become folded not overlapping each other, but in a staggered, zig-zag fashion, to save storing space.
The compartment 50 is made of metal construction, and is provided with a first, weather-proof sliding door 70 (see FIG. 10 ), a second sliding door 72 , facing the interior of the building, and two pairs of third service sliding door systems 74 a, 74 b and 75 a, 75 b (see FIGS. 8 and 12 ) at both sides of the compartment 50 , serving to allow access from the side for re-connecting the auxiliary anchor cables 18 after the use of the rescue sleeve and the cable having been cut and removed to facilitate smooth and trouble-free folding-back of the sleeve into its stand-by position.
The operation of the rescue-sleeve system is illustrated in FIG. 13 . Hence, in case of emergency, the door 70 is pulled aside (see FIG. 10 ) and the winch systems 52 and 54 released for free wheel rotation of their drums. Consequently, under the force of the springs 60 and 62 , the plate 64 will shoot (to the left in FIG. 7 ) and cause the folded sleeve to become ejected out through the opening 10 b and paid down over the funnel shaped section 10 c provided for that purpose.
Now, the position of FIG. 14 is reached, where the sleeve 12 freely hangs down, except for the knee section(s) 34 that start shaping the sleeve towards the operative position of FIG. 1 .
The auxiliary cables 18 (having been attached and prepared in the folded position of the sleeve as already explained) hang freely down as shown, ready to be picked up by the rescue team and tied to any available stationary object. The free end of the sleeve is tied by at-least the tension cable 27 as already explained with reference to FIG. 1 and the system is ready for its life saving goal.
While the above description contains many specificities, these should not be construed as limitations on the scope of the invention, but rather as exemplification of the preferred embodiments. Those skilled in the art will envision other possible variations that are within its scope. Accordingly, the scope of the invention should be determined not by the embodiment illustrated, but by the appended claims. | A system for the evacuation of individuals trapped in multiple story buildings by gliding down a rescue sleeve. The sleeve ( 12 ) is composed of sections ( 20 ), each section being made of a sheet material strengthened by a circumferential rigid support member ( 22 ), the sections are connected to each other to form a continuous envelope. At least a pair of cables ( 26; 27 ) are provided, thread along the sleeve, one ( 26 ) at the bottom and one ( 27 ) at the top generatrix thereof. A pair of winch systems ( 52; 54 ) are provided for winding the cables ( 26; 27 ) into a dedicated location ( 50 ) at the building story from which rescue is requested, so that the sleeve ( 12 ) becomes folded into a compact package. Coil springs ( 60; 62 ) are used for selectively ejecting and unfolding the sleeve down to ground level where it becomes tied to stationary objects ( 16; 17 ). | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to magnetoresistive random access memory (MRAM), and more specifically, to read and write conductors for MRAM.
BACKGROUND OF THE INVENTION
[0002] Integrated circuit designers have always sought the ideal semiconductor memory: a device that is randomly accessible; can be written to or read from very quickly; is non-volatile, but indefinitely alterable; and consumes little power. Magnetoresistive random access memory (MRAM) technology has been increasingly viewed as offering all of these advantages.
[0003] An MRAM memory cell contains a non-magnetic conductor forming a lower electrical contact, a pinned magnetic layer, a barrier layer, a free magnetic layer, and a second non-magnetic conductor. The pinned magnetic layer, tunnel barrier layer, and free magnetic layer are collectively termed the magnetic tunnel junction (MTJ) element.
[0004] Information can be written to and read from the MRAM cell as a “1” or a “0,” where a “1” generally corresponds to a high resistance level, and a “0” generally corresponds to a low resistance level. Directions of magnetic orientations in the magnetic layers of the MRAM cell cause resistance variations. Magnetic orientation in one magnetic layer is magnetically fixed or pinned, while the magnetic orientation of the other magnetic layer is variable so that the magnetic orientation is free to switch direction. In response to the shifting state of the free magnetic layer, the MRAM cell exhibits one of two different resistances or potentials, which, as described above, are read by the memory circuit as either a 37 1” or a “0.” It is the creation and detection of these two distinct resistances or potentials that allows the memory circuit to read from and write information to an MRAM cell.
[0005] A bit of information may be written into the MTJ element of an MRAM cell by applying orthogonal magnetic fields directed within the XY-plane of the MTJ element. Depending on the strength of the magnetic fields, which are created by a current passing through the write line, the free magnetic layer's polarization may remain the same or switch direction. The free magnetic layer's polarization then may continue to be parallel to the pinned magnetic layer's polarization, or anti-parallel to the pinned magnetic layer's polarization.
[0006] A bit of information is retrieved from the MTJ element by measuring its resistance via a read current directed along the Z-axis, transverse to the XY-plane. The state of the MTJ element can be determined by the read conductor measuring the resistance of the memory cell. The MTJ element is in a state of low resistance if the overall orientation of magnetization in the free magnetic layer is parallel to the orientation of magnetization of the pinned magnetic layer. Conversely, the MTJ element is in a state of high resistance if the overall orientation of magnetization in the free magnetic layer is anti-parallel to the orientation of magnetization in the pinned magnetic layer.
[0007] Conventional MRAM structures, such as that depicted in FIG. 1 , typically have a write conductor 20 and a read conductor 26 , separated by a liner 17 , together forming a word line 32 . Other layers may be included, but are omitted for clarity. The word line 32 of a conventional MRAM structure is typically formed in a first insulating layer (typically an oxide layer) 10 , with an MTJ element 28 formed over the word line 32 . Typically, the read conductor 26 is less than 500 nm wide and less than 50 nm thick. The dimensions of the read conductor 26 and the liner 17 separate the MTJ element 28 from the write conductor 20 .
[0008] Conventional MRAM structures electrically isolate the write conductor 20 from the MTJ element 28 to protect the MTJ element 28 from a voltage created when a current is applied to the write conductor 20 to write a bit of information onto the MTJ element 28 . However, by isolating the write conductor 20 from the MTJ element 28 , a higher current is necessary to achieve the same electromagnetic field to write a bit of information if the write conductor 20 was not electrically isolated. The higher current results in higher voltages applied to the MTJ element 28 .
BRIEF SUMMARY OF THE INVENTION
[0009] The present invention seeks to reduce the amount of current required for a write operation by using a process for forming the read conductor within a recessed write conductor, the write conductor itself formed within a trench of an insulating layer. The present invention protects the MTJ from the voltages created by the write conductor by isolating the write conductor and enabling the reduction of current necessary to write a bit of information.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The above-described features and advantages of the invention win be more clearly understood from the following detailed description, which is provided with reference to the accompanying drawings in which:
[0011] FIG. 1 depicts a conventional MRAM cell structure.
[0012] FIG. 2 depicts a stage of processing of an MRAM device, in accordance with an exemplary embodiment of the invention;
[0013] FIG. 3 depicts a further stage of processing of the FIG. 2 MRAM device;
[0014] FIG. 4 depicts a further stage of processing of the FIG. 3 MRAM device;
[0015] FIG. 5 depicts a further stage of processing of the FIG. 4 MRAM device;
[0016] FIG. 6 depicts a further stage of processing of the FIG. 5 MRAM device;
[0017] FIG. 7 depicts a further stage of processing of the FIG. 6 MRAM device;
[0018] FIG. 8 depicts a further stage of processing of the FIG. 7 MRAM device;
[0019] FIG. 9 depicts a further stage of processing of the FIG. 8 MRAM device;
[0020] FIG. 10 depicts a further stage of processing of the FIG. 9 MRAM device;
[0021] FIG. 11 depicts a further stage of processing of the FIG. 10 MRAM device;
[0022] FIG. 12 depicts a further stage of processing of the FIG. 11 MRAM device;
[0023] FIG. 13 depicts a further stage of processing of the FIG. 12 MRAM device;
[0024] FIG. 14 depicts a further stage of processing of the FIG. 13 MRAM device;
[0025] FIG. 15 depicts a further stage of processing of the FIG. 14 MRAM device;
[0026] FIG. 16 depicts a further stage of processing of the FIG. 15 MRAM device;
[0027] FIG. 17 is a cutaway perspective view of a semiconductor chip containing a plurality of MRAM devices according to an exemplary embodiment of the invention; and
[0028] FIG. 18 is a schematic diagram of a processor system incorporating an MRAM device in accordance with an exemplary embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] In the following detailed description, reference is made to specific exemplary embodiments of the invention. It is to be understood that other embodiments may be employed, and that structural and electrical changes may be made without departing from the spirit or scope of the present invention.
[0030] The term “semiconductor substrate” is to be understood to include any semiconductor-based structure that has an exposed semiconductor surface. The semiconductor structure should be understood to include silicon, silicon-on-insulator (SOI), silicon-on-sapphire (SOS), doped and undoped semiconductors, epitaxial layers of silicon supported by a base semiconductor foundation, and other semiconductor structures. The semiconductor substrate need not be silicon-based. The semiconductor could be silicon-germanium, germanium, or gallium arsenide. When reference is made to a semiconductor substrate in the following description, previous process steps may have been utilized to form regions or junctions in or over the base semiconductor or foundation. Also, the invention may be formed over non-semiconductor substrates.
[0031] The steps below are discussed as being performed in an exemplary order, however this order may be altered and still maintain the spirit and scope of the invention.
[0032] Referring now to the drawings, where like elements are designated by like reference numerals, FIG. 2 depicts a cross-section of an MRAM memory cell during an intermediate stage of processing, wherein a first insulating layer (preferably an oxide layer) 10 is formed over a substrate 8 , for example, a semiconductor substrate. The oxide layer 10 is preferably comprised of silicon oxide, but could be comprised of other well known oxide materials such as silicon dioxide, aluminum oxide, or tetraethylorthosilicate (TEOS). For simplicity of description, the substrate 8 is omitted in FIGS. 3-17 .
[0033] With reference to FIG. 3 , a trench 12 is etched into the oxide layer 10 by chemical etching, reactive ion etching (RIE), or other means of creating a trench in the oxide layer 10 . The trench 12 creates an oxide layer 10 having a first upper level 13 and second lower level 15 , both first and second levels connected by a sidewall region 11 .
[0034] In FIG. 4 , a liner 14 is deposited on the silicon oxide layer 10 . The liner 14 can be formed of a material selected from the group including, but not limited to, tantalum (Ta), titanium (Ti), titanium-tungsten (TiW), titanium-nitride (TiN), tungsten-silicide (WSi 2 ), tungsten-nitride (WN), or chromium (Cr). The liner 14 is optional, but preferred because it serves as an adhesion layer for a later formed ferromagnetic cladding layer 16 ( FIG. 5 ).
[0035] It should be noted that trench 12 may optionally be filled with material used to form the liner 14 , or any other subsequent layer, and then, through etching or abrasion of the structure, the trench 12 could be redefined. This ensures that each subsequent layer is formed within the trench 12 .
[0036] As depicted in FIG. 5 , a ferromagnetic cladding layer 16 is deposited over the liner 14 . The ferromagnetic cladding layer 16 can be formed from a variety of materials, including, but not limited to, nickel-iron (Ni—Fe), cobalt-iron (Co—Fe), cobalt-nickel-iron (Co—Ni—Fe), iron (Fe), nickel (Ni), cobalt (Co), or other highly permeable materials. The ferromagnetic cladding layer 16 provides a closed magnetic path (flux closure) around a subsequently formed write conductor 20 ( FIG. 7 ). The ferromagnetic cladding layer 16 also substantially attenuates fringe magnetic fields that can interfere or corrupt bit information stored in the MTJ elements of neighboring memory cells.
[0037] Referring to FIG. 6 , a barrier layer 18 is provided over the ferromagnetic cladding layer 16 . The barrier layer 18 may be formed of a conventional insulator, for example, a low pressure chemical vapor deposition (CVD) oxide, a nitride, such as Si 3 N 4 , low pressure or high pressure TEOS, or boro-phospho-silicate glass (BPSG). The barrier layer 18 is an optional layer, and is preferable if the resistance of the cladding material used to form the ferromagnetic cladding layer 16 is greater than 1/10 the resistance of the conductor material used to form the write conductor 20 ( FIG. 7 ). The barrier layer 18 is also preferable if the cladding material used to form the ferromagnetic cladding layer 16 is not fully removed from the regions between the write conductor 20 ( FIG. 7 ) and the read conductor 26 ( FIG. 11 ) during further processing. The barrier layer 18 serves as an adhesion layer, and prevents the migration of the conductive material used to form the write conductor 20 ( FIG. 7 ) into the lower layers.
[0038] It should be noted that if the barrier layer 18 is not formed, a liner 17 ( FIG. 6A ) could be formed over the ferromagnetic cladding layer 16 . The liner 17 can be formed of a material selected from the group including, but not limited to, tantalum (Ta), titanium (Ti), titanium-tungsten (TiW), titanium-nitride (TiN), tungsten-silicide (WSi 2 ), tungsten-nitride (WN), or chromium (Cr). The liner is optional, but preferred in the absence of the barrier layer 18 because it serves as an adhesion layer for the write conductor 20 ( FIG. 7 ).
[0039] In FIG. 7 , a write conductor 20 is formed over the barrier layer 18 . The write conductor 20 is preferably made of copper. It should be noted that the write conductor 20 could be made of other conductive materials, including, but not limited to, tungsten, platinum, gold, silver, or aluminum.
[0040] In FIG. 8 , a second insulating layer 22 is deposited (the oxide layer 10 being the first insulating layer). The second insulating layer 22 can be formed of a variety of materials, including, but not limited to, silicon nitrides, alumina oxides, oxides, high temperature polymers, or a dielectric material.
[0041] In FIG. 9 , the layers that have been formed on the first level 13 of the oxide layer 10 are removed, for example, by chemical-mechanical polishing (CMP) or RIE dry etching, creating an oxide layer 10 with a trench 12 that has a liner 14 , a ferromagnetic cladding layer 16 , a barrier layer 18 , a write conductor 20 , and a second insulating layer 22 .
[0042] Referring to FIG. 10 , a third insulating layer 24 is formed over the entire FIG. 9 structure. The third insulating layer 24 is optional. Preferably, a read conductor 26 is formed over the third insulating layer 24 and within the trench, as shown in FIG. 11 . However, it should be noted that the read conductor 24 could be formed directly over the second insulating layer as shown in FIG. 11A . The read conductor 26 is preferably formed of copper (Cu), but could be made of any other conductive material, including, but not limited to, tungsten, platinum, gold, silver, tantalum, or aluminum.
[0043] The excess material used to form the read conductor 26 is then removed through mechanical abrasion, for example, conventional CMP methods, creating a planarized surface in which the topmost surface of the read conductor 26 is planar to the topmost surface of the third insulating layer 24 ( FIG. 12 ). Planarizing the structure of FIG. 11A would result in the structure depicted in FIG. 12A , specifically, a topmost surface of the read conductor 26 is planar to a topmost surface of the second insulating layer 22 .
[0044] Referring to FIGS. 13 and 13 A, layers that will form an MTJ element 28 are next formed. The MTJ element 28 is formed by three layers, a pinned magnetic layer 28 a , a tunnel barrier layer 28 b , and a free magnetic layer 28 c . It should be noted that a variety of other layers could be included, but are omitted for purposes of clarity. It should also be noted that the three functional layers could be formed in reverse order.
[0045] FIG. 14 depicts the deposition of a hard mask 30 . The hard mask 30 serves as an etch barrier and protects the underlying MTJ element 28 during any further processing. The MTJ element 28 is patterned, or etched, as shown in FIGS. 15 and 15 A. In FIGS. 16 and 16 A, the hard mask 30 is removed, and the resulting structure is an MRAM structure wherein the read conductor 26 is formed within a recess of the write conductor 20 . The preceding processes result in a self-aligned, low-resistant, and efficient formation of read and write conductors.
[0046] FIG. 17 is a cutaway perspective view of a semiconductor chip 100 containing a plurality of MRAM devices 170 manufactured in accordance with FIGS. 2-16 . In accordance with an exemplary embodiment of the invention, each of a plurality of MRAM devices 170 has a read conductor 26 formed in a trench of a write conductor 20 . The etching to form the MTJ elements 28 assures discrete MTJ element islands formed over the read conductor 26 . A sense line 38 is positioned orthogonally above the MTJ elements 28 . The sense line 38 is preferably formed of copper (Cu). It should be noted that the sense line 38 could be made of other conductive materials, including, but not limited to, tungsten-nitride, tungsten, platinum, gold, silver, or aluminum. The sense line 38 is activated during a read or write operation. The sense line 38 , in conjunction with the read conductor 26 or write conductor 20 , selects the MTJ element 28 in the array that will either be written to or read from.
[0047] FIG. 18 illustrates an exemplary processing system 900 utilizing the MRAM memory device as described in connection with FIGS. 2-17 . The processing system 900 includes one or more processors 901 coupled to a local bus 904 . A memory controller 902 and a primary bus bridge 903 are also coupled the local bus 904 . The processing system 900 may include multiple memory controllers 902 and/or multiple primary bus bridges 903 . The memory controller 902 and the primary bus bridge 903 may be integrated as a single device 906 .
[0048] The memory controller 902 is also coupled to one or more memory buses 907 . Each memory bus accepts memory components 908 which include at least one MRAM memory device 170 contains a plurality of MTJ memory elements formed in accordance with the present invention. The memory components 908 may be a memory card or a memory module. Examples of memory modules include single inline memory modules (SIMMs) and dual inline memory modules (DIMMs). The memory components 908 may include one or more additional devices 909 . For example, in a SIMM or DIMM, the additional device 909 might be a configuration memory, such as a serial presence detect (SPD) memory. The memory controller 902 may also be coupled to a cache memory 905 . The cache memory 905 may be the only cache memory in the processing system. Alternatively, other devices, for example, processors 901 may also include cache memories, which may form a cache hierarchy with cache memory 905 . If the processing system 900 includes peripherals or controllers which are bus masters or which support direct memory access (DMA), the memory controller 902 may implement a cache coherency protocol. If the memory controller 902 is coupled to a plurality of memory buses 907 , each memory bus 907 may be operated in parallel, or different address ranges may be mapped to different memory buses 907 .
[0049] The primary bus bridge 903 is coupled to at least one peripheral bus 910 . Various devices, such as peripherals or additional bus bridges may be coupled to the peripheral bus 910 . These devices may include a storage controller 911 , a miscellaneous I/O device 914 , a secondary bus bridge 915 , a multimedia processor 918 , and a legacy device interface 920 . The primary bus bridge 903 may also be coupled to one or more special purpose high speed ports 922 . In a personal computer, for example, the special purpose port might be the Accelerated Graphics Port (AGP), used to couple a high performance video card to the processing system 900 .
[0050] The storage controller 911 couples one or more storage devices 913 , via a storage bus 912 , to the peripheral bus 910 . For example, the storage controller 911 may be a SCSI controller and storage devices 913 may be SCSI discs. The I/O device 914 may be any sort of peripheral. For example, the I/O device 914 may be a local area network interface, such as an Ethernet card. The secondary bus bridge may be used to interface additional devices via another bus to the processing system. For example, the secondary bus bridge may be a universal serial port (USB) controller used to couple USB devices 917 via to the processing system 900 . The multimedia processor 918 may be a sound card, a video capture card, or any other type of media interface, which may also be coupled to one additional device such as speakers 919 . The legacy device interface 920 is used to couple legacy devices, for example, older styled keyboards and mice, to the processing system 900 .
[0051] The processing system 900 illustrated in FIG. 18 is only an exemplary processing system with which the invention may be used. While FIG. 18 illustrates a processing architecture especially suitable for a general purpose computer, such as a personal computer or a workstation, it should be recognized that well known modifications can be made to configure the processing system 900 to become more suitable for use in a variety of applications. For example, many electronic devices which require processing may be implemented using a simpler architecture which relies on a CPU 901 coupled to memory components 908 and/or memory devices 170 . These electronic devices may include, but are not limited to audio/video processors and recorders, gaming consoles, digital television sets, wired or wireless telephones, navigation devices (including system based on the global positioning system (GPS) and/or inertial navigation), and digital cameras and/or recorders. The modifications may include, for example, elimination of unnecessary components, addition of specialized devices or circuits, and/or integration of a plurality of devices.
[0052] The above description and accompanying drawings are only illustrative of exemplary embodiments, which can achieve the features and advantages of the present invention. It is not intended that the invention be limited to the embodiments shown and described in detail herein. The invention can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the invention. Accordingly, the invention is not limited by the foregoing description, but rather is limited only by the scope of the appended claims. | The present invention seeks to reduce the amount of current required for a write operation by using a process for forming the read conductor within a recessed write conductor, the write conductor itself formed within a trench of an insulating layer. The present invention protects the MTJ from the voltages created by the write conductor by isolating the write conductor and enabling the reduction of current necessary to write a bit of information. | 7 |
CROSS REFERENCE TO RELATED INVENTIONS
[0001] This application claims the benefit of priority of U.S. Provisional Patent Application Ser. No. 61/191,862, filed Sep. 12, 2008, which is incorporated herein by reference in its entirety.
REFERENCE TO SEQUENCE LISTING
[0002] This application contains a Sequence Listing submitted as an electronic text file named “R0445_ST25.txt”, having a size in bytes of 45 kb, and created on Sep. 3, 2009. The information contained in this electronic file is hereby incorporated by reference in its entirety pursuant to 37 CFR §1.52(e)(5).
FIELD OF THE INVENTION
[0003] This invention pertains to novel methods of producing infectious HCV Genotype 1 viruses in cell culture and is useful for screening, testing and evaluating various HCV inhibitors.
BACKGROUND OF THE INVENTION
[0004] Hepatitis C virus (HCV) is a major health problem and the leading cause of chronic liver disease throughout the world. (Boyer, N. et al. J. Hepatol. 2000 32:98-112). Patients infected with HCV are at risk of developing cirrhosis of the liver and subsequent hepatocellular carcinoma and hence HCV is the major indication for liver transplantation.
[0005] According to the World Health Organization, there are more than 200 million infected individuals worldwide, with at least 3 to 4 million people being infected each year. Once infected, about 20% of people clear the virus, but the rest can harbor HCV the rest of their lives. Ten to twenty percent of chronically infected individuals eventually develop liver-destroying cirrhosis or cancer. The viral disease is transmitted parenterally by contaminated blood and blood products, contaminated needles, or sexually and vertically from infected mothers or carrier mothers to their offspring. Current treatments for HCV infection, which are restricted to immunotherapy with recombinant interferon-α alone or in combination with the nucleoside analog ribavirin, are of limited clinical benefit particularly for genotype 1. There is an urgent need for improved therapeutic agents that effectively combat chronic HCV infection
[0006] HCV has been classified as a member of the virus family Flaviviridae that includes the genera flaviviruses, pestiviruses, and hepaciviruses which includes hepatitis C viruses (Rice, C. M., Flaviviridae: The viruses and their replication , in: Fields Virology , Editors: Fields, B. N., Knipe, D. M., and Howley, P. M., Lippincott-Raven Publishers, Philadelphia, Pa., Chapter 30, 931-959, 1996). HCV is an enveloped virus containing a positive-sense single-stranded RNA genome of approximately 9.4 kb. The viral genome consists of a 5′-untranslated region (UTR), a long open reading frame encoding a polyprotein precursor of approximately 3011 amino acids, and a short 3′ UTR. The 5′ UTR is the most highly conserved part of the HCV genome and is important for the initiation and control of polyprotein translation.
[0007] Genetic analysis of HCV has identified six main genotypes showing a >30% divergence in the DNA sequence. Each genotype contains a series of more closely related subtypes which show a 20-25% divergence in nucleotide sequences (Simmonds, P. 2004 J. Gen. Virol. 85:3173-88). More than 30 subtypes have been distinguished. In the US approximately 70% of infected individuals have type 1a and 1b infection. Type 1b is the most prevalent subtype in Asia. (X. Forms and J. Bukh, Clinics in Liver Disease 1999 3:693-716; J. Bukh et al., Semin. Liv. Dis. 1995 15:41-63). Unfortunately Type 1 infections are less responsive to the current therapy than either type 2 or 3 genotypes (N. N. Zein, Clin. Microbiol. Rev., 2000 13:223-235).
[0008] The genetic organization and polyprotein processing of the nonstructural protein portion of the ORF of pestiviruses and hepaciviruses is very similar. These positive stranded RNA viruses possess a single large open reading frame (ORF) encoding all the viral proteins necessary for virus replication. These proteins are expressed as a polyprotein that is co- and post-translationally processed by both cellular and virus-encoded proteinases to yield the mature viral proteins. The viral proteins responsible for the replication of the viral genome RNA are located towards the carboxy-terminal. Two-thirds of the ORF are termed nonstructural (NS) proteins. For both the pestiviruses and hepaciviruses, the mature nonstructural (NS) proteins, in sequential order from the amino-terminus of the nonstructural protein coding region to the carboxy-terminus of the ORF, consist of p7, NS2, NS3, NS4A, NS4B, NS5A, and NS5B.
[0009] The NS proteins of pestiviruses and hepaciviruses share sequence domains that are characteristic of specific protein functions. For example, the NS3 proteins of viruses in both groups possess amino acid sequence motifs characteristic of serine proteinases and of helicases (Gorbalenya et al. Nature 1988 333:22; Bazan and Fletterick Virology 1989 171:637-639; Gorbalenya et al. Nucleic Acid Res. 1989 17.3889-3897). Similarly, the NS5B proteins of pestiviruses and hepaciviruses have the motifs characteristic of RNA-directed RNA polymerases (Koonin, E. V. and Dolja, V. V. Crit. Rev. Biochem. Molec. Biol. 1993 28:375-430).
[0010] The actual roles and functions of the NS proteins of pestiviruses and hepaciviruses in the lifecycle of the viruses are directly analogous. In both cases, the NS3 serine proteinase is responsible for all proteolytic processing of polyprotein precursors downstream of its position in the ORF (Wiskerchen and Collett Virology 1991 184:341-350; Bartenschlager et al. J. Virol. 1993 67:3835-3844; Eckart et al. Biochem. Biophys. Res. Comm. 1993 192:399-406; Grakoui et al. J. Virol. 1993 67:2832-2843; Grakoui et al. Proc. Natl. Acad. Sci. USA 1993 90:10583-10587; Ilijikata et al. J. Virol. 1993 67:4665-4675; Tome et al. J. Virol. 1993 67:4017-4026). The NS4A protein, in both cases, acts as a cofactor with the NS3 serine protease (Bartenschlager et al. J. Virol. 1994 68:5045-5055; Fulla et al. J. Virol. 1994 68: 3753-3760; Xu et al. J. Virol. 1997 71:53 12-5322). The NS3 protein of both viruses also functions as a helicase (Kim et al. Biochem. Biophys. Res. Comm. 1995 215: 160-166; Jin and Peterson Arch. Biochem. Biophys. 1995, 323:47-53; Warrener and Collett J. Virol. 1995 69:1720-1726). Finally, the NS5B proteins of pestiviruses and hepaciviruses have the predicted RNA-dependent RNA polymerase activity (Behrens et al. EMBO 1996 15:12-22; Lechmann et al. J. Virol. 1997 71:8416-8428; Yuan et al. Biochem. Biophys. Res. Comm. 1997 232:231-235; Hagedorn, PCT WO 97/12033; Zhong et al. J. Virol. 1998 72:9365-9369).
[0011] Currently there are a limited number of approved therapies are currently available for the treatment of HCV infection. New and existing therapeutic approaches to treating HCV and inhibition of HCV NS5B polymerase have been reviewed: R. G. Gish, Sem. Liver. Dis., 1999 19:5; Di Besceglie, A. M. and Bacon, B. R., Scientific American, October: 1999 80-85; G. Lake-Bakaar, Current and Future Therapy for Chronic Hepatitis C Virus Liver Disease, Curr. Drug Targ. Infect Dis. 2003 3(3):247-253; P. Hoffmann et al., Recent patents on experimental therapy for hepatitis C virus infection (1999-2002), Exp. Opin. Ther. Patents 2003 13(11):1707-1723; F. F. Poordad et al. Developments in Hepatitis C therapy during 2000-2002 , Exp. Opin. Emerging Drugs 2003 8(1):9-25; M. P. Walker et al., Promising Candidates for the treatment of chronic hepatitis C, Exp. Opin. Investig. Drugs 2003 12(8):1269-1280; S.-L. Tan et al., Hepatitis C Therapeutics: Current Status and Emerging Strategies, Nature Rev. Drug Discov. 2002 1:867-881; R. De Francesco et al. Approaching a new era for hepatitis C virus Therapy™ inhibitors of the NS3-4A serine protease and the NS5B RNA-dependent RNA polymerase, Antiviral Res. 2003 58:1-16; Q. M. Wang et al. Hepatitis C virus encoded proteins: targets for antiviral therapy, Drugs of the Future 2000 25(9):933-8-944; J. A. Wu and Z. Hong, Targeting NS5B-Dependent RNA Polymerase for Anti-HCV Chemotherapy Cur. Drug Targ .- Inf. Dis 0.2003 3:207-219.
[0012] Despite advances in understanding the genomic organization of the virus and the functions of viral proteins, fundamental aspects of HCV replication and pathogenesis remain unknown. A major challenge in gaining experimental access to HCV replication is the lack of an efficient cell culture system that allows production of infectious virus particles. Although infection of primary cell cultures and certain human cell lines has been reported, the amounts of virus produced in those systems and the levels of HCV replication have been too low to permit detailed analyses. This is especially true for genotype 1a HCV viral particles, despite a recent report which details the production of low levels of infectious genotype 1a virus using HCV RNA that contains a combination of five cell culture-adaptive mutations (Yi et al., Proc. Natl. Acad. Sci. USA 2006 103(7):2310-2315).
[0013] Two groups have reported the generation of genotype-1a replication system using highly permissive sublines of Huh-7 human hepatoma cells. Blight et al. ( J. Virol. 2003 77:3181-3190) were able to select G418 resistant colonies supporting replication of genotype 1a derived subgenomic replicons in a hyper-permissive Huh-7 subline, Huh-7.5, that was generated by curing an established G418-resistant replicon cell line of the cubgenomic Con1 replicon RNA that had been used to select it by treatment with interferon-alpha (Blight et al., J. Virol. 2002 76:13001-13014). Sequence analysis of replicating HCV RNAs inside of such selected cell lines showed that the most common critical mutations were located at amino acid position 470 of NS3 (P1496L) within domain II of the NS3 helicase, and the NS5A mutation (S2204I). In another case, Grobler et al. ( J. Biol. Chem. 2003 278:16741-16746), used a systematic mutational approach to reach the similar conclusion that both P1496L and S2204I combination was necessary to get genotype 1a replication in a highly permissive Huh-7 subline which was selected in an independent but similar way. However, genotype-1a RNAs with these two enhanced mutations does not undergo replication in the Huh-7 cell line, indicating limited usefulness of this system.
SUMMARY OF THE INVENTION
[0014] The present invention is based on the surprising effect of using human serum to improve the production of infectious HCV genotype 1 virus particles in cell culture systems. The availability of HCV genotype 1 virus (principally associated with liver disease in most regions of the world) that can undergo the complete viral cycle in cultured cells is beneficial for the discovery and development of novel therapies for the treatment of HCV.
[0015] Accordingly, the present invention provides a method for increasing the production of HCV genotype 1 virus particles in cultured cells comprising transfecting cultured cells with a replication competent HCV genotype 1 polynucleotide that comprises the adaptive mutations, Q1067R, V16551, K1691R, K2040R, S2204I, incubating the transfected cultured cells in the presence of 2-10% human serum, and collecting the medium from the transfected cultured cells that contains infectious HCV genotype 1 virus particles. The present invention further provides a method of screening for a HCV genotype 1 inhibitor comprising transfecting cultured cells with a replication competent HCV genotype 1 polynucleotide that comprises the adaptive mutations, Q1067R, V16551, K1691R, K2040R, S2204I; incubating the transfected cultured cells in the presence of 2-10% human serum; collecting the medium from the transfected cultured cells that contains infectious HCV genotype 1 virus particles; infecting native cultured cells with the infectious HCV genotype 1 virus particles in the presence or absence of a molecule being screened for HCV inhibitory activity; and measuring the level of HCV present in the infected cultured cells wherein a decrease in the level of HCV in the presence of the molecule compared to the absence of the molecule indicates that the molecule is a HCV genotype 1 inhibitor.
[0016] The foregoing and other advantages and features of the invention, and the manner in which the same are accomplished, will become more readily apparent upon consideration of the following detailed description of the invention taken in conjunction with the accompanying examples, which illustrate exemplary embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 . Human serum does not enhance HCV replication. Rof-400c cells were transfected with in vitro transcribed RNA that encoded for the HCV strain H77S or a replication defective mutant (GND). At the indicated time post-transfection the intracellular RNA was purified and then used to determine the amount of HCV RNA.
[0018] FIG. 2 . Human serum does enhance production of infectious HCV. Rof-400c cells were transfected with in vitro transcribed RNA that encoded for the HCV strain H77S or a replication defective mutant (GND). At the indicated time post-transfection the medium was collected and used to infect naive cells. After three days, the intracellular RNA was purified and then used to determine the amount of HCV RNA.
[0019] FIG. 3 . Detection of HCV Core protein in infected cells by immunofluorescence analysis. Medium collected from cells transfected with in vitro transcribed RNA that encoded for the HCV strain H77S was used to infect naive cells. After four days, the expression of the HCV Core protein was analyzed by immunofluorescence.
[0020] FIG. 4 . Detection of HCV Core protein in infected cells by immunoperoxidase analysis. Medium collected from cells transfected with in vitro transcribed RNA that encoded for the HCV strain H77S was used to infect naive cells. After four days, the expression of the HCV Core protein was analyzed after immunoperoxidase staining
[0021] FIG. 5 . Kinetics of infectious virus production for H77S and H77S RO-51-5B. Rof-0c cells were transfected with in vitro transcribed RNA that encoded for the HCV strain H77S or the chimeric stain H77S RO-51-5B. At the indicated time points, medium was collected and used to infect naive cells in order to determine the infectious virus titer which was measured as the end point dilution that resulted in 50% of the wells containing infected cells (tissue culture infected dose TCID50).
[0022] FIG. 6 . Potency of an NS5B inhibitor and HCV entry inhibitor against the GT 1a infectious virus. Rof-0c cells were infected with either H77S or the chimera H77S RO-51-5B. At the time of infection, the cells were treated with a serial dilution of either the NS5B inhibitor HCV-796 or the HCV entry inhibitor JS81. After three days, the intracellular RNA was purified and used to determine the amount of HCV RNA.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0023] As used herein, the term “replication competent polynucleotide” refers to a polynucleotide that replicates when present in a cell. For instance, a complementary polynucleotide is synthesized. As used herein, the term “replicates in vitro” indicates the polynucleotide replicates in a cell that is growing in culture. The cultured cell can be one that has been selected to grow in culture, including, for instance, an immortalized or a transformed cell. Alternatively, the cultured cell can be one that has been explanted from an animal. “Replicates in vivo” indicates the polynucleotide replicates in a cell within the body of an animal, for instance a primate (including a chimpanzee) or a human. In some aspects of the present invention, replication in a cell can include the production of “infectious” virus particles, i.e., virus particles that can infect a cell and result in the production of more infectious virus particles.
[0024] A replication competent polynucleotide includes at least one adaptive mutation. As used herein, an “adaptive mutation” is a change in the amino acid sequence of the polyprotein that increases the ability of a replication competent polynucleotide to replicate compared to a replication competent polynucleotide that does not have the adaptive mutation.
[0025] One adaptive mutation that a replication competent polynucleotide referred in the present invention includes an arginine at about amino acid 1067, which is about amino acid 41 of NS3. Most clinical HCV isolates and molecularly cloned laboratory HCV strains include a glutamine at this position, thus this mutation can be referred to as Q1067R. A second adaptive mutation is an isoleucine at about amino acid 1655, which is about amino acid 629 of NS3. Most clinical HCV isolates and molecularly cloned laboratory HCV strains include a valine at this position, thus this mutation can be referred to as V 16551. A third adaptive mutation is an arginine at about amino acid 1691, which is about amino acid 34 of NS4A. Most clinical HCV isolates and molecularly cloned laboratory HCV strains include a lysine at this position, thus this mutation can be referred to as K1691R. A fourth adaptive mutation is an arginine at about amino acid 2040, which is about amino acid 68 of NS5A. Most clinical HCV isolates and molecularly cloned laboratory HCV strains include a lysine at this position, thus this mutation can be referred to as K2040R. A fifth adaptive mutation that a replication competent polynucleotide referred in the present invention includes an isoleucine at about amino acid 2204, which is about amino acid 232 of NS5A. Most clinical HCV isolates and molecularly cloned laboratory HCV strains include a serine at this position, and this mutation has been referred to in the art as S2204I.
[0026] As used herein, the term “polynucleotide” refers to a polymeric form of nucleotides of any length, either ribonucleotides or deoxynucleotides, and includes both double- and single-stranded DNA and RNA. A polynucleotide may include nucleotide sequences having different functions, including for instance coding sequences, and non-coding sequences such as regulatory sequences and/or non-translated regions. A polynucleotide can be obtained directly from a natural source, or can be prepared with the aid of recombinant, enzymatic, or chemical techniques. A polynucleotide can be linear or circular in topology and can be, for example, a portion of a vector, such as an expression or cloning vector, or a fragment.
[0027] The terms “coding region” and “coding sequence” are used interchangeably and refer to a polynucleotide region that encodes a polypeptide and, when placed under the control of appropriate regulatory sequences, expresses the encoded polypeptide. The boundaries of a coding region are generally determined by a translation start codon at its 5′ end and a translation stop codon at its 3′ end. A coding region can encode one or more polypeptides. For instance, a coding region can encode a polypeptide that is subsequently processed into two or more polypeptides. A regulatory sequence or regulatory region is a nucleotide sequence that regulates expression of a coding region to which it is operably linked. Nonlimiting examples of regulatory sequences include promoters, transcription initiation sites, translation start sites, internal ribosome entry sites, translation stop sites, and terminators. “Operably linked” refers to a juxtaposition wherein the components so described are in a relationship permitting them to function in their intended manner. A regulatory sequence is “operably linked” to a coding region when it is joined in such a way that expression of the coding region is achieved under conditions compatible with the regulatory sequence.
[0028] “Polypeptide” as used herein refers to a polymer of amino acids and does not refer to a specific length of a polymer of amino acids. Thus, for example, the terms peptide, oligopeptide, protein, polyprotein, proteinase, and enzyme are included within the definition of polypeptide. This term also includes post-expression modifications of the polypeptide, for example, glycosylations, acetylations, phosphorylations and the like. A “hepatitis C virus polyprotein” refers to a polypeptide that is post-translationally cleaved to yield more than one polypeptide.
[0029] The terms “5′ non-translated RNA,” “5′ non-translated region,” “5′ untranslated region” and “5′ noncoding region” are used interchangeably, and are terms of art (see Bukh et al., Proc. Nat. Acad. Sci. USA 1992 89: 4942-4946). The term refers to the nucleotides that are at the 5′ end of a replication competent polynucleotide.
[0030] The terms “3′ non-translated RNA,” “3′ non-translated region,” and “3′ untranslated region” are used interchangeably, and are terms of art. The term refers to the nucleotides that are at the 3′ end of a replication competent polynucleotide.
[0031] A cell has been “transformed” or “transfected” by exogenous or heterologous DNA or RNA when such DNA or RNA has been introduced inside the cell. The transforming or transfecting DNA or RNA may or may not be integrated (covalently linked) into chromosomal DNA making up the genome of the cell. For example, in prokaryotes, yeast, and mammalian cells, the transforming DNA may be maintained on an episomal element such as a plasmid. With respect to eukaryotic cells, a stably transformed cell is one in which the transforming DNA has become integrated into a chromosome so that it is inherited by daughter cells through chromosome replication. This stability is demonstrated by the ability of the eukaryotic cell to establish cell lines or clones comprised of a population of daughter cells containing the transforming DNA.
[0032] The term “subject” as used herein refers to vertebrates, particular members of the mammalian species and includes, but not limited to, rodents, rabbits, shrews, and primates, the latter including humans.
[0033] The term “sample” refers to a sample of tissue or fluid isolated from a subject, including but not limited to, for example, plasma, serum, spinal fluid, lymph fluid, the external sections of the skin, respiratory, intestinal and genitourinary tracts, tears, saliva, milk, blood cells, tumors, organs, and also samples of in vitro cell culture constituents (including but not limited to, conditioned medium resulting from the growth of cultured cells, putatively viral infected cells, recombinant cells, and cell components).
[0034] The term “HCV genotype 1 inhibitor” refers to a molecule that inhibits any function of HCV genotype-1 and may act at any step in the life cycle of the virus from initial attachment and entry to release, and may include but is not limited to an attachment inhibitor, entry inhibitor, a fusion inhibitor, a trafficking inhibitor, a replication inhibitor, a translation inhibitor, a protein processing inhibitor, or a release inhibitor. The molecule can be from a wide range and may include but is not limited to an organic molecule, a peptide, a polypeptide (for instance, an antibody), a polynucleotide (for instance an antisense oligonucleotide, siRNA, microRNA), or a combination thereof.
EXAMPLES
[0035] The following preparations and examples are given to enable those skilled in the art to more clearly understand and to practice the present invention. They should not be considered as limiting the scope of the invention, but merely as being illustrative and representative thereof.
Materials and Methods
Cell Culture
[0036] The Rof-0 cells are a human hepatocellular carcinoma cell line derived from the Huh-7 cell line. The Rof-0 cells stably maintain a HCV genotype (GT) 1b replicon. A cell line with diminished responsiveness to interferon-α was generated by maintaining the Rof-0 cells in the presence of 400 units/ml IFN-α2a (Roferon®, Hoffmann-LaRoche Inc.) as well as G418 (Geneticin®, Invitrogen) to maintain selection of the replicon. The cell line that resulted is called Rof-400. The HCV replicon was cured from Rof-0 and Rof-400 cells by maintaining the cells in the presence of 2′-C-methyl adenosine and resulted in the cell lines Rof-0c and Rof-400c. The cell lines were cultured Dulbecco's Modified Eagle Medium (DMEM) supplemented with Glutamax™ and 100 mg/ml sodium pyruvate (Invitrogen). The medium is further supplemented with 10% (v/v) fetal bovine serum (FBS, Invitrogen) and 1% (v/v) penicillin/streptomycin.
Plasmids
[0037] A plasmid encoding the full-length GT 1a strain H77 with 5 cell culture adaptive mutations was engineered as follows. The TQ-1 plasmid, which encodes for the GT 1a H77 subgenomic replicon, and the TX-2 plasmid, which also encodes for the H77 subgenomic replicon and encodes the AsiSI and RsrII restriction sites flanking the NS5B coding sequence, were digested with the restriction enzymes AgeI and NsiI. The 6400 base pair fragment that resulted from the digest was purified. The plasmid HCV 1a H77 was digested with AgeI and NsiI and the 5100 base pair fragment that resulted was purified. The purified fragments from the TQ-1 and TX-2 digestion were separately ligated with the HCV 1a H77 digestion product resulting in the plasmid pUC HCV 1a H77, which contains three adaptive mutations (K1691R, K2040R, and S2204I), and pUC HCV1a-H77.AsiSIRsrII, which contains the same three adaptive mutations plus the AsiSI and RsrII restrictions sites used to cassette in NS5B sequences. Two additional adaptive mutations (Q1067R and V16551) were introduced into both vectors using the Quick Change site-directed mutagenesis kit according to the manufacturer's instructions (Stratagene). This resulted in the plasmids pUC H77S (SEQ ID NO:1) and pUC H77S.AsiSIRsrII (SEQ ID NO:2). A replication defective construct was generated by introducing a mutation in the NS5B active site (D2738N) using the Quick Change site-directed mutagenesis kit according to the manufacturer's instructions (Stratagene) generating the construct pUC H77S GND.
[0038] A chimeric H77S virus that encodes the NS5B sequence from a clinical isolate was generated by digesting pUC H77S.AsiSIRsrII and a PCR product for the clinical isolate RO-51 NS5B sequence with AsiSI and RsrII. The fragments were ligated together resulting in the plasmid pUC H77S RO-51-5B (SEQ ID NO:3).
Virus Production
[0039] The plasmids that encode for the full-length HCV genome were linearized with the restriction enzyme SpeI and then treated with Mung bean nuclease. The linearized template was used in an in vitro RNA transcription reaction using the T7 Ribomax Express Kit (Promega) according to the manufacturer's instructions. For RNA transfection, four million Rof-0c or Rof-400c cells were electroporated with 2-10 μg of in vitro transcribed RNA. After electroporation, the cells were resuspended in DMEM containing either 5% (v/v) FBS or 2%-10% (v/v) human serum (HS, Bioreclamation). At the indicated time points the medium was collected, spun at 3000 RPM, and aliquoted to assay for infectious virus production.
Infectious Virus Assays
[0040] Medium collected from the transfected Rof-0c or Rof-400c cells was assayed for infectious virus by incubating with naive Rof-0c or Rof-400c. After incubating the naive cells for 72-96 hours, either the cellular RNA was extracted to quantify HCV RNA or the cells were fixed to analyze for expression of HCV proteins.
[0041] The presence of HCV RNA was examined after purification of total cellular RNA using the PerfectPure RNA 96 Cell Kit (5 Prime) according to the manufacturer's instructions. To quantitate the amount of HCV RNA, cDNA was amplified using either the Taqman Universal PCR mix (Applied Biosystems) or the TaqMan EZ RT-PCR kit (Applied Biosystems) with a set of primers and probe complementary to a region within the 5′ untranslated region (UTR). The primer and probe sequences are: (HCV 20F) CGACACTCCACCATAGATCACT (SEQ ID NO:4); (HCV 114R) GAGGCTGCACGACACTCATACT (SEQ ID NO:5); (HCV P43) FAM-CCCTGTGAGGAACTACTGTCTTCACGCAGA-TAMRA (SEQ ID NO:6).
[0042] The expression of HCV proteins in infected cells was examined and quantified by either an immunofluorescence assay or an immunoperoxidase assay. The cells were fixed by incubating in 2% formaldehyde for 1 hour at room temperature. Following fixation, the cells were permeabilized by a 5 minute incubation in PBS containing 0.2% TX-100 and 0.1% Na citrate. For fluorescent imaging, the permeabilized cells were blocked using 3% normal goat serum and 0.5% bovine serum albumin for 30 minutes and then stained with a mouse monoclonal antibody specific for HCV core (ab2740, Abcam) for 20 minutes. After washing, the cells were incubated with a secondary antibody (A11032, Invitrogen) for 20 minutes. The cells were mounted using 1 drop of Permafluor (Thermo Scientific) and imaged. The number of infected foci were counted in order to determine the infectious titer in focus forming units/ml.
[0043] The infectious titer could also be determined using an immunoperoxidase assay. The cells were fixed and permeabilized as described above. The cells were then blocked using the ImmPRESS Anti-Mouse Ig peroxidase Kit (MP-7402, Vector Labs) according to manufacturer's instructions. The cells were stained in block with a mouse monoclonal antibody specific to HCV core (ab2740, Abcam) for 1 hour. After washing, the cells were incubated for 30 minutes with ImmPRESS peroxidase:anti-mouse conjugate. The stained cells were visualized after a 10 minute incubation with ImmPACT DAB substrate (SK-4105, Vector Labs) followed by DAB enhancement (H-2200, Vector Labs). The infectious titer was determined as the end point dilution that resulted in 50% of the wells containing infected cells (tissue culture infected dose TCID50).
HCV Infectious Virus EC50 Determinations
[0044] The sensitivity of infectious HCV to antivirals was determined using the genotype 1a strains H77S or H77S RO-51-5B. The virus stocks were generated by transfecting the full-length genome into Rof-0c cells, culturing the cells in DMEM containing 2-10% HS, and collecting the medium 7 days post-transfection. For EC50 determinations, the Rof-0c cells were plated at 10,000 cells per well into 96-well poly-D-lysine coated plates (BD Biosciences). Twenty-four hours post-plating, the medium was removed and 90 μl of the virus stock was added per well. The inhibitors, at 3-fold serial dilutions, were then added. Three days post-infection, the HCV RNA was quantified as described above. The EC50 values were defined as the concentration at which 50% reduction in the levels of HCV RNA, as determined by quantitative RT-PCR, were observed.
Results
[0045] Human serum does not affect HCV RNA replication. Studying the in vitro replication of an infectious GT 1a strain is currently limited by the low viral titers produced. In order to improve infectious virus production, the effect of human serum was examined. A cured Huh-7 cell line, Rof-400c, was transfected with the full-length GT 1a virus strain H77S and the cells were cultured in medium containing either 10% FBS or 10% HS. The amount of intracellular HCV RNA was determined over 5 days. Cells cultured in either HS or FBS contained a similar amount of HCV RNA through all time points tested ( FIG. 1 ). The addition of HS to transfected cells does not appear to increase the replication of HCV RNA.
[0046] Human serum does increase the production of infectious HCV. In the same experiment described above, the effect of human serum on the production of infectious HCV particles was examined. The medium was removed every 24 hours post-transfection for five days and then inoculated onto naive cells to measure infectious virus production. The presence of infectious virus was determined by quantifying the amount of intracellular HCV RNA within naive cells after a 72 hour incubation in the presence of supernatant collected at the indicated time point. The amount of intracellular HCV RNA detected in the infected naive cells was equivalent between cells infected with supernatant collected from cells transfected either H77S or the replication-defective mutant and cultured in FBS ( FIG. 2 ). This indicates that the amount of infectious HCV released from the cells cultured in FBS could not be differentiated from the residual HCV RNA that remained from the transfection. However, there was an increase in the amount of intracellular HCV RNA recovered from the infected naive cells that were inoculated with medium from the transfected cells cultured with HS ( FIG. 2 ). The transfected cells cultured in HS, released infectious HCV and the amount increased throughout the five day assay. These experiments demonstrate that HS does not increase the replication of HCV RNA but does increase the production of infectious virus.
[0047] In order to verify that infectious particles were released from the transfected cells cultured in HS, naive cells were inoculated with supernatant collected at various time points and then analyzed for expression of HCV core protein. The presence of HCV core protein was confirmed in cells stained for immunofluorescence and for immunoperoxidase analysis ( FIG. 3 and FIG. 4 ). These results demonstrated that the increase in HCV RNA detected in naive cells infected with medium from transfected cells cultured with HS ( FIG. 2 ) is a result of a productive HCV infection.
[0048] Peak production of infectious HCV. The experiments described above demonstrated that transfected cells cultured in HS released infectious particles over a five day period. In order to determine the peak time point for virus production, transfected cells were cultured in HS for up to 11 days. Medium was collected from the transfected cells and used to inoculate naive cells. The presence of infectious particles was quantified by an end-point dilution assay that determined the TCID50/ml. Rof-0c cells were transfected with H77S and at 7 days post-transfection the infectious titer peaked at approximately 6000 TCID50/ml ( FIG. 5 ). The peak HCV infectious titer obtained from transfected cells cultured in HS was 60-fold higher than that previously reported for cells cultured in FBS (Yi et al., Proc. Natl. Acad. Sci. USA 2006 103(7):2310-2315).
[0049] Generation of a NS5B chimeric virus. A NS5B cassette system has been established using the HCV replicon that facilitates the cloning and analysis of any NS5B sequence (Le Pogam et al., J. Antimicrob. Chemother. 2008 61:1205-1216). The NS5B cassette has been used to analyze the phenotypic response, from a panel of NS5B isolates, to various non-nucleoside and nucleoside inhibitors. The AsiSI and RsrII restriction sites, which are utilized for cloning the NS5B sequences, were cloned into the full-length H77S genome. The consensus sequence, from a clinical isolate known to replicate within the H77 cassette replicon, was cloned into the H77S NS5B cassette resulting in the chimeric virus H77S RO-51-5B. The production of infectious virus from H77S RO-51-5B transfected cells was examined. Similar to H77S, the peak time point for infectious virus production was at day 7 although the titer of H77S RO-51-5B was decreased by 3-fold compared to H77S ( FIG. 5 ). This data demonstrates that the NS5B cassette system can be used to generate chimeric infectious viruses.
[0050] Potency of HCV inhibitors against GT1a virus. Virus stocks were generated by collecting medium at 7 days post-transfection from cells cultured in presence of HS. The HCV stocks were analyzed to determine if they would be sufficient to measure the potency of HCV inhibitors. Rof-0c cells were plated in a 96-well plate, infected with either H77S or H77S RO-51-5B, and then treated with either a known non-nucleoside inhibitor (HCV-796) or a known entry inhibitor (JS81). The potency of HCV-796 against infectious H77S was 32±4 nM and is similar to what has been reported ( FIG. 6 ). The potency of JS81 against H77S RO-51-5B was 139±23 ng/ml and is also similar to reported data ( FIG. 6 ). These experiments provide evidence that the GT 1a infectious virus, grown in the presence of HS, can be used to measure the potency of HCV inhibitors. | The present invention provides for novel methods of producing high levels of infectious HCV genotype 1 virus particles in cell culture systems. The availability of HCV genotype 1 virus (principally associated with liver disease in most regions of the world) that can undergo the complete viral cycle in cultured cells is beneficial for the discovery and development of novel therapies for the treatment of HCV. | 2 |
CLAIM OF PRIORITY
[0001] This is a continuation-in-part application that claims the benefit of U.S. patent application bearing Ser. No. 09/758,407 filed Jan. 10, 2001 which claimed priority to U.S. Provisional Application bearing serial No. 60/176,126 filed Jan. 14, 2000.
BACKGROUND OF INVENTION
[0002] The present invention relates to the building industry and specifically to mounting equipment and a method for supporting an object over a roof or above ground.
[0003] Mounting equipment or sometimes referred to herein as a mounting system, is used to attach objects such as solar panels including photovoltaic (PV) modules and solar pool heating panels, solar heating collectors (referred to sometimes as domestic hot water collectors), satellite dishes, air conditioning units, etc. The mounting equipment is typically fastened at its base end to either a foundation, directly to the earth, or to support structures on a building such as roof rafters.
[0004] The roofs of building structures have been used for placement of objects with the primary reason for location upon a roof is the lack of alternative space.
[0005] Air conditioning units, because of their relative heavy weight, provide a downward force upon the roof in any weather condition. However, a problem exists for other objects such as satellite dishes and solar panels, which can, in certain windy conditions, be lifted off the mounting equipment to which they are attached because the force of the wind applied against the surface area on the side or underside of the object creates an uplift condition which is greater than the attachment strength of the mounting equipment.
[0006] Besides the need for compliance with governmental building code requirements, a more time efficient method for installing a mounting system, particularly to a roof, is highly desired by installers. A faster installation reduces the labor costs associated with each install.
[0007] One of the problems with present installations is the fact that more than one lag bolt or other type of fastening bolt is required for each mounting plate that is fastened to the roof. The risk is high that some of the lag bolts will drill at an angle other than perpendicular to the roof rafter. The severity of the angle and the trajectory of the lag bolt penetration into the rafter could cause the rafter to split; further reducing the structural integrity of the mounting system.
[0008] For many years, existing solar mounting systems were installed using a threaded pipe nipple that screwed into a mounting plate commonly called a “floor flange” in the trade. The threaded floor flange has been commercially available as a standard plumbing item for many years. U.S. Pat. No. 5,603,187 issued to Merrin et al. is typical of the prior art.
[0009] The Merrin design, as well as similar prior art, have a common design limitation. They require multiple bolts be installed offset from the threaded vertical support flange or stanchion. Also, because of the floor flange design, it would not permit industry standard flashing to install flat on the roof; primarily due to the base flashing circumference interfering with the height of the floor flange.
[0010] A mounting system based upon the Merrin patent, while appropriate for roof mounting of heavy objects such as air conditioners, is not practical for use with lighter objects such as solar panels or satellite dishes. The Merrin design precludes direct (bolted) attachment to the roof rafter by each of the mounting holes present on the base plate; primarily due to the width of the rafter in relation to the spacing of the mounting holes. Further, Merrin views rafter attachment as a limitation and therefore teaches away from using rafters for structural support. Therefore, Merrin teaches attachment to the roof decking which generally consists of only ½″ plywood or a composite sheeting; either of which do not provide the strength of a bolt mounted to a rafter in an uplift condition.
SUMMARY OF INVENTION
[0011] The disclosure contained in U.S. Pat. No. ______ is incorporated herein by reference.
[0012] This invention presents a mounting system for supporting objects such as solar panels and satellite dishes. Also claimed is an end clamp that provides superior frictional engagement of the object to the mounting equipment.
[0013] Definitions
[0014] Alignment Means—a means to align a roof mount such as a guide tunnel.
[0015] Fastening Means—a means to fasten the base mount portion of the mounting equipment to a roof rafter, or ground racking system.
[0016] Support Means—a term used to collectively refer to the various parts necessary to support an object. Support means includes one or more horizontal members upon which the weight of an object will be supported, and clamps to secure the object to the horizontal member(s).
[0017] Attachment Means—Means by which the support means is attached to the base mount. One example is by the use of a bolt threadably engaging a stanchion located on the opposite side of a horizontal member. The base portion of the stanchion is threaded into the base mount.
[0018] Securing Means—Means to secure the object upon the horizontal member(s). The securing means comprises either a pair of end clamps each having a raised distal heel, or a wedge or half-moon washer and substitute for a heel and used with end clamps having no heel. The securing means is secured to the adjacent horizontal member and, as tightened, it frictionally engages a portion of the object to maintain it in a secure position upon the horizontal member.
[0019] The mounting equipment comprises at least one base mount and associated support clamps and support rails, and are not limited to roof top installations. They can be installed over pipe supports or attached to other support systems or ground racking systems. Types of ground racking systems include, but are not limited to pipe supports, pole mounted installations, building facades and patio covers.
[0020] First Example
[0021] By way of a first example, for new construction or reroofing, a roof mount would be attached prior to installation of the roof flashing. The component parts for supporting a solar panel or satellite dish would be assembled and attached to the roof mount over the flashing. Features of the invention are as follows:
[0022] 1. a new base mount (also referred to as a roof mount) having a threadable elongated member or stanchion which requires a single lag bolt positioned directly beneath the stanchion for fastening to a roof rafter. A guide tunnel is also provided on the roof mount for proper drill angle into the rafter.
[0023] 2. A support design comprising either a composite or aluminum extruded horizontal members and associated equipment for attachment to a plurality of roof mounts which will support a mounted object such as a solar panel. Although a particular C-shaped design is depicted in the drawings, any design to facilitate the securing means is considered to be part of the support design. The purpose of the horizontal members is to provide: 1) support for the weight of an object positioned upon the member; and, 2) to facilitate the securing means of the object to the member by the use of a pair of end clamps for each member used.
[0024] 3. A securing means for securing the end of a supporting object to the support design. One example of the securing means is a pair of cooperating end clamps each having a raised heel which enhances frictional engagement when being secured into position upon a horizontal member with an object to be secured therebetween.
[0025] Second Example
[0026] In a second example, the mounting system, instead of being fastened to a new roof rafter for support, is operatively fastened either: a) upon existing roofs or framework; or, b) over pipe supports or other support systems not necessarily located upon a roof. Here, the roof mount referred to earlier is not utilized although the other features described in paragraphs 2 , 3 , and 4 above pertain. For this example, the roof mount is replaced as the means to fasten the mounting system with an alternative means such as that described in U.S. Pat. No. 5,746,029 issued to Ullman and which is herein incorporated by reference.
[0027] Roof Mount (For Example 1)
[0028] In order to utilize my mounting system, a roof mount must first be fastened to a rafter. The roof mount can be manufactured from any material commonly used in the building trade to support objects upon a roof. Preferably, the mount is machined from aluminum and comprises a threaded cavity with an insertion opening for threadably receiving a vertical stanchion. Directly below the cavity is an aperture for insertion of a lag bolt for attachment to the rafter. This is a unique feature of my support base. Only one lag bolt or other type of fastening bolt is required. For a one bolt design, having the attachment force positioned directly beneath the stanchion provides the highest level of attachment strength.
[0029] Additionally, a special hollow can be machined at the base of the channel to allow clearance for the bolt head when installed so that it does not contact the bottom surface area of the stanchion. This permits maximum threadable engagement of the stanchion to the base.
[0030] The base section of the roof mount comprises a base for direct contact with the decking surface of a roof and a vertically extending cylindrical member having the threaded cavity and an offset wall having a guide tunnel. It is not necessary that, the guide tunnel be part of the cylindrical member. It is however, preferable to maintain a minimum distance between channel and guide tunnel so that it is easy to use the guide tunnel to drill a pilot hole into a rafter and to thereafter align the pilot hole with the aperture by sliding the base section a minimal distance.
[0031] The distance between the cavity and guide tunnel however, must be sufficient so as not to compromise the overall structural integrity of the base section.
[0032] In an alternative design, the guide tunnel is not used and the roof mount base section simply incorporates my single bolt design described above which includes a base and a vertically extending cylindrical member having the threaded cavity.
[0033] The base can be of any geometrical shape such as circular, rectangle or square. All that is required is that the geometrical shape be sized accordingly so that it does not interfere with the alignment or use of commercially available flashing to the roof.
[0034] Once the lag bolt is fastened to the rafter, one end of the stanchion is screwed into the threaded cavity and the roof flashing is thereafter installed. For purposes of this specification, the base section and the stanchion/elongated member are collectively referred to as the roof mount. Although the mounting equipment may be installed days later, it is preferable to install the roof mount at this point.
[0035] Installation of Mounting System Upon Support Means
[0036] At least one horizontal member is provided as a means for supporting an object. The number of horizontal members used will be dependent upon the type of object to be supported.
[0037] The horizontal member is preferably made from extruded aluminum and can be manufactured to any length. Each horizontal member has a track that can be used by either T-nuts or slidable inserts which have been designed to fit within and slide along this track.
[0038] The T-nut has a threaded stem facing upward for engaging a clamp with a nut.
[0039] The slidable inserts can be designed to have: 1) a hole for allowing the threaded stem of a screw or the like to pass upwards while the headed end of the screw can not; or, 2) a female threaded hole for cooperative securement with the clamps as will be discussed now.
[0040] Clamps are used to grip an edge portion of an adjacent object and secure that object in position once the clamp has been fastened to the adjacent horizontal member. The gripping end of the clamp can have a surface which is flat or serrated. One clamp is provided for each slidable insert or T-nut. The clamp has a hole or aperture and is positioned so that either a fastening bolt can be inserted through and secured to the threaded hole of the threadable insert, or it can be secured to the upward facing threaded T-nut stem or, a threaded stem of sufficient length extends upwards through the aperture in the slidable insert and through the aperture in the clamp. Thereafter, a nut is used to threadably engage the threaded stem and fasten the clamp to the horizontal member.
[0041] There are two types of clamps available: end clamps and bi-module clamps.
[0042] Bi-module clamps are primarily used for securement of the sides of adjacent objects such as two solar panel modules.
[0043] A module is a set of photovoltaic cells while a solar panel is a plurality of modules. End clamps would secure the sides of a solar panel. In any case, bi-module clamps are used to secure the sides of two adjoining solar modules to an adjacent horizontal member.
[0044] Each horizontal member uses a pair of end clamps for securement of an object therebetween such as a solar panel. Each end clamp has a section or end referred to as a lip and preferably has a slight rise or heel on its bottom surface distally positioned from the lip end. The lip has a bottom surface that can be described as a gripping surface for engaging an object.
[0045] The slight rise or heel provides functional advantages when securing an object to a horizontal member. First, the slight rise prevents twisting of the end clamp while it is being bolted or secured into position on the horizontal member. Second, when the gripping surface of the lip engages an object, the rise forces the clamp inward at 90 degrees to fully engage the object.
[0046] In the case of a solar panel, this design prevents the end clamp from inadvertently separating the module frame from its glass. Also, the rise provides spring tension against the module frame, providing full engagement as the module laminate glass and frame flex under-extreme stresses caused by weather conditions such as high wind and snow.
[0047] Besides an end clamp having a raised heel portion as described above, an alternative heel means for facilitating the securement of an object between two end clamps can be by more than one piece performing the same function such as a wedge or half-moon shaped washer positioned between an end clamp having no heel and the adjacent horizontal member. The purpose of the wedge or washer would be to angle the end clamp the same as if the end clamp had a raised heel portion. However, the single unitized piece is the preferred embodiment.
[0048] The heel design incorporated into the end clamp can be of any length or shape. It does not have to be continuous across the extrusion so long as it can function to place inward pressure against an object to be secured between an end clamp and another end clamp or bi-module clamp.
[0049] As stated earlier, the securing means, besides using a pair of end clamps having respective heels, can also employ a heel means located between each end clamp not having a heel and the horizontal member. The heel means can be, but should not be considered limited to, the use of a wedge or half-moon shaped washer or other protrusion that, when positioned between the bottom side of the end clamp and the top surface of the horizontal member, will provide the same inward force against the object when tightened to the horizontal support rail.
[0050] The support system includes the horizontal members, slidable inserts or T-nuts, end clamps, optional bi-module clamps and the attachment means.
BRIEF DESCRIPTION OF DRAWINGS
[0051] [0051]FIG. 1 is a perspective view and illustrates the position of the base section of the roof mount above a rafter and a drill positioned for drilling a pilot hole.
[0052] [0052]FIG. 2 is a view taken along line 2 - 2 of FIG. 1 and which shows a drilled pilot hole.
[0053] [0053]FIG. 3 indicates the roof mount displaced so that the pilot hole is in alignment with the support channel.
[0054] [0054]FIG. 4 is an exploded view showing the lag bolt and stanchion relationship to the roof mount.
[0055] [0055]FIG. 5 is a perspective view when the lag bolt and stanchion are assembled to the roof mount.
[0056] [0056]FIG. 6 is a view taken along line 6 - 6 of FIG. 5.
[0057] [0057]FIG. 7 is a perspective view illustrating the relationship of the assembled roof mount to flashing material.
[0058] [0058]FIG. 8 is a perspective view of the package comprising a pair of elongated C-shaped members and associated equipment.
[0059] [0059]FIG. 9 is a view taken along line 9 - 9 of FIG. 8.
[0060] [0060]FIG. 9 a is a end view of an elongated U-shape member depicting a linear positioning groove for a drill bit to make a hole.
[0061] [0061]FIG. 10 is a perspective view illustrating the attachment of an elongated C-shaped member to a plurality of stanchions.
[0062] [0062]FIG. 11 is a perspective view illustrating the slidable relationship of clamps relative to the C-shaped member and the positioning of a solar module.
[0063] [0063]FIG. 12 is an exploded view of the relationship of an end clamp to a slidable insert.
[0064] [0064]FIG. 13 is an exploded view of the relationship of a bi-module clamp to a slidable insert.
[0065] [0065]FIG. 14 is a perspective view of an assembled solar panel having 4 modules.
[0066] [0066]FIG. 15 is a side view showing a secured end clamp in relationship to the side of a solar panel.
[0067] [0067]FIG. 16 is a view taken along line 16 - 16 of FIG. 15.
[0068] [0068]FIG. 17 is a side view showing a secured bi-module clamp in relationship to the adjacent sides of two solar modules.
[0069] [0069]FIG. 18 is a view taken along line 18 - 18 of FIG. 17.
[0070] [0070]FIG. 19 is a perspective partial view of installation of an object and mounting equipment upon an existing roof utilizing the end clamp of my invention.
[0071] [0071]FIG. 20 is a perspective partial view of installation of an object and mounting equipment upon pipe supports.
[0072] [0072]FIG. 21 is a first alternative end clamp to that shown in FIG. 12.
[0073] [0073]FIG. 22 is a second alternative end clamp to that shown in FIG. 12.
[0074] [0074]FIG. 23 is an alternative clamping means utilizing a wedge.
[0075] [0075]FIG. 24 is a first alternative design of a slidable insert to that shown in FIG. 12.
[0076] [0076]FIG. 25 is an alternative means for providing a threaded member to that shown in FIG. 24.
DETAILED DESCRIPTION
[0077] [0077]FIG. 1 through FIG. 6 illustrate the sequence for installing my roof mount to a rafter.
[0078] [0078]FIG. 1 illustrates the general relationship of base section 17 to a roof having decking 12 and rafter 14 .
[0079] Base section 17 comprises a base 16 and a cylindrical member 18 integral with and extending away from base 16 . Cylindrical member 18 has an offset wall area.
[0080] As illustrated in FIG. 2, base section 17 has a guide tunnel 20 which extends from the top of cylindrical member 18 to the bottom of base 16 . The purpose of guide tunnel 20 is to provide perpendicular alignment of drill bit 24 to rafter 14 for the drilling of pilot hole 26 . Perpendicular alignment is important because it minimizes the probability of rafter splits, as can occur when a pilot hole is drilled which is not in perpendicular alignment to the rafter.
[0081] Cylindrical member 18 further has a cavity 22 , the top of cavity 22 defining an insertion opening 28 . The walls of cavity 22 are threaded for engaging a stanchion 42 as will be discussed later.
[0082] Defining the bottom of cavity 22 is top surface 30 . A hole 32 extends from top surface 30 through base 16 . Hole 32 has a common axis of symmetry with cavity 22 and is designed to accept the stem 36 of a fastening bolt 34 as shown in FIG. 4.
[0083] With the alignment as shown in FIG. 1, drill bit 24 is inserted into guide tunnel 20 and a pilot hole 26 is drilled into rafter 14 as shown in FIG. 2.
[0084] Base section 17 is then displaced along decking 12 until pilot hole 26 is aligned with hole 32 as shown in FIG. 3.
[0085] [0085]FIG. 4 illustrates the relationship of fastening bolt 34 and stanchion 42 to base section 17 . Once hole 32 is aligned with pilot hole 26 , fastening bolt 34 is inserted through washer 40 and screwed into rafter 14 . Fastening bolt head 38 remains within cavity 22 . Stanchion 42 has a male threaded end 44 and is inserted through insertion opening 28 for threadable engagement within cavity 22 .
[0086] Distal from threaded end 44 is female threaded end 46 for frictional engagement of mounting bolt 48 and washer 50 . FIG. 5 and FIG. 6 illustrate the assembled roof mount 10 fastened to rafter 14 . Roof mount 10 comprises base section 17 , stanchion 42 along with threadably connected mounting bolt 40 and washer 50 .
[0087] In practice, the rafters 14 and decking 12 will be installed prior to the installation of roof mount 10 . A single pilot hole 26 is drilled for each roof mount which, due to my design, will be perpendicular to the roof rafter and minimize the risk of rafter split. The number of roof mounts used will be determined by the size of the object to be mounted.
[0088] Once the pilot hole is drilled, base section 17 is slid a short distance and fastening bolt 34 is inserted to fasten base section to rafter 14 . Again, because only one hole is drilled into the rafter for each roof mount 10 , less labor time is required than with typical floor flanges.
[0089] Once all roof mounts 10 have been fastened to their respective rafters, flashing 52 must be installed to protect the roof from the risk of future water damage. FIG. 7 illustrates the arrangement of multiple flashings 52 over a plurality of roof mounts 10 . Following flashing installation, the decking 12 is typically layered with roofing material (not shown).
[0090] Although my mounting system can be utilized for a variety of objects to be mounted above a roof, the following procedure will address installation of a solar panel having multiple modules.
[0091] Once the roof is in a condition for installing a solar panel, a pair of C-shaped elongated horizontal members 54 are provided. Each horizontal member 54 has a base wall 56 and a pair of side walls 58 and 60 . A linear groove 62 runs along the bottom surface of base wall 56 as can be seen in FIG. 9 a and FIG. 10.
[0092] [0092]FIG. 9 a also illustrates a pair of horizontal ledges 64 and 66 extending inward from sidewalls 58 and 60 toward each other. These ledges extend the length of sidewalls 58 and 60 . A pair of protruding lips 68 and 70 extend inward from the distal end of sidewalls 58 and 60 relative to base wall 56 . A track area is defined by the surface area of ledges 64 and 66 which face lips 68 and 70 respectively. The purpose of the track will be discussed below.
[0093] [0093]FIG. 10 illustrates the attachment of horizontal members 54 to roof mounts 10 . Initially, mounting bolts 48 and washers 50 are removed from stanchions 42 . Horizontal member 54 is positioned along each flashing cone. As shown in FIG. 9 a, a drill is used to drill mounting holes 72 along groove 62 on base wall 56 for each roof mount. Once the first mounting hole 72 is drilled, additional mounting holes can be drilled by simply measuring the distance from the last hole drilled when the spacing between the rafters is known.
[0094] The support means can also be modified to be fastened to an existing roof by use of base mounts 810 as shown in FIG. 19. The attachment means comprises base mount 810 which joins to member 54 . An insert is used to threadably sandwich member 54 between the insert and base mount 810 for additional structural support. Alternatively, base mount 810 can be directly bolted to member 54 but this configuration would not provide the structural support as if base mount 810 were bolted to the insert.
[0095] The support means can also be modified to be fastened to ground raking system 700 as shown in FIG. 20. The attachment means comprises a U-shaped member 710 which joins to member 54 having a pipe member therebetween. The ends of U-shaped member 710 are operatively attached to member 54 by the use of an insert (not shown) which essentially serves as the base mount although located within member 54 . Alternatively, U-shaped member 710 can be directly bolted to member 54 but this configuration would not provide the structural support as if U-shaped member 710 were bolted to the insert.
[0096] Once all mounting holes 72 have been drilled, horizontal member 54 , is positioned the above flashing cones with mounting holes 72 aligned with female threaded end 46 . Mounting bolts 48 and washers 50 are then used to frictionally engage horizontal members 54 to respective roof mounts 10 . FIG. 11 shows horizontal members 54 assembled to roof mounts 10 .
[0097] At least two slidable inserts 74 are provided for each horizontal member 54 and a general configuration is illustrated in FIG. 12 and FIG. 13. Insert 74 has a female threaded hole 80 . The outer configuration of insert 74 is designed to be slidably received within track area of horizontal member 54 . The required number of inserts 74 is dependent upon the number of clamps needed to secure the solar panel. There are two types of clamps available: end clamps 76 and bi-module clamps 78 .
[0098] End clamp 76 is illustrated in FIG. 12 and has a hole 82 for alignment with threaded hole 80 on insert 74 . End clamp 76 has a notched surface 84 for frictionally engaging the solar panel and securing it between notched surface 84 and horizontal member 54 when end clamp bolt 86 has its threaded stem 88 passed through washer 90 and hole 82 for engagement with threaded hole 80 on insert 74 . FIG. 15 and FIG. 16 show the solar panel in frictional engagement between notched surface 84 and horizontal member 54 .
[0099] Two end clamps 76 are used to secure a solar panel therebetween and along each horizontal member 54 when each end clamp 76 is threadably fastened to insert 74 using bolt 86 . A solar panel is defined as at least one solar module and can be a number of modules in series as illustrated in FIG. 14. Therefore, four end clamps 76 are used to secure a solar panel to two horizontal members 54 .
[0100] A bi-module clamp 78 is illustrated FIG. 13. They are used to secure the sides of two adjoining solar panel modules and to a horizontal member 54 when bi-module clamp 78 is threadably fastened to insert 74 using a bolt 104 . The use of bi-module clamps 78 and end clamps 76 in my mounting system is best illustrated in FIG. 14.
[0101] The number of bi-module clamps required for each horizontal member 54 is determined by the formula:
[0102] number of bi-module clamps=(number of modules −1).
[0103] Each bi-module clamp 78 has a top side 92 , a bottom side 94 , a pair of side walls 96 . Holes 98 located on top side 92 and bottom side 94 have a common axis of symmetry and are for alignment with threaded hole 80 on insert 74 . Top side 92 extends perpendicularly away from side walls 96 in either direction forming overhangs 100 having notched surfaces 102 . Notched surfaces 102 are for frictionally engaging the solar module and securing it between notched surface 102 and horizontal member 54 when bolt 104 has its threaded stem 106 passed through washer 90 and holes 98 for engagement with threaded hole 80 on insert 74 . FIG. 17 and FIG. 18 show a pair of solar modules in frictional engagement between notched surfaces 102 and horizontal member 54 .
[0104] As a slidable insert 74 is threadably engaged and frictionally positions either bi-module clamp 78 or end clamp 76 along member 54 , insert 74 also frictionally engages an area of member 54 . This relationship is illustrated in FIG. 16 and FIG. 18. This engagement changes the structural properties of member 54 to that of a structural square for enhanced strength. In addition, when engaged to the module or solar panel frame, the structural properties of the module frame combine with horizontal member 54 and form a rigid inter-locking trussed cross-section.
[0105] Alternatives to that shown in FIG. 12 are shown in FIG. 24 and FIG. 25. Rather than having a bolt with a threaded stem which threads downward into insert 74 , FIG. 24 shows a slidable insert 274 having an upward rising threaded stem 288 . FIG. 25 shows insert 74 where bolt 390 having male stem 388 is screwed into from below to have the same final configuration as that shown in FIG. 24.
[0106] Each end clamp 76 has a heal means, or slight rise 108 on its bottom surface distally positioned from its clamping surface and is illustrated in FIG. 12 and FIG. 15. Rise 108 prevents end clamp 76 from twisting while fastening bolt 86 to insert 74 .
[0107] Alternative designs to end clamp 76 shown in FIG. 12 are presented in FIG. 21 and FIG. 22. Rather than having an aperture located on the portion of the clamp which contacts member 54 as is the case for clamp 76 , apertures 172 and 272 for end clamps 176 and 276 shown respectively in FIG. 21 and FIG. 22 are located on the horizontal portion which includes notched surface 184 and 284 . Alternative end clamps 176 and 276 also incorporate a heel means, or raised heels 186 and 286 respectively.
[0108] Besides the heel means of the end clamp designs mentioned which incorporate a heel, an alternative heel means, which performs the same function as a unitized heel, i.e. preventing the twisting of the end clamp while being secured to horizontal member 54 and forcing the clamp inward at 90 degrees to fully engage the object by the notched surface can be accomplished with the combination shown in FIG. 23. Here, end clamp 376 can be the same design as for end clamp 76 but excluding heel portion 108 . The function of the heel is performed by a second item, denoted as wedge 386 . The width of wedge 386 must be sufficient so it will contact both top sides of member 54 . Alternatively, a pair of smaller wedges can be positioned on each top side of member 54 directly below end clamp 376 to provide the proper inward angle toward the object to grip.
[0109] As stated earlier, the securing means, besides being an end clamp having a heel, can also be an end clamp not having a heel used in combination with a wedge or half-moon shaped washer or other protrusion that, when positioned between the bottom side of the end clamp and the top surface of the horizontal member, will provide the same inward force against the object when tightened to the horizontal support rail.
[0110] As best illustrated in FIG. 14, horizontal members 54 along with the associated component parts, namely slidable inserts 74 , end clamps 76 and bi-module clamps 78 and the attachment means to roof mount 10 comprise a solar panel support structure.
[0111] [0111]FIG. 8 illustrates the unitized packaging for the mounting components, namely a pair of horizontal members 54 and the associated number of inserts 74 , bi-module clamps 78 , and a pair of end clamps 76 . The ends of the horizontal members 54 are secured by tape or other packaging material 110 . Packaging material 110 not only maintains the relationship of horizontal members 54 to one another, it also prevents the inserts and clamps from escaping.
[0112] As can be best seen in FIG. 9 a, the outward facing surface 112 of the open side of horizontal member 54 has ridges. These ridges extend the length of each member 54 and form mating or interlocking surfaces when the open sides of two horizontal members 54 are aligned and contacted with one another. FIG. 9 illustrates two horizontal members 54 mated to one another and show a bi-module clamp 78 and an end clamp 76 in view.
[0113] During assembly, the inserts and clamps are placed into a horizontal member 54 . Packing such as paper (not shown) is also inserted to prevent the inserts and clamps from excessive movement and potential wear and damage. The second horizontal member 54 is thereafter mated to the other member by cooperatively engaging along surfaces 112 . Outside packaging is thereafter used to seal the open ends. | A new mounting system for elevating and supporting objects such as solar panels and satellite dishes either upon a roof or above ground.
The mounting system utilizes extruded aluminum horizontal members and a means to secure an object upon the horizontal members. This means to secure is an end clamp having a lip for gripping and either having a heeled distal end or one that instead of incorporating a heel, uses a wedge or half-moon washer to perform the same function. The heel, positioned above the horizontal member prevents the end clamp from rotating as it is screwed into frictional engagement with the member. Such rotation is undesirable since it would reduce the area of the lip in gripping contact with an adjacent object. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims benefit of priority of U.S. Provisional Patent Application Ser. No. 61/441,899, filed Feb. 11, 2011, entitled “DIRECT SEARCH FROM IPTV REMOTE NATIVE APPLICATION TO WEB APPLICATION ON SECOND DISPLAY”, owned by the assignee of the present application and herein incorporated by reference in its entirety.
BACKGROUND
Internet delivery of digital content to IPTVs continues to increase, as does the popularity of IPTVs themselves. In these systems, content delivery is often performed after searches initiated by users of content service providers. However, performing such searches is cumbersome. While some current systems have been made more convenient by the provision of powerful remote controls on which searches may be entered, the user is still required to perform the manual action of opening a remote control application, navigating to a search field, and entering a search term.
SUMMARY
Systems and methods are provided that allow a user to directly launch a second display application with a requested search term from within the context of a native application on a second display, including a browser application. In this way, the user is immediately brought to the search page with relevant search results. This process is occasionally termed a “direct search” herein. The search term may be derived from the native application which in turn may derive from the context of the IPTV. Such a context could be metadata from a currently playing content item, e.g., on a Blu-ray® disc in a Blu-ray® player, or from a TV channel. The second display application may be a web application or a native remote controller or other application. In this way, the user is saved the trouble of having to open the second display application and perform the search manually, reducing the difficulties of the systems disclosed above.
Variations of the systems and methods will also be seen. For example, instead of a web application or a native remote controller application, the user may also employ received parameters to perform a direct search as well. Such implementations may be useful when a user is passed keywords or content metadata via e-mail, instant messaging, text messaging, and the like. In this implementation of the invention, the recipient need not navigate to a search facility or second display application in order to perform a search on the same.
In one exemplary implementation, the following steps may be performed. When the native IPTV remote control application launches the second display application, which may be a web application, the search term is added to a launch script (using an API which may be hosted by a server such as a management server) together with the requested action, e.g., to search for similar items. The server then configures the second display application to go directly to the search results upon launch. The server may then redirect the launch URL/URI to the second display application. The second display application loads on the second display, e.g., in a browser therein. The second display application automatically uses a search service to search for the term which had been set by the server. The second display application then shows the search results on the second display.
Where the second display application is not a web application, analogous steps may be performed, but the same are then performed in the context of the native application.
In this way, the user can directly launch a search within the context of the second display application, without having to load the second display application in a separate initial step.
The second displays serve as a visual aid to the IPTV, but generally do not require additional investment by the user because the same make use of a device, e.g., a smartphone, laptop computer, tablet computer, an internet appliance, etc., which most users would already have in their possession. Such a second display provides a complementary functionality to a content playback device such as an IPTV because of the second display's strength in supported languages and character font sets, data entry, processing power, and user experience in content management.
Where the second display application is a web application, the same may be scripting or non-scripting. The second display application may also be a Java application or any other sort of application that may communicate with a server. For example, the ASP/.NET framework with RPC can be employed to write the second display application. Where the web application running on the second display is written in HTML or HTML with Javascript, the same may be loaded by any device with a browser, and so the same is not limited to only a small set of compatible devices or expensive remote controls. Where a smartphone is employed, a mobile version of the second display user interface may be employed, with an appropriate listing of fields and an appropriate mobile resolution.
Communications with service providers may take place through a proxy server, and the proxy server presents to service providers the authentication credentials of the content playback device, so that the second displays appear to the service providers as authenticated content playback devices.
As noted above, the second displays may include any device that can run an application that communicates with a content playback device, including, but not limited to, personal computers, laptop computers, notebook computers, netbook computers, handheld computers, personal digital assistants, mobile phones, smart phones, tablet computers, hand-held gaming devices, gaming consoles, Internet appliances, and also on devices specifically designed for these purposes, in which case the special device would include at least a processor and sufficient resources and networking capability to run the second display application.
The content playback device can take many forms, and multiple content playback devices can be coupled to and selected within a given local network. Exemplary content playback devices may include IPTVs, DTVs, digital audio systems, or more traditional video and audio systems that have been appropriately configured for connectivity. In video systems, the content playback device includes a processor controlling a video display to render content thereon.
In a general method of operation, a user employing a second display has a user account with a source or clearinghouse of services. Here, the source or clearinghouse is represented as a user account on a management server, but it should be understood that the user account may be with a service provider directly. The user account may have information stored thereon related to what content playback devices are associated with the user account. When a user logs on, they may see this list of content playback devices and may choose a particular content playback device. If there is only one content playback device on the network, or if the user is browsing in a way that the content playback device identity is not needed, then this step may be omitted. Moreover, a user may control content playback devices that are not included in a user account. For example, content playback devices may be discoverable and controllable, e.g., via infrared or Bluetooth® or the network or otherwise, that are not part of the user account with a management server or with a service provider. It may even be possible for a user to playback content on such a content playback device, if a service provider has made available content that can be delivered without access made to a user account.
Once a content playback device has been chosen, a list of services may be displayed. The list of services may be customized to those that have content playable on the chosen content playback device, or all available content may be displayed, in which case, e.g., a notation may be displayed adjacent the content item as to whether it is playable on the selected device. Such customization may also apply to the search results obtained as a result of the direct search routine, as described in greater detail below.
Where no content playback device has been selected, all available content may be displayed. If no content playback device has been selected, but the user account includes stored information about which content playback devices are available, then all content may be displayed, or a subset of all content may be displayed based on the known content playback devices associated with the account, or notations may be presented about which content playback devices can play which content, or a combination of these. In some cases, a content service provider may require a content playback device to be chosen so as to determine if content from that service provider may be played back. In other cases, no content playback device need be chosen and the user may simply choose and queue content for later playback by a content playback device to-be-determined at a later time.
Assuming multiple services are available, the user then selects a service to browse. In many cases, access to a service requires becoming affiliated with the service. Details of such affiliation processes are provided in U.S. patent application Ser. No. 12/982,463, filed Dec. 30, 2010, entitled “Device Registration Process from Second Display”, owned by the assignee of the present application and incorporated by reference herein.
Once the content playback device is affiliated with the services, the user may choose which service they wish to browse. Where a content playback device has not been chosen, the user may still choose services and browse, but the content offerings may be less specific to a given content playback device. The service presents a list of available content items. The presentation may be in any number of forms, including by category, by keyword, or in any other form of organization. The proxy server presents an authentication credential of the content playback device to the content server. In some cases, credentials for accessing the various services may be stored in the user account, and presented by the proxy server or management server to the content server when needed.
Individual services may employ their own DRM schemes which the current systems and methods may then incorporate. For example, if a video content service provider only allows a predetermined number of devices on which their content may be played back, then this rule may be enforced or duplicated within the context of the current system and method. Moreover, changes to such service provider rules or other parameters may be periodically polled for by the proxy server and/or management server, or the same may be polled for at a subsequent login of the service, e.g., at the time the affiliation is renewed. In other words, upon login, the system and method may poll for and receive a token associated with the given service provider, the token providing information to the system about the service provider as well as about the user account with the service provider.
The system and method may include a management server as mentioned above which, along with the content playback device, communicates with at least one content server such that the content server provides content items for presentation at the content playback device. The system and method may further include a proxy server communicating with the management server and the second displays. In some cases, the proxy server may be merged with the management server, or in other cases a separate proxy server may be provided for each content server or service provider.
In one aspect, the invention is directed to a method of causing a second display application to launch and search on a search item, including: receiving a search item; upon reception of the search item, instantiating a second display application and causing the second display application to search on the search item; and displaying the results of the search.
Implementations of the invention may include one or more of the following. The receiving a search item may include receiving a search term in a search field. The search field may be disposed in a browser on the second display. The search item may include metadata from a content item, a keyword, a search term, a category, an image file, or an audio file. The causing the second display application to search on the search item may include sending an identifier corresponding to the search item to a server along with an identifier associated with an action corresponding to the search item. The action corresponding to the search item may be to find assets or services related to the search item. The assets or services may be related to the search item by metadata. The search item may include metadata from a content item, and the receiving a search item may include receiving metadata from a Blu-ray® disk or from a streamed video program. The method may further include displaying a prompt for a user to create a shortcut associated with the search to be directly launched, and upon user input, creating the shortcut. The second display application may be a native remote controller application. The second display may be a tablet computer, a smart phone, a laptop computer, a desktop computer, an internet appliance, or a computing device with internet access. The displaying the results of the search may include only displaying services for which the second display or an associated content playback device are affiliated, or may include displaying services for which the second display or an associated content playback device are unaffiliated, and further comprising displaying a screen or a link whereby the content playback device or the second display may become affiliated with the service.
In another aspect, the invention is directed to a non-transitory computer-readable medium, comprising instructions for causing a computing device to implement the above method.
In another aspect, the invention is directed to a method of causing a second display application to launch and search on a search item, including: receiving a search item; upon reception of the search item, adding the search item to a launch script; sending a signal to configure a second display application to instantiate a search results page upon launch; redirecting a launch URL/URI to the second display application; and returning search results to the second display for display.
Implementations of the invention may include one or more of the following. The receiving a search item may include receiving a search term entered in a browser. The method may further include performing a search on services or assets similar to the search item, where the similarity may be in metadata. If a found service is unaffiliated with a user account or content playback device associated with the second display, the method may further include causing the display of a link or page where a user account or content playback device associated with the second display may become affiliated with the service.
In another aspect, the invention is directed to a non-transitory computer-readable medium, comprising instructions for causing a computing device to implement the above method.
Advantages of certain embodiments of the invention may include one or more of the following. A direct search as described here allows the seamless searching of a large array of service provider offerings from within the confines of an already used native application, negating the need to search separately or to separately open a second display application.
Other advantages will be apparent from the description that follows, including the figures and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Like reference numerals denote like elements throughout.
FIG. 1 is a block diagram of an exemplary system in accordance with one aspect of the present principles.
FIG. 2 is a sequence diagram illustrating a method according to another aspect of the present principles.
FIG. 3 is a flowchart illustrating an exemplary method according to a further aspect of the present principles.
FIG. 4 is a flowchart illustrating an exemplary method according to yet another aspect of the present principles.
FIG. 5 is a flowchart illustrating an exemplary method according to a further aspect of the present principles.
FIG. 6 is a flowchart illustrating an exemplary method according to a further aspect of the present principles.
FIGS. 7 (A)-(C) schematically illustrate how a user interface on a second display, particularly one associated with a native application, can lead to the launching of a second display application with search results automatically entered and searched on.
FIG. 8 is a block diagram of an exemplary modular second display system in accordance with a further aspect of the present principles.
FIG. 9 is a block diagram of an exemplary modular server system in accordance with a further aspect of the present principles.
FIG. 10 is a flowchart illustrating an exemplary method according to a further aspect of the present principles.
FIG. 11 is a block diagram of an exemplary second display in accordance with a further aspect of the present principles.
FIG. 12 is a block diagram of an exemplary server in accordance with a further aspect of the present principles.
FIG. 13 illustrates an exemplary computing environment, e.g., that of the second display, proxy server, management server, or content server.
DETAILED DESCRIPTION
Referring initially to FIG. 1 , a direct search system 10 is shown including a content playback device 12 coupled to a local network 16 , which may be wired, wireless, or a combination of both. Also coupled to the local network 16 are one or more second displays 14 a - 14 c , an exemplary one of which is (in below figures) termed second display 14 i . A number of servers may be accessed by the content playback device 12 and the second display 14 i through the local network 16 and the internet 25 , including a management server 18 , a proxy server 22 , and one or more content servers 24 corresponding to service providers (only one is shown in FIG. 1 ).
The second display 14 a includes a user interface 23 for a second display application which when launched may in turn automatically perform a search on a desired search item, the nature of which is described in greater detail below, and the results of which are illustrated as search results 29 . For example, if a user is playing a Blu-ray® disc, watching IPTV channels, or browsing the Internet, various opportunities will be seen on which to search. For example, a user may desire to search content related to that being watched on the Blu-ray® disc, e.g., similar movies, sequels, or the like. If a user often performs the same search, they may set that search as a default, and in that case the search and second display initialization may be accomplished by clicking an icon or the like.
A search is generally made of assets and services available or accessible by a server, e.g., the management server and the accessible content servers. The results of the search may be displayed on the second display user interface 23 or on the content playback device 12 . Where the search finds an asset, the same may be generally listed on the second display and subsequently played back on the content playback device 12 , although in some cases, the asset may also be played back on the second display 14 a.
An authentication credential of the content playback device may also be logged with the user account, this credential often required for access to services and content items. In some cases, a found asset or service may be automatically launched, and in this case, the same may access the authentication credential, or receive the same from the content playback device, if required to perform the launch.
Using the system 10 of FIG. 1 , a user of the second display 14 a is provided with a convenient way to perform a search so as to directly initialize the second display application with the search results loaded. In this way, the user is saved the inconvenience of having to initialize the second display application, enter a search term, and perform the search. The convenient and flexible user interface 23 of the second display 14 a may then be leveraged to choose content from the found results for playback on the content playback device 12 .
Details of individual components are now described.
The content playback device 12 may be, e.g., an IPTV, a digital TV, a digital sound system, a digital entertainment system, a digital video recorder, a video disc player, a combination of these, or any number of other electronic devices addressable by a user on the local network 16 . For the sake of simplicity, in this specification, the content playback device 12 will generally be exemplified by an IPTV, in which case it will typically include a processor that controls a visual display and an audio renderer such as a sound processor and one or more speakers. The processor may access one or more computer-readable storage media such as but not limited to RAM-based storage, e.g., a chip implementing dynamic random access memory (DRAM), flash memory, or disk-based storage. Software code implementing present logic executable by the content playback device 12 may also be stored on one of the memories disclosed below to undertake present principles. The processor can receive user input signals from various input devices including a remote control device, a point-and-click device such as a mouse, a keypad, etc. A TV tuner may be provided in some implementations, particularly when the content playback device 12 is embodied by an IPTV, to receive TV signals from a source such as a set-top box, satellite receiver, cable head end, terrestrial TV signal antenna, etc. Signals from the tuner are then sent to the processor for presentation on the display and sound system. A network interface such as a wired or wireless modem communicates with the processor to provide connectivity to the Internet through the local network 16 . It will be understood that communications between the content playback device 12 and the internet 25 , or between the second display 14 i and the internet, may also take place through means besides the local network 16 . For example, the second display 14 i may communicate with the content playback device 12 through a separate mobile network.
The one or more second displays 14 a - 14 c each bear a processor and components necessary to operate an application for, e.g., service provider and content selection, as well as for client aspects of a direct search system. In particular, the processor in the second display may access one or more computer-readable storage media such as but not limited to RAM-based storage, e.g., a chip implementing dynamic random access memory (DRAM), flash memory, or disk-based storage. Software code implementing present logic executable by the second display may also be stored on one of the memories disclosed below to undertake present principles. Further, the second display 14 i can receive user input signals from various input devices including a point-and-click device such as a mouse, a keypad, a touchscreen, a remote control, etc. A network interface such as a wired or wireless modem communicates with the processor to provide connectivity to the local network and to wide area networks such as the Internet as noted above.
The servers 18 , 22 , and 24 have respective processors accessing respective non-transitory computer-readable storage media which may be, without limitation, disk-based and/or solid state storage. The servers communicate with a wide area network such as the Internet via respective network interfaces. The proxy server 22 may in some cases be combined with the management server 18 , although in many cases it may be preferable to separate the servers to better accommodate server load. The servers may mutually communicate via the internet 25 . In some implementations, the servers may be located on the same local network, in which case they may communicate with each other through the local network without accessing the internet. For example, in one exemplary implementation, the management server 18 and the proxy server 22 may be disposed in the same data center, so communication between the two may stay within the data center.
While an exemplary method of the system is described below, certain method steps especially pertinent to certain arrangements of the second display will be described here.
Responsive to the second display 14 i sending a request to the proxy server 22 for an executable utility, the proxy server 22 returns the utility to each second display 14 i . Running the utility causes the instantiation of an application. The implementation discussed here includes a web application, but it will be understood that other types of applications may also be employed as described above.
The second display 14 i , executing the web application, prompts a user to input to each second display 14 i login information. The login information may be common or may differ between second displays. The proxy server 22 , responsive to reception of correct login information from the content playback device 12 , returns the local IP address of the content playback device 12 to the second display 14 i , because the same has previously been registered to a user account in which such information is maintained. The proxy server 22 may also return a list of content playback devices on the local network, responsive to which the second display 14 i may select one for content playback. In turn, each second display 14 i uses the local content playback device address to access the content playback device 12 directly to request information about the content playback device 12 , which information is returned from the content playback device 12 to the second display 14 i such that the local address of the content playback device 12 need not be globally addressable. Each second display 14 i may also select content for playback on different content playback devices. The second display 14 i sends the information about the content playback device 12 to the proxy server 22 , requesting a list of services available to the content playback device 12 from one or more service providers. The services may be dependent on the device characteristics of the content playback device 12 chosen. For example, if the chosen content playback device 12 is an IPTV, video services may be returned. If the chosen content playback device 12 is an audio system, audio services may be returned.
The proxy server 22 relays the request for a list of services to the management server 18 , which returns the list to the proxy server 22 , with the proxy server 22 in turn sending the list to the second display 14 i for presentation of information on the second display 14 i . Responsive to a user selection of an item on the list, the second display 14 i sends a request for a software asset corresponding to the selected content item to the proxy server 22 . The proxy server 22 requests a service login of the content server 24 providing the content, and the content server 24 provides to the proxy server 22 a list of content items, assets, categories, or services, and the proxy server 22 relays the list to the second display 14 i , which is presented on the second display 14 i so that the user can navigate to enter a selection. Responsive to the selection, the second display 14 i sends a command to the content playback device 12 to access and play back the selection.
The command to play the local content item may be in a number of forms. The second display 14 i may communicate to the proxy server 22 the request on behalf of the content playback device 12 , and this request may be via the local network or via other means. Alternatively, the second display 14 i may transmit a request to the content playback device 12 that it itself formulates the request, and this transmission may be by way of the local network, the internet generally, or via other means such as other wired or wireless transmission schemes, including via USB, IR, Bluetooth®, or any other schemes. If the second display 14 i is configured to address the content playback device 12 at a non-local level, e.g., at the server level, then the second display 14 i may be physically located virtually anywhere and still be able to queue content or to command the content playback device 12 to play content. In this case, however, server load would increase over the case where the second display and content playback device communicated directly or over a local network.
Certain method steps of an arrangement of the content playback device are described here. Using a network interface, the content playback device 12 can communicate with a management server 18 on the Internet and with one or more content servers 24 , also on the internet and communicating with the management server 18 . The management server 18 receives and stores a local IP address of the content playback device 12 . The content playback device 12 communicates with the management server 18 to arrange for content items from the content server 24 , operated by a service provider, to be played back on the content playback device 12 . In more detail, the content playback device 12 sends login information to the management server 18 which returns to the content playback device 12 a user token that must subsequently be presented by the content playback device 12 to the content server 24 to obtain content from the content server 24 .
FIG. 2 is a sequence diagram illustrating an exemplary implementation of a method for enabling a user to employ a second display to browse content playback devices, service providers, content items and select the same for playback by a content playback device. FIG. 2 assumes that the user has already created an account with a management server and has affiliated one or more content playback devices with that account.
At state 52 , a user turns on the content playback device 12 . At state 54 the content playback device sends login information including, e.g., username and password, to the management server 18 , which at state 56 returns to the content playback device a user token that may subsequently be presented by the content playback device to a content server 24 to obtain content from that server. The management server 18 in addition stores the local IP address of the content playback device 12 .
At state 58 , the user turns on the second display 14 i and instantiates a web browser session in which control may be exercised over the content playback device. Other types of sessions may also be employed as has been noted. A utility is executed on the second display 14 i , at state 60 , which sends a request to the proxy server 22 , which returns in state 62 a web application, e.g., HTML with JavaScript, for the second display to execute for browsing services and content items. This application may make, e.g., asynchronous JavaScript and XML calls to the proxy server 22 and to the content playback device 12 to obtain information to control the content playback device 12 .
At state 64 , using the JavaScript received from the proxy server 22 , the second display 14 i prompts the user to input to the second display 14 i the account login information, including, e.g., the same username and password that the content playback device provided to the management server 18 in state 54 during device registration. Of course, the account login information may differ as well. It will be appreciated that the servers 18 , 22 , and 24 communicate necessary account information between them as needed to realize the principles described here.
The proxy server 22 responds to a correct user name and password from the second display 14 i in an authentication request state 63 . The proxy server 22 verifies the user name and password with the management server 18 (states 67 and 69 ), creates and transmits a session token to the second display, obtains information about content playback devices affiliated with the user account, and completes the authentication in state 65 . The proxy server 22 may return to each second display the information about all content playback devices 12 that are affiliated with the user account associated with the user name and password, including their local IP addresses which were stored by the management server 18 after login at 54 (and subsequently provided to the proxy server 22 ). In more detail, the proxy server 22 sends a token to the second display 14 i , the token associated with a content playback device, and this token gets communicated in future transactions between the second display and the proxy server, so that the proxy server 22 knows what content playback device the content item is intended for. Each user with each second display may then choose a content playback device and browse the services and content options available through the services in state 96 and subsequent steps.
The second display 14 i , using the local IP address returned as noted above, accesses the content playback device directly, in the sense of communicating through the local network. To select a particular content playback device, the second display 14 i requests information about the content playback device 12 at state 70 , including language information, digital rights management (DRM) information, etc., as desired, which information is returned from the content playback device to the second display 14 i at state 72 . Since the second display 14 i knows the IP address of the content playback device 12 and consequently communicates directly with the content playback device 12 , the second display 14 i communicates using a local web address of the content playback device 12 that need not be globally addressable, and may so communicate as long as the second display 14 i and content playback device 12 are on the same local network.
Each second display 14 i may send the client information received at state 72 to the proxy server 22 , requesting a list of services available to the content playback device 12 , or that the content playback device 12 is entitled to, from one or more of the content servers 24 . The proxy server 22 relays the request to the management server 18 , which returns the requested service list to the proxy server 22 . The proxy server 22 in turn sends the services list to the second display for presentation of available services on the second display. Each user browses the services and their content on the second display just as though it were the actual content playback device.
A user can input, using, e.g., a second display input device, a selection of a service on the list that was returned to the second display. In response, the second display, at state 74 , sends a request for the corresponding service to the proxy server 22 along with the service token that that second display may have received from the content server 24 via the management server 18 .
Responsive to the request, the proxy server 22 requests a service login at state 86 of the content server 24 providing the selected service. At state 88 , the content server 24 provides to the proxy server 22 a list of content items, assets, categories or services, as the case may be, for the particular content server 24 . If desired, the proxy server 22 may also request of the content server 24 a list of options, and the list may be returned, e.g., in extended markup language (XML) format, to the proxy server 22 which relays the content items, assets, categories, services, etc., available for selection to the second display at the state 80 .
The content available for selection is presented on the second display so that the user can navigate (in state 97 ) the display to enter a selection. Responsive to the selection, the second display at state 98 sends a command to the content playback device 12 to play the selection, and in particular sends a playlist id or reference identifier indicating the selection. At state 100 , the content playback device 12 , using its authentication credentials, sends the playlist id or reference identifier to the proxy server 22 , which returns the required playlist data in state 102 . The content playback device 12 can then request the content URL with the playlist data in state 104 , which may be responded to with a return of the content URL for playback of the content item on the content playback device 12 in state 106 .
Variations of the system and method are now described.
If the content playback device were already playing content, the new content commanded to be played by the second display may be placed in a queue in the content playback device and played when the current content completes. In any case, once the content has been commanded to be played, the user may continue to browse the second display for other content, to play or to add to the queue. Other users may employ their own second displays to do the same. A user may also desire to switch devices and resume playback on a different device by, e.g., navigating to a “recently viewed” list and selecting the last video played after switching control to the desired device.
The above description has been for the case where the proxy server 22 is employed to hide the content source, e.g., a content URL, from the second display 14 i . That is, the proxy server 22 provides an API for the second display to use so that the content and/or content URL cannot be accessed directly. In this way, the details of the management server transactions to access the services remain desiredly unknown. In many cases, the second display 14 i may have stored thereon little or no details about the content playback device 12 . In some cases, however, the URL may be directly provided from the proxy server 22 or the proxy server 22 may even be bypassed, e.g., in cases where the content item is intended for free distribution, e.g., movie trailers or the like. Similarly, while the above description has focused on content item playback on content playback device 12 , certain content items, e.g., those which are intended for free distribution, may be played back on the second display 14 i itself, if the same has been appropriately configured.
In the case where multiple second displays request content to be played at or near the same time, a simple rule such as the first-in-time may prevail. Alternatively, a priority scheme may be configured, such that certain second displays take precedence over other second displays. Alternatively, a plurality of user profiles may be employed, and precedence may be based on the identity of specific users.
The control device may command the content playback device to play content by sending, to the content playback device over the local network, commands coded as if they were sent from an infrared remote control, e.g., the commands may be in the Sony Infrared Remote Control System (SIRCS) protocol.
FIG. 3 illustrates a general method 30 by which a direct search and second display launch may be performed. The method 30 is meant to be illustrative, and illustrate steps performed by both a server and a second display.
A first step is that a user indicates a search subject or search item (step 108 ). The search subject or search item may be indicated in a number of ways, and the same may constitute a number of different types of data objects.
For example, a search term may be identified in any native application (step 112 ). For example, a native application on the second display may take the form of a remote controller application. The remote controller application may then control any or all aspects of playback of content playback devices on the system, e.g., digital video recorders, Blu-ray® disc players, or other such devices. In the remote controller application, a term may be identified and then used as a search item. In many cases, the native application will have a search field built in. In other cases, the native application will provide a number of fields that describe a content item that is being played back. For example, the native application may indicate that a song from a given album is being played back. By an act of the user, an aspect of the played-back song may be used in a search. For example, the user may highlight the album name, click on the same, and retrieve search results relating to that album name. In the same way, a search field may be provided in which a user may enter a search term. Other search facilities within a native application will also be understood.
Another way for a user to indicate a search item or subject is to have the term identified in a browser. That is, the second display may have a browser invoked, and the same may be pointed to a given webpage. A term may be identified in the webpage and then used in the direct search system (step 114 ). For example, the browser may include a search entry field, or clicking on a term in the browser window may lead to a search being performed on the clicked-on term. In another implementation, a website may have a content item featured or otherwise listed: by dragging an icon or the like associated with the content item on to a screen region associated with a server, e.g., the management server, the same may be directed to search on metadata associated with the content item to find like items throughout the management server ecosystem.
Another way for a user to indicate a search item or subject is to use metadata found from identified or played content items (step 116 ). For example, a user may be playing back a television show or playing a movie from a BD. In either case, metadata will generally be available from the streamed or played back content. It will be seen that this step may overlap in some cases with step 112 , at least where the search term in step 112 constitutes metadata. Such metadata may include, e.g., genre or rating information. By clicking on an icon or column heading corresponding to the same, services or assets may be found that are similar to the subject item. In a specific implementation, the remote controller software operating the given content playback device running on the second display may include a “SHOW ME MORE” button that when clicked finds similar content items, or services offering similar content items, as may be available from the server.
Another way for a user to indicate a search item or search subject is to use a non-metadata aspect of a content item (step 118 ). For example, a user may search for items similar to a given image, once the image has been subjected to some level of image analysis. In the same way, a user may search on a particular category of services or assets. It will be understood, of course, that in some implementations category data is stored as metadata.
Once a user has indicated the search subject or search item, a search is performed on available services and/or assets by the server (step 122 ). The server may search a listing of associated content providers, as well as content offerings from those content providers. The second display application then is instantiated and the search is run and results displayed (step 124 ).
A number of steps may be taken once the results are found, to provide different sets of results. In one step, the found results may be filtered based on known content playback devices (step 132 ). For example, a user may have a limited number of types of content playback devices, and the existing content playback devices may not be able to play back all the assets found. In this case, the found results may be filtered so that only those are shown that are capable of being played by the user.
In another example, if the search results include a number of found services, the results may be filtered such that services are only displayed for which a user has an affiliation set up (step 126 ). In this way, a user need not sift through a large number of results, many of which may be unavailable to the user due to lack of affiliation.
In a related example, all found services may be displayed to the user, including unaffiliated ones, but the user may be offered an option to create an affiliation with the same (step 128 ). In this way, a user may have more results to sift through, but they may be conveniently given the option to create an affiliation to playback a found result.
FIG. 4 illustrates a flowchart 40 that describes in greater detail how a search term is used in combination with a second display application initialization to provide search results upon launch. In a first step, a search term is identified in any way (step 134 ). The various ways have been noted in FIG. 3 by steps 112 , 114 , 116 , and 118 . Other ways will also be noted. A next step in the flowchart 40 is that the search term is added to a launch script using an API, which is generally hosted by a server. The particular action requested may also be added to the launch script where necessary or where not clear from the context, e.g., “SHOW ME MORE”, “FIND SIMILAR GENRE”, etc. where no action is supplied, a default action may be defined, e.g., “SHOW SIMILAR ITEMS”.
The management server then verifies the credentials of the request (using, e.g., referrer_id, user_token, or the like), and sets the search term and action, configuring the second display application to go directly to a set of search results upon launch (step 138 ). The second display application, e.g., a web application, then loads (step 142 ), and, if a search term is set, employs a search service to search on the terms set by the server in steps 136 and 138 (step 144 ). The nature of the search service or facility may include such as is generally known. The search results are then displayed on the second display (step 146 ).
FIG. 5 illustrates a flowchart 50 where the method steps are specifically for a second display. In a first step, the search term is identified by the methods noted above (step 148 ). A next step is that the search term and associated action, if necessary, are sent to a server, where they are added to a launch script (step 152 ). The second display application then loads on the second display (step 154 ). The second display application employs the search term in a corresponding search (step 156 ). Finally, the second display application displays the search results (step 158 ).
FIG. 6 illustrates a flowchart 60 where the method steps are specifically for a server. Some of the steps are similar to steps in the flow chart 50 , however, flowchart 60 represents the server side of the steps. In a first step, the server receives the search term and the action (if necessary) from the second display, e.g., from a native remote controller application or browser (step 101 ). A next step is that the search term and action are added to the launch script by the server API (step 103 ). A next step is that a signal is sent from the server to the second display to configure the second display application to go directly to the search results upon launch of the second display application (step 105 ). The server then causes redirection of the launch URL or URI to the second display application (step 107 ). The search is then conducted (step 109 ). The search may be conducted on the given server or on a separate server. The results of the search are then returned to the second display (step 111 ).
FIGS. 7 (A)-(C) schematically illustrate how a user interface on a second display, particularly one associated with a native application, can lead to the launching of the second display application with search results automatically entered and searched on. In FIG. 7(A) , a second display 14 i is illustrated with a first user interface 23 corresponding to a native application. An identified term 15 is illustrated which may correspond to any identified term in the first user interface, e.g., those identified in step 112 of FIG. 3 . FIG. 7(A) then illustrates (right side) how a second display application 29 may be initialized with a launched search on services and assets using the identified term 15 . In FIG. 7(B) , a second display 14 i is illustrated with a second user interface 23 corresponding to a browser application. An identified term 17 is illustrated which may correspond to a term in a search field or a term in a browser window, e.g., those identified in step 114 of FIG. 3 . FIG. 7(B) then illustrates (right side) how a second display application 29 may be initialized with a launched search on services and assets using the identified term 17 . In FIG. 7(C) , a second display 14 i is illustrated with a third user interface 23 corresponding to a media player application, e.g., for operating a BD player. An identified term 19 is illustrated which may correspond to any identified term in the first user interface, e.g., those identified in step 116 of FIG. 3 , e.g., metadata from a content item. FIG. 7(C) then illustrates (right side) how a second display application 29 may be initialized with a launched search on services and assets using the identified term 19 .
Aspects of various components are described below.
FIG. 8 illustrates one implementation of a second display 70 . The second display 70 includes a display module 115 for use in, e.g., browsing services and displaying search results. The display module 115 may also be employed in browsing lists and selecting items related to the content playback device. For example, a list of content playback devices accessible to the local network and/or addressable by the second display may be displayed using the display module 115 , and the user may choose a content playback device from among them. In addition to choosing content playback devices, a user may review a list of accessible service providers using the display module 115 . For example, such service providers may include those offering video-on-demand services for movies and other video content, audio content, or any number of other sites on which content may be browsed and selected. In one implementation, where a content playback device has been chosen, the results may be filtered based on the capability of the content playback device to render the content. In another implementation, the display module 115 may display not just content accessible to the local network, but also content resident on the local network, such as content stored on a digital video recorder or Blu-ray® player.
In some implementations, the display module 115 may be a module that produces an output signal for display by another device. In this case, the actual display may be external to the second display itself For example, in the case of a Blu-ray® player being used as a second display, the display module 115 may be a unit that produces, e.g., an HDMI output signal, while the actual display may be performed by the TV that is connected to that HDMI output.
The second display 70 also includes a module for network communications 117 that allows the second display to communicate with the local network as well as, in some cases, specific devices directly. In particular, as part of the network communications module 117 , a communications module 123 for communications with a content playback device is provided. The content playback device communications module 123 allows the second display to communicate with the content playback device either over the local network, via the internet, or directly. Such direct communications may include various types of wired or wireless transmission schemes, including WiFi, USB, infrared, Bluetooth®, or the like.
Also within the network communications module 163 may be an optional web-browsing module 119 through which the above-noted content items may be browsed in the case where the second display application is a web application. The web-browsing module 119 may be implemented in a number of ways, including by executing application code written in HTML, Javascript, or the like. A web-browsing module implemented in such a way allows the same to be implemented across many platforms, allowing any number of types of second displays to be employed. In some cases, special applications, e.g., helper applications, may be employed to communicate with particular proprietary or non-web-based technologies. Where the second display application is non-web-based, and is written in, e.g., native code, the web-browsing module 119 may be replaced with an analogous module allowing service and content selection and other functionality as has been described, e.g., for selection of content playback devices from within the context of a native remote controller application.
Also within the network communications module 117 may be a direct search launch module 121 . The direct search launch module 121 may be employed to perform any of the steps, or a portion of such steps, in FIGS. 3-5 .
It is noted that the above modules may be implemented in hardware, non-transitory software, or a combination of the above. Typically, the same will be implemented within the context of a laptop computer, a tablet computer, a smart phone, or the like.
Referring to FIG. 9 , a server 110 is illustrated in which may be implemented certain methods according to the present principles. The server 110 includes a storage module 177 in which may be stored data and computer-executable instructions to implement the functionality described above. To some extent, content may be stored in the storage module 177 . However, in general, content delivered to second displays will be stored at, or at least accessible from, service providers and content servers.
The server 110 further includes a network communications module 179 . Through the module 179 , communications may be had with proxy servers, content providers, and second displays. For example, the network communications module 179 may include a second display communications module 181 through which communications with second displays may be implemented and conducted. The module 179 may further include a content provider communications module 183 for respective communications with content providers. The second display communications module 181 may include an API module 185 allowing manipulation and communication of various second display application parameters. For example, the API module 185 may be employed to add a given search term received from the second display to a launch script, to configure a second display application to go directly to a set of search results on launch, and to direct a launch URL to the second display application.
FIG. 10 is a flowchart 80 illustrating a method which may be employed within the context of the principles described, and in particular to allow storage and reuse of searches. In flowchart 80 , a first step is that a user performs a search (step 125 ). In an alternative implementation, a user may have chosen a service or asset from a list (step 127 ). If a user commonly performs such a search, or commonly plays a particular asset, or commonly searches a particular service, the user may choose to have the search for a given service or asset stored as a direct launch search (step 129 ). In this way, by activating a convenient button such as an icon, the user may cause the second display application to initialize with the given search, asset, or service as a search parameter. For example, a user may have an interest in a given artist. By clicking a “SEARCH THIS ARTIST” button set up in a procedure such as step 129 , a set of search results in the second display application may be easily retrieved, e.g., the search results relating to new content from the artist or related content. An identifier of the direct launch search may be stored (step 131 ), e.g., as a cookie where the second display is a web application.
Referring to FIG. 11 , an implementation of a second display 90 which may operate according to the principles described here is illustrated. In this implementation, the second display 90 includes various memory locations bearing computer-readable instructions capable of performing various steps. First, the second display 90 includes a processor 145 and memory 135 bearing computer-readable instructions capable of identifying the search term. For example, the identified search term may include metadata, data in a search field, data on a browser page, and so on, as has been described above. The second display 90 may further include memory 137 bearing computer-readable instructions capable of sending the search term, and associated action if necessary, to a server such as a management server.
The second display 90 further includes memory 139 bearing computer-readable instructions capable of loading and running the second display application employing a modified launch script. The second display 90 further includes memory 141 bearing computer-readable instructions capable of running a search initiated by the modified launch script. Finally, the second display 90 may further include memory 143 bearing computer-readable instructions capable of displaying the results of the directly launched search.
Other memories will also be understood, including those with instructions which create shortcuts for searches, those which include instructions for native remote controller applications, those which receive and display a list of services associated with the user account, those which filter a displayed service according to a category or the like, and those which provide for user selection of the services and assets, among others.
Referring to FIG. 12 , an implementation of a server 100 is illustrated, and as in the case of the second display 90 , includes various memories bearing computer-readable instructions capable of performing various steps. The server may be, e.g., a proxy server, a management server, or any other sort of server as described above. The server 100 includes a processor 145 and memory 147 bearing computer-readable instructions capable of receiving a search term, and associated action if necessary, from a second display. The server 100 may further include memory 149 bearing computer-readable instructions capable of operating or running an API to add the search term and the action to a launch script for a second display. The server 100 may further include memory 151 bearing computer-readable instructions capable of sending a signal to configure the second display application to go directly to a set of search results upon launch. The server 100 may further include memory 153 bearing computer-readable instructions capable of redirecting a launch URL to the second display application.
The server 100 may further includes memory 155 bearing computer-readable instructions capable of performing a search or receiving a set of search results. In other words, the server 100 may perform the search itself or a different server may perform the search and deliver the results to the server 100 , in either case for subsequent redelivery to a second display. The server 100 may further include memory 157 bearing computer-readable instructions capable of returning the search results to the second display. Other memories will also be understood, although these are not specifically shown in FIG. 12 .
Systems and methods have been disclosed that allow improvement of the user experience of the IPTV without adding to the hardware costs of the unit. As disclosed above, users may employ the system and method to directly launch a second display application with a requested search term. Using the described systems and methods, the user need not perform an initial step of initializing the second display application and manually entering a search term.
One implementation includes one or more programmable processors and corresponding computing system components to store and execute computer instructions, such as to execute the code that provides the second display or various server functionality, e.g., that of the proxy server 22 , management server 18 , and content server 24 . Referring to FIG. 13 , a representation of an exemplary computing environment 200 for a second display or for any of the servers is illustrated.
The computing environment includes a controller 159 , a memory 174 , storage 172 , a media device 163 , a user interface 164 , an input/output (I/O) interface 166 , and a network interface 168 . The components are interconnected by a common bus 180 . Alternatively, different connection configurations can be used, such as a star pattern with the controller at the center.
The controller 159 includes a programmable processor and controls the operation of the second display and servers and their components. The controller 159 loads instructions from the memory 174 or an embedded controller memory (not shown) and executes these instructions to control the system. In its execution, the controller 159 may provide the second display control of a content playback device system as, in part, a software system. Alternatively, this service can be implemented as separate modular components in the controller 159 or the second display.
Memory 174 , which may include non-transitory computer-readable memory 175 , stores data temporarily for use by the other components of the second display 14 i , and the same may include memories 135 - 143 and 147 - 157 , as discussed above. In one implementation, memory 174 is implemented as RAM. In other implementations, memory 174 also includes long-term or permanent memory, such as flash memory and/or ROM.
Storage 172 , which may include non-transitory computer-readable memory 173 , stores data temporarily or long-term for use by other components of the second display and servers, such as for storing data used by the system. In one implementation, storage 172 is a hard disc drive or a solid state drive.
The media device 163 , which may include non-transitory computer-readable memory 161 , receives removable media and reads and/or writes data to the removable media. In one implementation, the media device 163 is an optical disc drive or disc burner, e.g., a writable Blu-ray® disc drive 162 .
The user interface 164 includes components for accepting user input from the user of the second display, and presenting information to the user. In one implementation, the user interface 164 includes a keyboard, a mouse, audio speakers, and a display. The controller 159 uses input from the user to adjust the operation of the second display 14 i.
The I/O interface 166 includes one or more I/O ports to connect to corresponding I/O devices, such as external storage or supplemental devices, e.g., a printer or a PDA. In one implementation, the ports of the I/O interface 166 include ports such as: USB ports, PCMCIA ports, serial ports, and/or parallel ports. In another implementation, the I/O interface 166 includes a wireless interface for wireless communication with external devices. These I/O interfaces may be employed to connect to one or more content playback devices.
The network interface 168 allows connections with the local network and optionally with content playback device 12 and includes a wired and/or wireless network connection, such as an RJ-45 or Ethernet connection or “WiFi” interface (802.11). Numerous other types of network connections will be understood to be possible, including WiMax, 3G or 4G, 802.15 protocols, 802.16 protocols, satellite, Bluetooth®, infrared, or the like.
The second display and servers may include additional hardware and software typical of such devices, e.g., power and operating systems, though these components are not specifically shown in the figure for simplicity. In other implementations, different configurations of the devices can be used, e.g., different bus or storage configurations or a multi-processor configuration.
Various illustrative implementations of the present invention have been described. However, one of ordinary skill in the art will recognize that additional implementations are also possible and within the scope of the present invention. For example, while media content services have been focused on, the user may also browse services for other types of business or consumer transactions, such as video rentals, home shopping sites, or the like on the second display. Search results may be found that are assets resident within the local network, e.g., content stored on a DVR or Blu-ray® player. In this case, no user account associated with a management server may be necessary. In addition, the second display may also include and manage information about other related devices, such as a media player and a game console.
While the system and method have described implementations in which content playback devices have been selected by a user before browsing, numerous other variations are possible. For example, a cache or cookie or other information may be employed to store information about content playback devices, so that no user choice is necessary. In another variation, a profile system may be employed that communicates content playback device information upon start-up according to a profile; e.g., a given content playback device may always be associated with and may authenticate itself with a given service provider. In this sense, a content playback device is still being chosen, but the choice does not require an affirmative step by the user. Use of any of these alternatives, or others, ensures that the content consumption of each content playback device is tracked. It further allows, as described, the proxy server to filter out content that the content playback device is incapable of playing. It is also noted that certain types of browsing may require no device choice at all, e.g., browsing shopping sites. Even in these implementations, some level of customization may occur, e.g., by consideration of the origination location as detected by the visiting second display's IP address.
In addition, the above description was primarily directed to implementations in which the local IP address of the second display was retrieved and stored on the server. However, other ways of discovering the second display are also possible. For example, device discovery is also possible using a broadcast method within the local network. Compatible devices that recognize the broadcast message will respond with their necessary credentials and information to indicate their compliance with the application for the second display. In many cases, broadcasting methods are primarily directed to native applications, not web applications; however, a broadcasting library may be employed to allow the implementation even within a web application.
While the above description has focused on implementations where a second display is coupled to a content playback device through a local network or over the internet, it will be understood that the same will apply to any method by which the two may communicate, including 3G, 4G, and other such schemes.
Accordingly, the present invention is not limited to only those implementations described above. | Apparatus and methods to implement a technique for using a second display with a network-enabled television. In one implementation, this feature allows the native application on the second display to directly launch the second display application with a requested search term so that the user is immediately brought to a search page with relevant search results. The search term may be derived from the native application which in turn derives from the context of the IP TV. Such a context could be metadata from a currently playing BD from a BD player or TV channel. The second display application may be a web application or a native remote controller application. The second display could be a smart phone that can often be found beside the user, or a laptop or tablet PC, a desktop PC, or the like. | 6 |
FIELD OF INVENTION
[0001] The present invention is directed to novel nucleotide sequences to be used for diagnosis, identification of the strain, typing of the strain and giving orientation to its potential degree of virulence, infectivity and/or latency for all infectious diseases including tuberculosis. The present invention also includes method for the identification and selection of polymorphisms associated with the virulence and/or infectivity in infectious diseases by a comparative genomic analysis of the sequences of different clinical isolates/strains of infectious organisms. The regions of polymorphisms, can also act as potential drug targets and vaccine targets. More particularly, the invention also relates to identifying virulence factors of M. tuberculosis strains and other infectious organisms to be included in a diagnostic DNA chip allowing identification of the strain, typing of the strain and finally giving orientation to its potential degree of virulence.
[0002] Although the present invention has been illustrated with specific reference to the polymorphic region in the Mycobacterium tuberculosis, the said invention is not to be understood and construed as being limited to Tuberculosis but is applicable to all infectious diseases.
BACKGROUND OF THE INVENTION
[0003] Microbial pathogens use a variety of complex strategies to subvert host cellular functions to ensure their multiplication and survival. Some pathogens that have co-evolved or have had a long-standing association with their hosts utilize finely tuned host-specific strategies to establish a pathogenic relationship.
[0004] During infection, pathogens encounter different conditions, and respond by expressing virulence factors that are appropriate for the particular environment, host, or both.
[0005] Although antibiotics have been effective tools in treating infectious disease, the emergence of drug resistant pathogens is becoming problematic in the clinical setting. New antibiotic or antipathogenic molecules are therefore needed to combat such drug resistant pathogens. Accordingly, there is a need in the art for screening methods aimed not only at identifying and characterizing potential antipathogenic agents, but also for identifying and characterizing the virulence factors that enable pathogens to infect and debilitate their hosts.
[0006] The mycobacteria are rod-shaped, acid-fast, aerobic bacilli that do not form spores. Several species of mycobacteria are pathogenic to humans and/or animals, and factors associated with their virulence. Tuberculosis is a worldwide health problem, which causes approximately 3 million deaths each year, yet little is known about the molecular basis of tuberculosis pathogenesis. The disease is caused by infection with Mycobacterium tuberculosis; tubercle bacilli are inhaled and then ingested by alveolar macrophages. As is the case with most pathogens, infection with M. tuberculosis does not always result in disease. The infection is often arrested by developing cell-mediated immunity (CMI) resulting in the formation of microscopic lesions, or tubercles, in the lung. If CMI does not limit the spread of M. tuberculosis, caseous necrosis, bronchial wall erosion, and pulmonary cavitations may occur. The factors that determine whether infection with M. tuberculosis results in disease are not well understood.
[0007] The tuberculosis complex is a group of four mycobacterial species that are so closely related genetically that it has been proposed treat they or combined into a single species. Three important members of the complex are Mycobacterium tuberculosis, the major cause of human tuberculosis; Mycobacterium africanum, a major cause of human tuberculosis in some populations; and Mycobacterium bovis, the cause of bovine tuberculosis. None of these mycobacteria is restricted to being pathogenic for a single host species. For example, M. bovis causes tuberculosis in a wide range of animals including humans in which it causes a disease that is clinically indistinguishable from that caused by M. tuberculosis. Human tuberculosis is a major cause of mortality throughout the world, particularly in less developed countries. It accounts for approximately eight million new cases of clinical disease and three million deaths each year. Bovine tuberculosis, as well as causing a small percentage of these human cases, is a major cause of animal suffering and large economic costs in the animal industries.
[0008] Antibiotic treatment of tuberculosis is very expensive and requires prolonged administration of a combination of several anti-tuberculosis drugs. Treatment with single antibiotics is not advisable as tuberculosis organisms can develop resistance to the therapeutic levels of all antibiotics that are effective against them. Strains of M. tuberculosis that are resistant to one or more anti-tuberculosis drugs are becoming more frequent and treatment of patients infected with such strains is expensive and difficult. In a small but increasing percentage of human tuberculosis cases the tuberculosis organisms have become resistant to the two most useful antibiotics, isoniazid and rifampicin. Treatment of these patients presents extreme difficulty and in practice is often unsuccessful. In the current situation there is clearly an urgent need to develop new methods for detecting virulent strains of mycobacteria and to develop tuberculosis therapies.
[0009] There is a recognized vaccine for tuberculosis, which is an attenuated form of M. bovis known as BCG. This is very widely used but it provides incomplete protection. The development of BCG was completed in 1921 but the reason for its avirulence was and has continued to remain unknown. Methods of attenuating tuberculosis strains to produce a vaccine in a more rational way have been investigated but have not been successful for a variety of reasons. However, in view of the evidence that dead M. bovis BCG was less effective in conferring immunity than live BCG, there exists a need for attenuated strains of mycobacteria that can be used in the preparation of vaccines.
[0010] A variety of compounds have been proposed as virulence factors for tuberculosis but, despite numerous investigations, good evidence to support these proposals is lacking. Nevertheless, the discovery of a virulence factor or factors for tuberculosis is very important and is an active area of current research. Such a discovery would not only enable the possible development of a new generation of tuberculosis vaccines but might also provide a target for the design or discovery of new or improved anti-tuberculosis drugs or therapies.
[0011] Present methods for the identification and characterization of mycobacteria in samples from human and animal diseases are by Zeil-Neilson staining, in-vitro and in vivo culture, biochemical testing and serological typing. These methods are generally slow and do not readily discriminate between closely related mycobacterial strains and species particularly, for example, Mycobacterium paratuberculosis and Mycobacterium avium. Mycobacteria are widespread in the environment, and rapid methods do not exist for the identification of specific pathogenic strains from amongst the many environmental strains, which are generally non-pathogenic. Difficulties with existing methods of mycobacterial identification and characterization have increased relevance for the analysis of microbial isolates from Crohn's disease (Regional Ileitis) in humans and Johne's disease in animals (particularly cattle, sheep and goats) as well as for M. avium strains from AIDS patients with mycobacterial superinfections. Although recognition of the causative agents of human leprosy and tuberculosis are clear, clinico-pathological forms of each disease exist, such as the tuberculoid form of leprosy, in which mycobacterial tissue abundance is low and identification correspondingly difficult. Improvements in the specific recognition and characterization of mycobacteria may also increase in relevance if current evidence linking diseases such as rheumatoid arthritis to mycobacterial antigens is substantiated. Emerging drug resistance to mycobacteria including M. avium isolates from AIDS patients, any Mycobacterium tuberculosis from TB patients is an increasing problem.
[0012] There is no data or technical information in the prior art, which permits to select specifically potential new targets and protective antigens for new drugs and vaccine compositions to treat and prevent infectious diseases, particularly tuberculosis. Furthermore, there is a need for the development of new tools for the selection of genes which encode for essential proteins or regulatory nucleotidic sequences in the survival or infection of mycobacterium species and useful for the design of anti-tuberculosis drugs and vaccines based on the knowledge of comparative mycobacterial genomics.
[0013] A method of using DNA probes for the precise identification of mycobacteria and discrimination between closely related mycobacterial strains and species by genotype characterization is essential. The method of genotypic analysis is further applicable to the rapid identification of phenotypic properties such as drug resistance and pathogenicity.
[0014] The invention aids in fulfilling these needs in the art. The method according to the invention has the advantage to reduce drastically the number of potential new targets and protective antigens by giving for the first time an exhaustive description of conserved SNPs in the tuberculosis. The isolated polynucleotides described in the present invention, which are highly conserved in genomic sequences of both virulent and avirulent, are by this characteristic essential for the survival or the virulence of these mycobacteria in the host. The identification of antigens and potentially therapeutic targets has been made by a method of comparative genomic analysis.
PRIOR ART
[0015] Patent application WO 02074903 describes a method of selection of purified nucleotidic sequences or polynucleotides encoding proteins or part of proteins carrying at least an essential function for the survival or the virulence of mycobacterium species by a comparative genomic analysis of the sequence of the genome of M. tuberculosis aligned on the genome sequence of M. leprae and M. tuberculosis and M. leprae marker polypeptides of nucleotides encoding the polypeptides, and methods for using the nucleotides and the encoded polypeptides are disclosed.
[0016] U.S. Pat. No. 6,228,575 provides oligonucleotide based arrays and methods for speciating and phenotyping organisms, for example, using oligonucleotide sequences based on the Mycobacterium tuberculosis, rpoB gene. The groups or species to which an organism belongs may be determined by comparing hybridization patterns of target nucleic acid from the organism to hybridization patterns in a database.
[0017] Patent application No. WO9954487 and U.S. Pat. No. 6,492,506 describes a method for isolating a polynucleotide of interest that is present or is expressed in a genome of a first mycobacterium strain and that is absent or altered in a genome of a second mycobacterium strain which is different from the first mycobacterium strain using a bacterial artificial chromosome (BAC) vector. This invention further relates to a polynucleotide isolated by this method and recombinant BAC vector used in this methQd. In addition the present invention comprises method and kit for detecting the presence of a mycobacteria in a biological sample.
[0018] U.S. Pat. No. 5,783,386 describes polynucleotides associated with virulence in mycobacteria, and particularly a fragment of DNA isolated from M. bovis that contains a region encoding a putative sigma factor. Also provided are methods for a DNA sequence or sequences associated with virulence determinants in mycobacteria, and particularly in M. tuberculosis and M. bovis. In addition, the invention provides a method for producing strains with altered virulence or other properties, which can themselves be used to identify and manipulate individual genes.
[0019] U.S. Pat. No. 5,955,077 relates to novel antigens from mycobacteria capable of evoking early (within 4 days) immunological responses from T-helper cells in the form of gamma-interferon release in memory immune animals after rechallenge infection with mycobacteria of the tuberculosis complex. The antigens of the invention are believed useful especially in vaccines, but also in diagnostic compositions, especially for diagnosing infection with virulent mycobacteria. Also disclosed are nucleic acid fragments encoding the antigens as well as methods of immunizing animals/humans and methods of diagnosing tuberculosis.
[0020] U.S. Pat. No. 6,596,281 describes two genes for proteins of M. tuberculosis have been sequenced. The DNAs and their encoded polypeptides can be used for immunoassays and vaccines. Cocktails of at least three purified recombinant antigens, and cocktails of at least three DNAs encoding them can be used for improved assays and vaccines for bacterial pathogens and parasites.
[0021] U.S. Pat. No. 5,700,683 provides specific genetic deletions that result in an avirulent phenotype of a mycobacterium. These deletions may be used as phenotypic markers of providing a means for distinguishing between disease-producing and non-disease producing mycobacteria.
[0022] U.S. Pat. No. 5,225,324 relates to a family of DNA insertion sequences (ISMY) of mycobacterial origin and other DNA probes which may be used a probes in assay methods for the identification of mycobacteria and the differentiation between closely related mycobacterial strains and species. The use of ISMY, and of proteins and peptides encoded by ISMY, in vaccines, pharmaceutical preparations and diagnostic test kits is also disclosed.
[0023] WO0066157 patent application provides for polypeptides encoded by open reading frames present in the genome of Mycobacterium tuberculosis but absent from the genome of BCG and diagnostic and prophylactic methodologies using these polypeptides.
[0024] U.S. Pat. No. 6,458,366 discloses compounds and methods for diagnosing tuberculosis. The compounds provided include polypeptides that contain at least one antigenic portion of one or more M. tuberculosis proteins, and DNA sequences encoding such polypeptides. Diagnostic kits containing such polypeptides or DNA sequences and a suitable detection reagent may be used for the detection of M. tuberculosis infection in patients and biological samples. Antibodies directed against such polypeptides are also provided.
[0025] S. T. Cole has sequences the complete genome sequence of the best-characterized strain of Mycobacterium tuberculosis, H37Rv. The sequence has been analyzed in order to improve our understanding of the biology of this slow-growing pathogen and to help the conception of new prophylactic and therapeutic interventions. [ Nature 393, 537-544 (1998)]
[0026] In a multicomponent analysis to determine the association of polymorphism to the degree of virulence and infectivity is in progress. These polymorphisms constitute a set of putative virulence markers that are being validated in 120 clinical isolates of tuberculosis. The study results in a set of virulence markers, which could be used in predicting the degree of virulence and infectivity of Mycobacterium infections.
[0027] There is no data or technical information in the prior art, which permits to select specifically potential new targets and protective antigens for new drugs and vaccine compositions to treat and prevent infectious diseases including mycobacterial diseases, particularly tuberculosis and leprosy.
SUMMARY OF THE INVENTION
[0028] The object of the present invention is to identify genes which encode for essential proteins or regulatory nucleotidic sequences in the survival or infection of mycobacterium species as also all infectious diseases and which could be useful for the design of drugs and vaccines based on the knowledge of comparative genomics.
[0029] Yet another object of the present invention is to provide for the identification of strains including mycobacterium in disease samples, for the specific recognition of pathogenic strains, for precisely distinguishing closely related strains including mycobacterial strains and for defining virulence and resistance patterns.
[0030] The method according to the invention has the advantage to reduce drastically the number of potential new targets and protective antigens by giving for the first time an exhaustive description of conserved SNPs in different M. tuberculosis strains, which cause tuberculsosis. The isolated polynucleotides described in the present invention, which are highly conserved in genomic sequences of virulent strains are essential for the survival or the virulence of these strains, in particular mycobacteria, in the host. The identification of antigens and potentially therapeutic targets has been made by a method of comparative genomic analysis.
[0031] The invention is directed to identifying virulence factors in M. tuberculosis & other infectious diseases, using both strands of DNA, RNA and/or proteins associated with the virulence factors, allowing identification of the strain, typing of the strain and finally giving orientation to its potential degree of virulence, infectivity and/or latency.
[0032] Accordingly this invention provides a nucleotide sequences for diagnosis, identification of the strain, typing of the strain and giving orientation to its potential degree of virulence, infectivity and/or latency of all infectious diseases having a SEQ ID nos 1 to 2531.
[0033] The invention is further directed to a method comprising of aligning the genomic sequences of different mycobacteria species to
[0034] a. Select a polynucleotide sequence highly conserved amongst the virulent strains and corresponds to an essential gene for the survival or the virulence of mycobacterium species
[0035] b. Select polymorphisms between virulent and avirulent strains to identify genes and regions conferring virulence to the former strains
[0036] c. And optionally, testing the polynucleotide selected for its capacity of virulence or involved in the survival of a mycobacterium species said testing being based on the activation or inactivation of said polynucleotide in a bacterial host or said testing being based on the activity of the product of expression of said polynucleotide in vivo or in vitro.
[0037] The invention further comprises of identification of following polymorphisms, having potential to be used as reagents and in diagnostics, drug and vaccine development for infectious diseases:
[0038] i. Identical nucleotide in. virulent strains/species, but a different nucleotide in avirulent strains/species at the same position
[0039] ii. Some of the virulent strains differ in the nucleotide sequence at specific positions and share the nucleotide sequence with that of avirulent strains.
[0040] Yet another object of the present invention is to provide for the identification of strains including mycobacterium in disease samples, for the specific recognition of pathogenic strains, for precisely distinguishing closely related strains including mycobacterial strains and for defining virulence and resistance patterns.
[0041] The method according to the invention has the advantage to reduce drastically the number of potential new targets and protective antigens by giving for the first time an exhaustive description of conserved SNPs in different M. tuberculosis strains, which cause tuberculsosis. The isolated polynucleotides described in the present invention, which are highly conserved in genomic sequences of virulent strains are essential for the survival or the virulence of these strains, in particular mycobacteria, in the host. The identification of antigens and potentially therapeutic targets has been made by a method of comparative genomic analysis.
[0042] The invention is directed to identifying virulence factors in M. tuberculosis & other infectious diseases, using both strands of DNA, RNA and/or proteins associated with the virulence factors, allowing identification of the strain, typing of the strain and finally giving orientation to its potential degree of virulence, infectivity and/or latency.
[0043] Accordingly this invention provides a nucleotide sequences for diagnosis, identification of the strain, typing of the strain and giving orientation to its potential degree of virulence, infectivity and/or latency of all infectious diseases having a SEQ ID nos 1 to 2531.
[0044] The invention is further directed to a method comprising of aligning the genomic sequences of different mycobacteria species to
[0045] a. Select a polynucleotide sequence highly conserved amongst the virulent strains and corresponds to an essential gene for the survival or the virulence of mycobacterium species
[0046] b. Select polymorphisms between virulent and avirulent strains to identify genes and regions conferring virulence to the former strains
[0047] c. And optionally, testing the polynucleotide selected for its capacity of virulence or involved in the survival of a mycobacterium species said testing being based on the activation or inactivation of said polynucleotide in a bacterial host or said testing being based on the activity of the product of expression of said polynucleotide in vivo or in vitro.
[0048] The invention further comprises of identification of following polymorphisms, having potential to be used as reagents and in diagnostics, drug and vaccine development for infectious diseases:
[0049] i. Identical nucleotide in virulent strains/species, but a different nucleotide in avirulent strains/species at the same position
[0050] ii. Some of the virulent strains differ in the nucleotide sequence at specific positions and share the nucleotide sequence with that of avirulent strains.
[0051] The invention relates to the identification and analysis of Non-synonymous SNPs to predict conservative and non-conservative amino acid substitutions. The effect of the substitution on the function of the proteins encoded provided a powerful insight in predicting SNPs correlating with virulence and infectivity in infectious diseases for example M. tuberculosis.
[0052] The invention further relates to proteins, RNA, DNA and metabolites encoded by the region carrying the polymorphisms in tuberculosis and other infectious disease causing organisms; which can be utilized for developing drugs and vaccines effective against tuberculosis and other infectious diseases, plays a important role in gene therapy, RNAi technology and imaging.
[0053] The invention is also directed to a process for the production of recombinant polypeptides and chimeric polypeptides comprising them, antibodies generated against these polypeptides, immunogenic or vaccine compositions comprising at least one polypeptide useful as protective antigens or capable to induce a protective response in vivo or in vitro against mycobacterium infections, immunotherapeutic compositions comprising at least such a polypeptide according to the invention, and the use of such nucleic acids and polypeptides in diagnostic methods, vaccines, kits, or antimicrobial therapy.
[0054] SEQ ID Nos. 1 to 1829 are single nucleotide polymorphisms.
[0055] SEQ ID Nos. 1830 to 2286 is an insertion/deletion (indel)
[0056] SEQ ID No 2287 to 2531 are regions of long polymorphism.
[0057] The present invention also includes primer sequences for amplifying the region around the polymorphism SEQ ID nos 1 to 2531
[0058] The nucleotide sequences flanking the polymorphisms of SEQ ID Nos. 1 to 2531 to a length of 35 nucleotides on either side are used in reagents and in diagnostics, drug development, RNAi, gene therapy and other such technologies.
[0059] SEQ ID Nos 1 to 2531 are used as targets for drug design using bioinformatics and other tools, drug development, for gene therapy and vaccine development. This invention also includes the use of proteins, RNA, DNA and metabolites encoded by the region carrying the polymorphisms having a SEQ ID Nos. 1 to 2531 for RNAi technology and antisense technologies.
[0060] This invention also includes a database for identification and selection of the polymorphisms having SEQ ID nos. 1 to 2531.
BRIEF DESCRIPTION OF THE FIGURES AND TABLES
[0061] FIG. 1 describes Entity Relationship Model.
[0062] FIG. 2 illustrates the identification of SNPs in M. tuberculosis strains H37Rv, CDC1551 and M. bovis BCG. A total of 1829 SNP's have been identified in the three genomes. Of these 1825 SNPs are identical in H37Rv and CDC1551, with a different nucleotide in BCG. 1579 of these are in ORFs while the rest (246) are in non-coding regions. The SNPs in the ORF are categorized into synonymous, non-synonymous SNPs. The latter are further categorized on the basis of the change in primary structure of the protein that results - conservative for no-change and non-servative for changed primary structure of protein encoded.
[0063] FIG. 3 illustrates the identification of indels in M. tuberculosis strains H37Rv, CDC1551 and M. bovis BCG. A total of 794 indels have been identified in the three genomes. Of these, 237 are present in both H37Rv and CDC1551 with respect to BCG, 178 in ORF and 59 are outside the ORF.
[0064] FIG. 4 illustrates Identification of long plymorphisms in M. tuberculosis strains H37Rv, CDC1551 and M. bovis BCG. 136 polymorphisms are present in the three genomes, 30 of them being identical to CDC1551 and H37Rv. 22 of these polymorphisms are present in the ORFs while 8 are outside the ORF.
[0065] FIG. 5 display shows a region of 10 kb of the BCG genome with three types of annotations: BCG ORF's, SNP's in H37Rv, and SNP's in CDC1551.
[0066] FIG. 6 shows the comparative genomics browser displaying BCG in the upper panel and H37Rv in the bottom panel. The segments labeled MUM-* are the perfect matches generated by the MUMmer tool, and the vertical lines show the alignment of the MUM segments in both genomes. The color coding of the ORF's is used to indicate the length of the ORF. This is very helpful to researchers because if an ORF in H37 aligns with an ORF in BCG but they have different colors, then there is a mutation that makes them have different lengths (see for example the genes in the MUTM-1280 region).
[0067] FIG. 7.1-7.25 are the primers used for the amplification to encompass the regions of polymorphisms.
[0068] Table 1 gives the list of Single Nucleotide Polymorphisms in Mycobacterium tuberculosis/M. bovis BCG.
[0069] Table 2 gives the list of Insertions/deletions (Indels) in Mycobacterium tuberculosis/M. bovis BCG.
[0070] Table 3 gives the list of long polymorphisms in Mycobacterium tuberculosis/M. bovis BCG.
[0071] Table 4 lists Polymorphisms in genes involved in cell wall synthesis.
[0072] Table 5 lists Polymorphisms in transcription factors.
[0073] Table 6 lists Polymorphisms in genes involved in lipid metabolism
[0074] Table 7 lists Polymorphisms in genes encoding membrane transport proteins
[0075] Table 8 lists Polymorphisms in genes implicated in virulence
DETAILED DESCRIPTION OF THE INVENTION
[0076] The Mycobacterium tuberculosis complex consists of six species— M. tuberculosis, M. bovis, M. caitotti, M. microtii and M. africanum. Of these, the genomes of two different strains of M. tuberculosis, which are virulent and infective to humans, have been completely sequenced, while the complete genome of M. bovis BCG, which is non-virulent and non-infective has also been sequenced. Only partial sequences are available for the other species. All Mycobacterium sequences available in the NCBI, EMBL, GENBANK, Sanger and TIGR databases were retrieved and compiled.
[0077] The total numbers of sequences retrieved are as follows:
Species name No of sequences retrieved Mycobacterium africanum 16 Mycobacterium canetti 03 Mycobacterium microtii 24 Mycobacterium tuberculosis 1274 Mycobacterium bovis 183
[0078] The complete genomes of Mycobacterium tuberculosis strains H37Rv (referred to as H37Rv) and CDC1551 (referred to as CDC1551) - both of which are virulent and infective to humans) and Mycobacterium bovis BCG (referred to as BCG)—non-virulent and non-infective in humans - were aligned and a database constructed. The structure of the database is given in FIG. 1 .
[0079] Sequences were aligned using the pairwise alignment tool “MUMmer-3.08” (www.tigr.org).
[0080] The use of MUMmer required three distinct steps:
[0081] 1. running MUMmer for each of the target genomes (CDC1551 and H37Rv) against the reference genome (BCG)
[0082] 2. parsing the MUMmer output using to produce a list of polymorphisms, and loading these data into a polymorphism database.
[0083] 3. generating feature files for visualization, and loading these features into a feature database.
[0084] BCG was chosen as the reference genome and compare the two tuberculosis strains, CDC1551 and H37Rv, against the reference. MUMmer uses fasta files as input and was run using the following command line:
run-mummer1 bovis.fasta cdc1551.fasta BCG-CDC which takes the format, program <reference> <query> <output>
[0085] The BCG-CDC parameter provides the file name prefix for the output files, the bovis.fasta parameter is the reference fasta file, and the CDC1551.fasta parameter is the name of the query fasta sequence file.
[0086] The database is generated using the scripts:
[0087] Parsing MUMmer .align file to extract polymorphism data
[0088] The file is parsed to extract useful information and stored it in a much simpler tab-delimited text file format. A custom perl script named mum-parse.pl which uses the Perl module Parse::RecDescent to create a recursive descent parser based on the grammar contained in the custom file Muinmer. pm. is used to run the following command line:
$ perl./mum-parse.pl—mummer1—outfile=../mummer/BCG-CDC./mummer/BCG-CDC.align
[0089] This creates three output files:
[0090] 1. BCG-CDC.gaps—this is the initial output file that simply lists the location of all exact matches in the two sequences.
[0091] 2. BCG-CDC.errorgaps—this is a processed version of the gaps file.
[0092] 3. BCG-CDC.align—this is the fully annotated file that is used to locate all polymorphisms.
[0093] Pairwise alignments of BCG-H37Rv and BCG-CDC1551 was done using the BCG genomic sequence as reference. Results of the alignment identified three types of polymorphisms:
[0094] 1. SNPs—single nucleotide polymorphisms in one or more of the sequences aligned.
[0095] 2. indels—insertion or deletion of one or more bases in the sequences aligned.
[0096] 3. Long polymorphic regions—regions with numerous changes in the sequences aligned.
[0000] Inserting the Annotation of the Complete Genomes into the Database
[0097] The gene annotation downloaded from either genbank or EMBL is included into the database by running the following script
$/work/mtb/scripts annot.pl—seq=[filename]—dbname=[NAME]—user=[NAME]—password=[PASS]
filename indicates either genbank or the EMBL genes annotation file.
Inserting the Data into the DB
[0098] To insert the CDC1551 SNP's into the DB the following command is run:
$ perl/work/mtb/scripts/snp-insert.pl—snp=../mummer/BCG-CDC.snp—user=[NAME]—password=[PASS]—query_acc=NC — 002755
[0099] To insert the H37Rv SNP's into the DB run the following command is run:
$ perl/work/mtb/scripts/snp-insert.pl—snp=../mummer/BCG-H37.snp—user=[NAME]—password=[PASS]—query_acc=NC — 000962
[0100] To determine whether SNP's are synonymous or non-synonymous, whether they are within or outside an open reading frame is first determined. All SNP's that lie within an ORF are taken and the amino acid for that codon containing the SNP is determined.
[0101] To determine if the BCG locations lie within ORF's run the following command is run:
$ perl/work/mtb/scripts/snp-orf-ref.pl—ref_seq=../seqs/bovis.fasta—user=[NAME]—password=[PASS]
[0102] All BCG locations within ORF's must have their amino acids determined. To do so, the following command is run:
$ perl/work/mtb/scripts/ref-aa.pl—ref_seq=../seqs/bovis.fasta—user=[NAME]—password=[PASS]
[0103] Next, the H37Rv and CDC1551 locations are mapped. To assign the CDC1551 ORF's the following command is run:
$ perl/work/mtb/scripts/snp-orf2.pl—query_seq=../seqs/CDC1551.fasta—user=[NAME]—password=[PASS]
[0104] To assign the H37Rv ORF's the following command is run:
$ perl scripts/snp-orf2.pl—query_seq=../seqs/H37Rv.fasta—user=[NAME]—password=[PASS]
[0105] To determine whether the CDC1551 SNP's are synonymous or non-synonymous the following command is run:
$ cd/work/mtb/scripts
$ perl s/work/mtb/scripts/synomous.pl—bcg_file=../seqs/bovis.fasta—query_seq=../seqs/CDC1551.fasta—user=[NAME]—password=[PASS]
[0106] To determine whether the H37Rv SNP's are synonymous or non-synonymous the following command is run:
$ cd /work/mtb/scripts
$ perl/work/mtb/scripts/synomous.pl—bcg_file=../seqs/bovis.fasta—bcg_file=../seqs/H37Rv.fasta—user=[NAME]—password=[PASS]
[0107] A set of summary columns are used to coallesce all the SNP data in one place. To do this, the following command is run:
$ perl/work/mtb/scripts/compare-snps.pl—user=[NAME]—password=[PASS]
[0108] To insert data into the SNP analysis table the SNP data from the SNP, SEQ_SNP and gene ontology tables is fetched and entered into the SNP_analysis table. This step also identifies the conservative and non-conservative amino acids.
[0109] To do this, the following program is run:
$ run.sh/work/mtb/scripts/
[0110] The SNP data in the database is thus complete.
[0000] Analysis of SNPs
[0111] The SNPs identified were of two kinds:
[0112] i. Identical nucleotide in CDC1551 and H37Rv, but a different nucleotide in BCG at the same position.
[0113] ii. One of the three sequences is polymorphic; the nucleotide sequence of CDC1551 and H37Rv are different from each other and one of them is identical to the BCG sequence at identical positions.
[0114] The SNPs thus identified were categorized according to their location in Open Reading Frames. SNPs falling within the ORF of both BCG and H37Rv were identified. The results were validated by determining if the SNPs were present in the ORFs of BCG and CDC1551.
[0115] The SNPs falling in ORFs were further categorized into synonymous and non-synonymous SNPs. A SNP was said to cause a non-synonymous change if:
[0116] 1) It occurs in an ORF
[0117] 2) It occurs in the *same* ORF in the genome it is being compared to.
[0118] In some cases a SNP can be in one ORF in the reference sequence but in another ORF in the comparison sequence, e.g. due to a frame-shift mutation earlier in the sequence.
[0119] So before we assign SNP's to ‘Non Synonymous’ or ‘synonymous’ groupings all SNP's which either did not fall in an ORF, or fell into different ORF's on the reference and comparison sequences were eliminated. The BCG and H37 genomes have been annotated with respect to one another. However CDC1551 has not been so thoroughly annotated, so it was not possible to immediately assess if an ORF in BCG was the corresponding ORF in CDC. Therefore, a metric was devised to eliminate spurious comparisons.
[0120] The non-synonymous SNPs thus identified was analysed to predict conservative and non-conservative amino acid substitutions. The effect of the substitution on the function of the proteins encoded was predicted. This provides a powerful insight in predicting SNPs correlating with virulence and infectivity in M.tuberculosis.
[0121] Below is an example of the output obtained from the database.
[0122] The above figure describes the SNP details, which is as follows:
[0123] Bovis_pos—Bovis position having a SNP.
[0124] Bovis_ORF—Y es indicates that the SNP in bovis is in bovis ORF. No indicates not in ORF.
[0125] Bovis_base—Indicates the SNP detailSNP pos ition in bovis
[0126] Bovis_AA—Displays the bovis amino acid after the codon translation.
[0127] Qry_name—Displays the name of a strain, example H37Rv or microtii
[0128] Qry_pos—Displays the position of a SNP in either CDC1551 or H37Rv with respect to bovis SNP position.
[0129] Qry_ORF—Displays Yes if the SNP falls in the ORF of the query (H37Rv or CDC1551)
[0130] Qry_base—Displays the query SNP.
[0131] Qry_AA—Displays the amino acid of the query (H37Rv or CDC1551).
[0132] Is_nsSNP—Displays SNPs synonymous (S), non-synonymous (NS) and SNPs in non-coding region (NC).
[0133] Conservative_subst—Displays homologous substitution in H37rv and CDC1551.
[0134] Fun_annotation—Will display the functional annotation of the query.
[0135] A list of Single nucleotide polymorphisms identified in the manner described above is given in Table 1.
[0136] A total of 1829 have been identified in the three genomes. Of these 1825 SNPs consist of having the same nucleotide in H37Rv and CDC1551, with a different nucleotide in BCG. Of thel829 SNPs, 1579 are in ORFs while the rest (246) are in non-coding regions. 811 H37Rv SNPs and 810 CDC1551 SNPs are synonymous while 1282 H37Rv and 1219 CDC1551 SNPs are non-synonymous. Out of 1219 CDC1551 nsSNPs, 312 SNPs have conservative amino acid substitution, 888 have non-conservative substitution and 19 results in truncated proteins. Out of 1282 H37Rv non-synomous SNPs, 304 have conservative amino acid substitution, 954 have non-conservative substitution and 24 results in truncated proteins. ( FIG. 2 )
[0000] Analysis of Indels (Insertions and Deletions):
[0137] Indels are insertions and deletions in the sequence with respect to BCG sequence. These indels could be of one or more nucleotides. Considering BCG as reference sequence, the indels in the both the strains of M.tuberculosis, H37rv and CDC1551 were identified.
[0138] To insert the indels from the align file of the mummer output into the database, the following java program is run:
$ java/work/mtb/scripts/indel
[0139] To enter functional annotation from the gene ontology database into the indels table, the following program is run:
$ java/work/mtb/scripts/indfunction
[0140] The list of indels identified is given in Table 2.
[0141] A total of 794 indels have been identified in the three genomes. Of these, 237 (H37Rv) and 237 (CDC1551) indels are present in both H37Rv and CDC1551 with respect to BCG. Of these, 178 are in ORF and 59 are outside the ORF. ( FIG. 2 )
[0000] Analysis of Long polymorphs:
[0142] Long polymorphs are insertions or deletions of long stretches of nucleotides with respect to BCG sequence.
[0143] To insert the long polymorphs from the align file of the mummer output into the database, following java program is run:
$ java/work/mtb/scripts/indel
[0144] To enter the functional annotation from the gene ontology database into the long polymorph table, following java program is run:
$ java/work/mtb/scripts/indfunction
[0145] A table listing the long polymorphisms is given in Table 3.
[0146] A total of 136 long polymorphisms have been identified in the three genomes. Of these, 30 (H37Rv) and 30 (CDC1551) indels are present in both H37Rv and CDC1551 with respect to BCG. Of these, 22 are in ORF and 8 are outside the ORF. ( FIG. 3 )
[0000] Functional Annotation of the Polymorphisms Identified
[0147] In order to identify polymorphisms with a putative functional association, a tool was built using the Gene Ontology DB (GO). The EMBL sequence DB has made putative GO assignments to most of the ORF's in the three TB genomes, so a local installation of GO was used together with the EMBL cross reference tables to identify TB polymorphisms based on their putative functional classification.
[0148] The annotation table consisting of the genbank features of the genes such as coding region, database reference and product information to name a few was constructed.
[0149] To inserts the gene ontology features such as term definition and name from the gene ontology database into the indels and long polymorph table, following program is run:
$ java/work/mtb/scripts/indfunctionl
[0150] The following are the list of attributes in the annotation table.
[0151] Accession no—This indicates the accession number of the sequences
[0152] Gene_start—This indicates the start of the coding region
[0153] Gene_end—This indicates the end of the coding region
[0154] Locus_tag—
[0155] db_xref—This indicates the gene indices representation of the gene
[0156] db_xref_GOA—This indicates the gene ontology identity of the gene product
[0157] id—This indicates the gene annotation
[0158] type—
[0159] strand—This indicates the forward or reverse strand of the sequence that is stored in the genbank
[0160] gene_name—This indicates the gene name
[0161] gene_link—This provides a hyperlink to the gene features form the genbank
[0162] note—This provides the general information and the protein information of the gene.
[0163] A front-end was constructed as an essential part of the database:
[0000] Front End of the Database:
[0164] The front-end displaying the results of alignment as follows:
[0165] The annotation table consists of genbank annotation about the genes in bovis, H37Rv and CDC1551. It specifies details including the coding region of a gene and its database reference.
[0166] The annotation id for the SNPs, indels and long polymorphs has been hyperlinked to obtain all the records pertaining to a particular gene.
[0167] The data pertaining to indels and long polymorphs have also been added to the front-end.
[0000] Description of the Queries:
[0168] The database is made queryable to retrieve the required features of SNPs, indels and long polymorphs respectively.
[0169] The main options to query the SNP information are:
[0000] Select SNPs
[0170] ALL—This displays all the records which satisfies the below features.
[0171] Identical in both queries—This query indicates that SNPs are present in BCG with respect to H37Rv and CDC1551.
[0172] Different bases in both queries—This query indicates different nucleotides in H37Rv and CDC1551.
[0173] Having SNPs in BCG-H37 only—This query specifies SNPs in BCG and H37Rv only and not in CDC1551.
[0174] Having SNPs in BCG-CDC only—This query specifies SNPS in BCG and CDC1551 only and not in H37Rv.
[0175] BCG-H37 SNPs—This query indicates, that SNPs are present in H37Rv with respect to BCG-position and may or may not be present in CDC1551 at that particular position.
[0176] BCG-CDC SNPs—This query indicates, that SNPs are present in CDC1551 with respect to BCG position and may or may not be present in H37Rv at that particular position.
[0177] The other options considered are:
[0178] Select BCG ORF—This provides an option to select the presence of BCG SNPs in BCG ORF or outside the BCG ORF.
[0179] Select query ORF—This provides an option to select the presence of query SNPs in query ORF or outside the query ORF.
[0180] Select synonymous—This provides an option to select if the SNP is synonymous or non-synonymous.
[0181] Select Conservative—This provides an option to select if the non-synonymous SNP results in conservative, non-conservative substitution or truncated protein.
[0182] Select function—This provides an option to select a required function, which includes cell wall synthesis, Transcription factor, Lipid metabolism, Membrane transport and Surface proteins.
[0183] An example of a query to extract SNP information from the database is shown below.
[0184] The result obtained from the above query is shown below:
[0185] The query has been designed in the similar way for both indels and long polymorphs.
[0186] The SNP analysis includes functional annotation id, which is hyperlinked to the functional annotation of the gene carrying the polymorphism. The functional annotation id consists of either one of the Swiss Prot, SPTREMBL or gene ontology id's. Similarly the indels and long polymorphs are also functionally annotated.
[0187] Genes with known involvement in virulence of Mycobacterium tuberculosis can also be accessed from the SNP database query or from the Long polymorphs database query respectively.
[0188] Polymorphisms involved in the following functions have been identified:
[0189] 1. Cell wall synthesis
[0190] 2. Transcription factor
[0191] 3. Lipid metabolism
[0192] 4. Membrane transport
[0193] 5. Surface proteins.
[0194] 6. Virulence genes
[0195] One such query for cell wall synthesis function is shown below
[0196] The output of the above query is shown below
[0197] The polymorphisms detected in genes involved in cell wall synthesis are listed in Table 4.
[0000] Visualization Tools
[0198] To increase the utility of the SNP data, two tools to visualize the Tuberculosis SNP data have been created: the first tool was based on the Generic Genome Browser developed at Cold Spring Harbor Lab (CSHL). This visualization tool could show a single TB genome along with any annotations, e.g. SNP locations for all other genomes.
[0199] The details of the browser is as follows:
[0200] The output displays the polymorphs in the region of interest.
[0201] Alternatively the output can be obtained by specifying the region of interest in the text box labeled as “landmark or region”. In case of SNP, the gene start and the gene end has to be specified and in case of indels or long polymorphs, the BCG start and BCG end must be specified.
[0202] By clicking the ruler at the region of interest across the genome, the view can be re-centered.
[0203] The display can also be zoomed in or out by selecting the required number of base pairs in the scroll down menu.
[0204] The required features can be displayed by selecting the options in the tracks checkbox as shown in FIG. 4
[0205] FIG. 4 display shows a region of 10 kb of the BCG genome with three types of annotations: BCG ORF's, SNP's in H37Rv, and SNP's in CDC1551.
[0206] To compare multiple genomes, a second tool based on the WormBase synteny browser was built. This tool can visualize two TB genomes at one time and was very useful in validating the polymorphisms the CDC1551 genome as shown in FIG. 5 .
[0207] FIG. 5 shows the comparative genomics browser displaying BCG in the upper panel and H37Rv in the bottom panel. The segments labeled MUM-* are the perfect matches generated by the MUMmer tool, and the vertical lines show the alignment of the MUM segments in both genomes. The color coding of the ORF's is used to indicate the length of the ORF. This is very helpful to researchers because if an ORF in H37 aligns with an ORF in BCG but they have different colors, then there is a mutation that makes them have different lengths (see for example the genes in the MUM-1280 region).
[0208] A methodical screening of all the regions of polymorphism identified above in clinical isolates with known disease profiles to further home-in on the polymorphisms associated with virulence and/or infectivity in M.tuberculosis is in progress.
[0000] 2. Screening of Regions of Polymorphisms
[0209] A set of five Mycobacterium tuberculosis strains with known virulence is being screened for the polymorphisms identified above.
[0210] Strains chosen: The following strains have been chosen for the study:
[0211] a. H37Rv—a reference laboratory strain known to be infective to mice, but is only mildly infective in humans. It has undergone a number of passages in the lab since its isolation. It is the standard used in studies on tuberculosis in different laboratories across the world.
[0212] b. Beijing strain—a clinical isolate with known virulence and infectivity in humans. 70% of the patients with tuberculosis in certain areas of India and China are infected with this strain. The strain was isolated from a patient in the Western Indian state of Mumbai.
[0213] c. S.I—a mild South Indian strain with only mild virulence and infectivity in humans isolated from a patient residing in the South Indian state of Hyderabad.
[0214] d. N.I.F—Fatal North Indian strain isolated from Safderjung hospital, Delhi where the patient developed pulmonary tuberculosis died.
[0215] e. N.I.NF—a non-fatal North Indian strain isolated from Safderjung hospital, Delhi. Known clinical progression of disease in the patient.
[0216] Primers have been designed to encompass the regions of polymorphisms. The list of the primers used for the amplification is given in the FIG. 6 . 1 - 6 . 25
[0217] Amplification and sequencing of regions around the polymorphisms: DNA from the five strains has been amplified under optimal conditions determined for each primer pair. The amplified fragments have been sequenced and the sequences obtained from different strains compared.
[0218] A few examples are given below:
60 70 80 90 100 110 +---------+---------+---------+---------+---------+----- BCG ACCGATCTCGCCGCGCAGACAATGGCTGGCTCAGCGGCGATGCTGCTGGAGCGGAT H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CD1551 ++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 120 130 140 150 160 170 ----+---------+---------+---------+---------+---------+ BCG GGACCAAGACCAGGGTGGCGCCAATGGCGAGCTGATGGGGCTGCGCGTGGACCTT H37Rv +++G+++++++++++++++++++++++++++++++++++++++++++++++++++ CD1551 +++G+++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++G+++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++G+++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++G+++++++++++++++++++++++++++++++++++++++++++++++++++ NIF +++G+++++++++++++++++++++++++++++++++++++++++++++++++++
[0219] Sequencing of the region from 1H-590622 to H-591026. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M. tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; NINF: non-lethal North Indian strain; BS: Beijing strain; NIF: Lethal North Indian strain. The gene coding for oxidoreductase activity is a virulence gene which does not show any differences between the M.tuberculosis strains, but has a conservative polymorphism with M.bovis BCG.
130 140 150 160 170 180 190 200 210 +--------+---------+---------+---------+---------+---------+---------+---------+ BCG CCAGGCCTCGATCGACGATCTGGCGTCTCTCGAAGAAGACTTTACCGTTGCACGTCGCCGTCTACCGGCGGGTGATTGCGG H37Rv +++++++++++++++++++++++++++++++++++++++++++-+++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++-+++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++-+++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++-+++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++-+++++++++++++++++++++++++++++++++++++ NIF +++++++++++++++++++++++++++++++++++++++++++-+++++++++++++++++++++++++++++++++++++
[0220] Sequencing of the region from 11-138548 to 11-139067. Sequences are amplified from different strains. BCG: M.bovis BCG; H 37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF: Lethal North Indian strain The insertion in BCG leads to a shorter protein with a different carboxyl terminal compared to the transcription factor encoded by the tuberculosis strains.
10 20 30 40 50 60 70 +---------+---------+---------+---------+---------+-----+--- BCG GTGGCGAGCCGGCAAACCCCTGCTGAGCTGGCCAGATGCGACTTGGCTAAGACCGCGGAGCGCG CDC1551 +++++++++++++++A++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++++++++A++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++-++++++++++++++++++++++++++++++++++++++++++++++++ NTNF +++++++++++++++-++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++-++++++++++++++++++++++++++++++++++++++++++++++++ 80 90 100 110 120 130 ------+---------+---------+---------+---------+---------| BCG AGCACACCCCGACGGCGACTGCGACAACTCCAAGCGTGGCCGGTAACGTGATGCCCA H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NTNF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 131 140 150 160 170 180 190 |--------+---------+---------+---------+---------+---------+--- BCG TGATTGTGCGTTCCCTTCCCGCTGCGTTGCGCGCGTGTGCGCGTCTGCAACCCCATGACCCGG CDC1551 +++G+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++G+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++G+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NTNF +++G+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++G+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 200 210 220 230 240 250 ------+---------+---------+---------+---------+---------+ BCG CCTTCACGTTTATGGATTACGAACAGGACTGGGACGGCGTTGCGATAACCCTGACGT CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NTNF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 251 260 270 280 290 300 310 |---------|---------+--------- +---------+---------+---------+-- BCG GGTCGCAGCTGTATCGGCGAACGCTGAATGTGGCACGGGAGCTGAGCCGTTGTGGTTCCAGGT CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++C+G H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++C+G BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++C+G NTNF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++C+G SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++C+G 320 330 340 350 360 370 -------+---------+---------+---------+---------+---------+ BCG CGCAGCTGTATCGGCGAACGCTGAATG--TGGCACGGGAGCTGAGCCGTTGTGGTTC CDC1551 -+TGA+C+CG+-++T++T+T+++CTCCGCA++G++TC+++-+AC+T+++C+CCT+++ H37Rv -+TGA+C+CG+-++T++T+T+++CTCCGCA++G++TC+++-+AC+T+++C+CCT+++ BS -+TGA+C+CG+-++T++T+T+++CTCCGCA++G++TC+++-+AC+T+++C+CCT+++ NTNF -+TGA+C+CG+-++T++T+T+++CTCCGCA++G++TC+++-+AC+T+++C+CCT+++ SI -+TGA+C+CG+-++T++T+T+++CTCCGCA++G++TC+++-+AC+T+++C+CCT+++
[0221] Sequencing of the region from H-3283171 to H-3283585. Two SNPs, one indel and a long polymorphism characterize this region. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I South Indian strain A2313; BS: Beijing strain; NIF: non-lethal North Indian strain. All the polymorphisms occur in the fadD28, a virulence gene involved in fatty acid synthesis. They result in a non-conservative substitution and probably have an important role in the degree of virulence imparted to the strain.
130 140 150 160 170 180 190 200 210 +---------+---------+---------+---------+---------+---------+---------+---------+ BCG TTGGCCCACGTGCTGAACTTGGTGACGTTGGCTGCGGTGACAAACAAGTTCTGATAGGTCGTTGCGCCCGTCGGCCCGAAG H37Rv +++++++++++++++++++++++++++++++++++++++++++++++C+++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++C+++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++A+++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++A+++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++A+++++++++++++++++++++++++++++++++ 211 230 240 250 260 270 280 290 ---------+---------+---------+---------+---------+---------+---------+--------- BCG ATGAGTTGGCCCATGAGTTGGGTGTATTGGGTGCTGAGTGTGGCCAGGCCCTGCAGCAGGGTCGGGATGATGTCGAACG H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 300 310 320 330 340 350 360 370 380 +---------+---------+---------+---------+---------+---------+---------+---------+ BCG GAAACTGCGCCGCTGCACTCGAAAGCGCGGTTGTCACCGCATTGGTGCCGCTCGCTAGGGCGGTCGCTTSCCCCGTTGCGG H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++++++++
[0222] Sequencing of the region from H-2051784 to H-2052209. This region is characterized by a SNP between M.bovis BCG and the tuberculosis strains and a second SNP common to the Asian strains and to BCG, but different from H37Rv and CDC1551. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. The SNP common to all the tuberculosis strains results in a conservative substitution in the PPE33b gene and does not affect the function of this gene. However the A to G substitution results in the truncation of the protein encoded by BCG.
150 160 170 180 190 200 210 220 230 240 +---------+---------+---------+---------+---------+---------+---------+---------+---------+ BCG CATCGTCGCCGGCGCGGGTCACTGGCGCCGCTCCTCCCCATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCACTGGCGCCGCTCCTCCC H37Rv +++++++++++++++++++++---------------------------------------------------------------------- CDC1551 +++++++++++++++++++++---------------------------------------------------------------------- SI +++++++++++++++++++++CTGGCGCCGCTCCTCCCCATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCACTGGCGCCGCTCCTCCC BS +++++++++++++++++++++CTGGCGCCGCTCCTCCCCATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCACTGGCGCCGCTCCTCCC NINF +++++++++++++++++++++CTGGCGCCGCTCCTCCCCATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCACTGGCGCCGCTCCTCCC 241 250 260 270 280 290 300 +---------+---------+---------+---------+---------+---------+ BCG CATCGCTTTGCTCTCTGCATCGTCGCCGGCGCGGGTCAATCGAAGATGCCCCGTCGCGTGTC H37Rv ------------------------------------++++++++++++++++++A+++++ CDC1551 ------------------------------------++++++++++++++++++H+++++ SI CATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCA++++++++++++++++++A+++++ BS CATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCA++++++++++++++++++A+++++ NINF CATCGCTTTGCTCTGCATCGTCGCCGGCGCGGGTCA++++++++++++++++++A+++++
[0223] Sequencing of the region from H-3006917 to H-3007246. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; M18: non-lethal North Indian strain. This region encloses a long polymorphism of 106bp inserted into a gene encoding an integral membrane protein in BCG and the Asian strains. This results in a longer integral membrane product in these strains as compared to H37Rv and CDC1551. The SNP also results in the introduction of a stop codon in H37Rv and CDC1551 further reducing the length of the membrane protein encoded by the latter.
40 50 60 70 80 90 100 110 120 +---------+---------+---------+---------+---------+---------+---------+---------+ BCG CTGGGTCAGCAGCGGGTGTGCGCTGATTTCGATGAAGGTGTGGTAGGCGCCGTCGGCGCCGCTACCGGCGGAAGCGATGGC BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++C+++++++++++++++++++++++++++++++++++++++++++++++++++++ 121 130 140 150 160 170 180 190 200 ---------+---------+---------+---------+---------+---------+---------+---------+ BCG CTGGCTGGAAATGCACGGGGTTGCGCATGTTGGTGGCCCAGTGTTCGGCGTCGAAGACCGGTTGGGTGTGCAAGTCTGCGT BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++GC++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 201 210 220 230 240 250 260 270 280 ---------+---------+---------+---------+---------+---------+---------+---------+ BCG AGGTGGTGGAGATGATTCCGATGGTGGGGGTCCGTGGGGTCAGATCGGCCAGCTCCGAACGCATCGCCGGCTGCAAAGCA BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 281 281 300 310 320 330 340 350 360 ---------+---------+---------+---------+---------+---------+---------+---------+ BCG TCCATGGCCGGATTGTGCGGGGCCACTTCGATATTGACCCGGCTGGCGAATCGGTCCCTAGCGCGCACGCGAGTGATCAA BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++A+++++A++C+++TTTGC++++++++C++G+C++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++A+++++A++C+++TTTGC++++++++C++G+C++++++
[0224] Sequencing of the region from H-3247737 to H-3248224 Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. All the polymorphisms observed occur in ppsA—the polyketide synthase gene and are synonymous substitutions. All the three Asian strains show identity to BCG in this region.
100 110 120 130 140 150 160 +---------+---------+---------+---------+---------+---------+----- BCG CGCGGTACACGTGTCGAACGGCGACAAACCCAAGGTTGCCTTGCCCGATACTCAGTTGGGTTCACA H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 170 180 190 200 210 220 230 ----+---------+---------+---------+---------+---------+---------+ BCG CTCAACGTGATTCGAAATCCACACTGATACTGGAGGTGATTACCGGCTGAAGCAAAGCGCATTGG H37Rv ++G++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++G++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++G++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF ++G++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 ++G++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF ++G++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[0225] Sequencing of the region from H-2052524 to H-2052863. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; N1NF: non-lethal North Indian strain; NIF: Lethal North Indian strain .A single nucleotide polymorphism occurring in the proton transport gene PPF,33b results in the introduction of a stop codon and hence truncation of the protein in BCG.
190 200 210 220 230 240 +---------+---------+---------+---------+---------+--------- BCG CATCGGCCGAAACGTGAGTAATCTGGGCGGCC---------------------------- CDC1551 ++++++++++++++++++++++++++++++++CGCTCAGCGCCCAGGGCATCGAAGAACA H37Rv ++++++++++++++++++++++++++++++++CGCTCAGCGCCCAGGGCATCGAAGAACA BS ++++++++++++++++++++++++++++++++CGCTCAGCGCCCAGGGCATCGAAGAACA NINF ++++++++++++++++++++++++++++++++CGCTCAGCGCCCAGGGCATCGAAGAACA SI ++++++++++++++++++++++++++++++++CGCTCAGCGCCCAGGGCATCGAAGAACA 250 260 270 280 290 +---------+---------+---------+---------+ BCG -------------------GTGGCTCGGGGCGGCCCACACC CDC1551 AGCCCAGGGTGGCCTTGTC+++++C++++++++++++++++ H37Rv AGCCCAGGGTGGCCTTGTC+++++C++++++++++++++++ BS AGCCCAGGGTGGCCTTGTC+++++C++++++++++++++++ NINF AGCCCAGGGTGGCCTTGTC+++++C++++++++++++++++ SI AGCCCAGGGTGGCCTTGTC+++++C++++++++++++++++
[0226] Sequencing of the region from H-1468644 to H-1469150. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551;S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. An insertion of 47bp is seen in all the tuberculosis strains in Mbl346c, a gene with DNA binding activity. A second polymorphism (SNP) is also seen immediately adjacent to the insertion in the same gene. The SNP results in splitting the gene into two genes while there is a single long gene in the M.tuberculosis strains.
190 200 210 220 230 240 +---------+---------+---------+---------+---------+---- BCG TGTTGGCTTCATCAGCACCCCGAGGTGTGTATTCAGGCGATCCGGGGCAGCG CDC1551 ++++++++++++++++++++++++++++--++++++++++++++++C+++T++++ H37Rv ++++++++++++++++++++++++++++--++++++++++++++++C+++T++++ NINF ++++++++++++++++++++++++++++--++++++++++++++++C+++T++++ SI ++++++++++++++++++++++++++++--++++++++++++++++C+++T++++ BS ++++++++++++++++++++++++++++--++++++++++++++++C+++T++++ 250 260 270 280 290 -----+---------+---------+---------+---------+ BCG GGGTCGGGGTGACGCGGTTCCGCCCAAAGGTCC--GTCACCCTGTG CDC1551 +++++++++++++++++++++++++++++++++AC+++++++++++ H37Rv +++++++++++++++++++++++++++++++++AC+++++++++++ NINF +++++++++++++++++++++++++++++++++AC+++++++++++ SI +++++++++++++++++++++++++++++++++AC+++++++++++ BS +++++++++++++++++++++++++++++++++AC+++++++++++
[0227] Sequencing of the region from H-455094 to H-455468. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. The region is characterized by the occurrence of two indels and two SNPs in a transcription regulator. All the tuberculosis strains appear to be identical in this region while BCG, has a different amino-acid sequence in the region.
60 70 80 90 100 110 120 +---------+---------+---------+---------+---------+---------+ BCG CAGATCGGCTCGGTCCGCTTCGCGATTTACCGCTCGGACTATGTGCAGTCGGTGACGGCTC CDC1551 ++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++ H37Rv ++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++ NTNF ++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++ 130 140 150 160 ---------+---------+---------+---------| BCG ++++++++++++++++++++++++++++++A+++++++++ CDC1551 ++++++++++++++++++++++++++++++A+++++++++ H37Rv ++++++++++++++++++++++++++++++A+++++++++ BS ++++++++++++++++++++++++++++++A+++++++++ NTNF ++++++++++++++++++++++++++++++A+++++++++ SI ++++++++++++++++++++++++++++++A+++++++++ NIF ++++++++++++++++++++++++++++++A+++++++++
[0228] Sequencing of the region from H-466229 to H-466536. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M. tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF: Lethal North Indian strain .The C to T transition occurs in a gene of unknown function and results in a synonymous substitution. However, the C to A change occurs in a transcription factor (Mb0393) and is a non-conservative substitution resulting in a slightly different protein in BCG.
130 140 150 160 170 180 190 200 +---------+---------+---------+---------+---------+---------+---------+ BCG CCGCCAGGGTTACACCGACGTCGACCAGTTCACACTCGAAAAGTAACCGGACAAAGCGCGCTGGCTACCCA CDC1551 ++++++++++++++++++++++++++++++++++++G++++++++++++++++++++++++++++++++++ H37Rv ++++++++++++++++++++++++++++++++++++G++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++++++G++++++++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++++++++++++++G++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++G++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++G++++++++++++++++++++++++++++++++++
[0229] Sequencing of the region from H-560625 to H-561248. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF: Lethal North Indian strain. A synonymous SNP occurs in a virulence gene and is identical in all the tuberculosis strains.
150 160 170 180 190 200 --+---------+---------+---------+---------+---------+ BCG GGCCCACGATTTGCAATGGTGACGAGTTGGCTGCCTCGGCGCTGGCGTACTAG H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++G+ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++G+ BS +++++++++++++++++++++++++++++++++++++++++++++++++++G+ SI +++++++++++++++++++++++++++++++++++++++++++++++++++G+ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++G+ NIF +++++++++++++++++++++++++++++++++++++++++++++++++++G+ 210 220 230 240 250 ---------+---------+---------+---------+---------+ BCG GCCGCCCCCGCGCTCATGAGCTGGACGAACTGCTCATGGAATGCGACCGC H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++ NIF +++++++++++++++++++++++++++++++++++++++++++++++++
[0230] Sequencing of the region from H-2046394 to H-2046928. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF: Lethal North Indian strain. The SNP in BCG results in splitting the gene PE-PGRS32 into two parts with the latter being truncated.
40 50 60 70 80 90 +---------+---------+---------+---------+---------+----- BCG ACGATCATCGGTGGTGGTGGAGCCGGTATGGTAGCTACCGCCACGCGGAAGCTGGT CDC1551 ++++++++++++++++++++++++A+++++++++++++++++++++++++++++ H37Rv ++++++++++++++++++++++++A+++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++A+++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++A+++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++A+++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++A+++++++++++++++++++++++++++++ 100 110 120 130 140 150 ----+---------+---------+---------+---------+---------+ BCG CGGCGGGCGCTTCATGGCGATGACGACCGGACCGGACAGGTCTATGCCGGACGCG CDC1551 ++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++++++++++++++++++++++++ 151 160 170 180 190 200 +--------+--------+---------+---------+---------+------ BCG GCGACCGCGGCCACCGGGGTGATAACGGCGTGCACCGGCGCGGTTCTCCCGGGGAA CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++ H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF +++++++++++++++++++++++++++++++++++++++++++++++++++++++ 210 220 230 240 250 260 ---+---------+---------+---------+---------+---------+ BCG TACCGGAGCCGCGCCGCCGACCGCACTGGCGAATACCAACGGGGCAATCGCTGC CDC1551 ++++++++++++++C++++++++++++++++++++++++++++++++++++++ H37Rv ++++++++++++++T++++++++++++++++++++++++++++++++++++++ NINF ++++++++++++++C++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++C++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++C++++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++C++++++++++++++++++++++++++++++++++++++
[0231] Sequencing of the region from 11-1373629 to 11-1374101. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M. tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF: Lethal North Indian strain. The two polymorphisms observed occur in a transcription factor and result in non-conservative substitutions.
220 230 240 250 260 270 280 +---------+---------+---------+---------+---------+---------+ BCG TCTCTCGGTCATTCGTGGTCGCAGGCGCCGCACTCGGTGTCTTCGGGGGGGGGGGGGGGGG H37Rv ++++++++++++++++++++++++++++++++++++++++++++++T++++--------- CDC1551 ++++++++++++++++++++++++++++++++++++++++++++++T++++--------- SI ++++++++++++++++++++++++++++++++++++++++++++++T++++--------- BS ++++++++++++++++++++++++++++++++++++++++++++++T++++--------- NINF ++++++++++++++++++++++++++++++++++++++++++++++T++++--------- NIF ++++++++++++++++++++++++++++++++++++++++++++++T++++--------- 290 300 310 320 330 340 ---------+---------+---------+---------+---------+---------+ BCG GGGGGGGGGGGAAGCGCGACCTCGAAGGCCACTGAAACGCCTTACGGAGACGCGACGAAC H37Rv -----------++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 -----------++++++++++++++++++++++++++++++++++++++++++++++++ SI -----------++++++++++++++++++++++++++++++++++++++++++++++++ BS -----------++++++++++++++++++++++++++++++++++++++++++++++++ NINF -----------++++++++++++++++++++++++++++++++++++++++++++++++ NIF -----------++++++++++++++++++++++++++++++++++++++++++++++++
[0232] Sequencing of the region from H-1622821 to H-1623282. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF:North Indian Fatal. The polymorphisms observed occur in a non-coding region outside the ORF.
150 160 170 180 190 200 210 220 230 +---------+---------+---------+---------+---------+---------+---------+---------+ BCG TGTGGCGCGCCTGGCTCAGATAACGCAACGCCGCAGGCGCGCGCCGCACGTCAAAAGTGGTGACCGGCAACGGCCGCAGCA CDC1551 ++++++++++++++++++++++++++++++++++++++++++A++++++++++++++++++++++++++++++++++++++ H37Rv ++++++++++++++++++++++++++++++++++++++++++A++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++A++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++A++++++++++++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++++++++++++++++++++A++++++++++++++++++++++++++++++++++++++
[0233] Sequencing of the region from 11)2295752 to H-2296046. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. The polymorphism observed occurs in the pks12 gene and results in a non-conservative substitution.
30 40 50 60 70 80 90 +---------+---------+---------+---------+---------+---------+ BCG TGGGCCGCTCTAGATGGGCGCCGCCCCGCGCAGATGCTCGAAGATCAGGGACGTCTGGGTA H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 ++T+++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 100 110 120 130 140 150 ---------+---------+---------+---------+---------+---------+ BCG CCTGCGACGTCGGCGTCGGCATTGAGGTTTTCGACCACGAACGAACGCAGGTCCTCGGTG H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 151 160 170 180 190 200 +--------+---------+---------+---------+---------+- BCG TCGCGAGCGGCGACGTGCAAGATGAAATCGTCGGCGCC------------ H37Rv ++++++++++++++++++++++++++++++++++++++GGCCAGAAAGTAG CDC1551 ++++++++++++++++++++++++++++++++++++++GGCCAGAAAGTAG BS ++++++++++++++++++++++++++++++++++++++GGCCAGAAAGTAG SI ++++++++++++++++++++++++++++++++++++++GGCCAGAAAGTAG NINF ++++++++++++++++++++++++++++++++++++++GGCCAGAAAGTAG 210 220 230 240 250 --------+---------+---------+---------+---------+ BCG ----------CTGCCGTTTGCGGCGGATCTGCTGGATGAAGCTGCGGA H37Rv ACATCCATCAC+++++++++++++++++++++++++++++++++++++ CDC1551 ACATCCATCAC+++++++++++++++++++++++++++++++++++++ BS ACATCCATCAC+++++++++++++++++++++++++++++++++++++ SI ACATCCATCAC+++++++++++++++++++++++++++++++++++++ NINF ACATCCATCAC+++++++++++++++++++++++++++++++++++++
[0234] Sequencing of the region from H-3086111 to H-3086539. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. The SNP seen in H37Rv occurs in a non-coding region while the deletion in BCG leads to truncation of the transcription regulator.
180 190 200 210 220 230 240 250 260 270 +---------+---------+---------+---------+---------+---------+---------+---------+---------+ BCG CGGTCGCGGGCGAAGCGTTTGAAGTCCACCGTCGCCAGGCCGCTGGTCATGGCGCTGGCCTGATCCCACAGACCCCAGCCCAGGGAGATGG H37Rv +++++++++++++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++ NIF +++++++++++++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++
[0235] Sequencing of the region from H-2295062 to H-2295633. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; A2313: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF:North Indian Fatal. The SNP observed occurs in the pks12 gene and results in a non-conservative substitution.
80 90 100 110 120 130 140 -+---------+---------+---------+---------+---------+---------+ BCG CGGCGAGTACAACGACGCTCGGGTCGATGTCCCGGTCCGATGGCTGCACGGCACCG-AGATC H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++ CDC1551 ++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++ NINF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++G+++++ 150 160 170 180 190 200 ---------+---------+---------+---------+---------+---------+ BCG CGGTGATCACGCCCGACCTGCTGGACGGCTATGCCGAGCGGGCCAGCGATTTCGAGGTGG H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NINF +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
[0236] Sequencing of the region from H-162341 to H-162761. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain. The deletion in BCG occurs in the region corresponding to a gene with putative enzyme activity and results in a loss of function in BCG.
120 130 140 150 160 170 180 190 200 210 +---------+---------+---------+---------+---------+---------+---------+---------+---------+ BCG CGCCCGCGCCACGACGTCACTACGCACATTCTATTCCGGAGACCCAGGCGAGGCGTCGGGGCGGCACCGTTTGCAGGCCCGGAATCCCTCC H37Rv ++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 ++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NTNF ++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++C++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 211 220 230 240 250 260 270 280 290 300 +---------+---------+---------+---------+---------+---------+---------+---------+---------+ BCG CCCTGAGCGGCCGCCGCAGTCGGCAGGAACCGGACATTGCGCGCGAACGGTGGCCGGACGGGGCAACTCGGCCGGCAGTAGACACCGGTG H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CDC1551 ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NTNF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 301 310 320 330 340 350 360 370 380 390 +---------+---------+---------+---------+---------+---------+---------+---------+---------+ BCG GTCAAAACCGCGACGACGAACCAGCCGTCGAACCGGGCGTCTTTGGACTGGACCGCCCGGTAGCAGCGTTCGAAGTCGTCGTGCACCCTT H37Rv ++++++++++++++++++++++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++++++++++ CDC1551 ++++++++++++++++++++++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++++++++++ BS ++++++++++++++++++++++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++++++++++ NTNF ++++++++++++++++++++++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++++++++++ SI ++++++++++++++++++++++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++++++++++ NIF ++++++++++++++++++++++++++++++++++++++++++++++++++++T++++++++++++++++++++++++++++++++++++
[0237] Sequencing of -the region from H-1478664 to H-1479140. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NIN: non-lethal North Indian strain; NIF:North Indian Fatal. The first T to C transition results in the truncation of the bacterial regulatory protein in BCG.
170 180 190 200 210 220 +---------+---------+---------+---------+---------+----- BCG CCACCTCGGTGGTGTTCGCCACCGCCCACTACGCGCTGGTGGATTTGGCCGACGTA H37Rv +++++++++++++++++++++++++++++++++++++++++++++++++++CT+CT CDC1551 +++++++++++++++++++++++++++++++++++++++++++++++++++CT+CT NINF +++++++++++++++++++++++++++++++++++++++++++++++++++CT+CT BS +++++++++++++++++++++++++++++++++++++++++++++++++++CT+CT SI +++++++++++++++++++++++++++++++++++++++++++++++++++CT+CT NIF +++++++++++++++++++++++++++++++++++++++++++++++++++CT+CT 230 240 250 260 270 280 ----+---------+---------+---------+---------+---------+ BCG CAACCGGGCCAGCGCGTGTTGATCCATGCCGGCACCGGCGGGGTGGGCATGGCGG CDC1551 AGGT++++++++++++++++++++++++++++++++++++++++++++++++++ NINF AGGT++++++++++++++++++++++++++++++++++++++++++++++++++ BS AGGT++++++++++++++++++++++++++++++++++++++++++++++++++ SI AGGT++++++++++++++++++++++++++++++++++++++++++++++++++ NIF AGGT++++++++++++++++++++++++++++++++++++++++++++++++++
[0238] Sequencing of the region from H-2296260 to H-2296692. Sequences are amplified from different strains. BCG: M.bovis BCG; H37Rv: M.tuberculosis strain H37Rv sequence from NCBI database; CDC: CDC1551; S.I: South Indian strain A2313; BS: Beijing strain; NINF: non-lethal North Indian strain; NIF:North Indian Fatal strain. The long polymorphism observed in the pks12 gene but does not alter the activity of the polyketide synthase enzyme. A total of 2755 polymorphisms including 1779 in ORFs and 313 in regions outside the ORF are being screened for association to virulence and/or infectivity in tuberculosis. A multicomponent analysis to determine the association of polymorphism to the degree. of virulence and infectivity is in progress. The polymorphisms which constitute a set of virulence markers are further being validated in 120 clinical isolates of tuberculosis.
[0239] The virulence factors thus identified could be used as:
[0240] i. Diagnostic markers in prediction of disease and its progress in the patient.
[0241] ii. Drug targets for development of new and effective treatments for TB.
[0242] iii. Candidate genes/sequences in DNA vaccine.
[0243] iv. In development of SiRNA technology for combating tuberculosis.
TABLE 1 List of SNP's in Mycobacterium tuberculosis / M. bovis BCG. De- scrip- Poly- tion mor- BCG H37Rv CDC of phism SNP SNP SNP SNP SNP ID Position Base AA Position Base AA Position Base AA ORF type GO ID Putative Function 1 467 G R 467 A H 467 A H Yes NS, NC P49993 nucleotide binding activity 2 1057 A I 1057 G V 1057 G V Yes NS, C P49993 nucleotide binding activity 3 2347 G G 2347 A D 2347 A D Yes NS, NC Q50790 DNA binding activity 4 2532 C L 2532 T L 2532 T L Yes S, NULL Null — 5 3751 G V 3751 T L 3751 T L Yes NS, C Q59586 DNA binding activity 6 4480 T L 4480 C S 4480 C S Yes NS, NC P71573 — 7 5752 A V 5752 G V 5752 G V Yes S, NULL Null — 8 6406 T N 6406 C N 6406 C N Yes S, NULL Null — 9 6446 T S 6446 G A 6446 G A Yes NS, NC P41514 nucleic acid binding activity 10 8285 T I 8285 C I 8285 C I Yes S, NULL Null — 11 8741 T R 8741 C R 8741 C R Yes S, NULL Null — 12 9143 C I 9143 T I 9143 T I Yes S, NULL Null — 13 9217 C A 9217 A D 9217 A D Yes NS, NC Q07702 DNA binding activity 14 10727 G V 10727 A I 10727 A I Yes NS, C P71575 integral to membrane 15 13197 C Null 13197 G Null 13197 G null Yes S, NULL Null — 16 13459 G D 13460 A D 13460 A D Yes S, NULL Null — 17 14400 G E 14401 A K 14401 A K Yes NS, NC P71582 integral to membrane 18 15116 G M 15117 C I 15117 C I Yes NS, NC P71583 enzyme activity 19 17856 C T 17857 T T 17857 T T Yes S, NULL Null — 20 21818 C A 21819 A S 21819 A S Yes NS, NC P71588 enzyme activity 21 22263 G A 22264 T A 22264 T A Yes S, NULL Null — 22 23173 A L 23174 C R 23174 C null Yes NS, NC P71588 enzyme activity 23 23713 T L 23714 C L 23714 C L Yes S, NULL Null — 24 24293 T Q 24294 C R 24294 C R Yes NS, NC P71590 — 25 24533 C C 24534 T Y 24534 T Y Yes NS, NC P71590 — 26 24678 G H 24679 A Y 24679 A Y Yes NS, C P71590 — 27 24761 C G 24780 T D 24762 T D Yes NS, NC P71590 — 28 25287 G R 25306 C G 25288 C G Yes NS, NC P71590 — 29 26034 G P 26053 C A 26035 C A Yes NS, NC P71591 electron transport 30 27450 G Null 27469 A Null 27451 A null No nc, NULL Null — 31 29442 T L 29462 C P 29444 C P Yes NS, NC P71595 — 32 29979 C P 29999 A Q 29980 A Q Yes NS, NC P71596 — 33 30736 A K 30756 G K 30737 G K Yes S, NULL Null — 34 31041 G R 31057 C R 31038 C R Yes S, NULL Null — 35 32608 A N 32624 C H 32568 C N Yes NS, NC P71599 — 36 33788 A Null 33804 G Null 33748 G null No nc, NULL Null — 37 36288 G A 36304 T A 36248 T A Yes S, NULL Null — 38 36522 C S 36538 T S 36482 T S Yes S, NULL Null — 39 36596 G K 36612 A K 36556 A K Yes S, NULL Null — 40 39742 G H 39758 A H 39702 A H Yes S, NULL Null — 41 41228 A Null 41244 C Null 41188 C null No nc, NULL Null — 42 41437 T G 41453 C G 41397 C G Yes S, NULL Null — 43 42265 A F 42281 C C 42225 C C Yes NS, NC P71696 integral to membrane 44 43929 G V 43943 A V 43889 A V Yes S, NULL Null — 45 45177 A A 45191 G A 45137 G A Yes S, NULL Null — 46 49989 A Null 50003 G Null 49949 G null No nc, NULL Null — 47 52012 T S 52026 C G 51972 C G Yes NS, NC P71705 integral to membrane 48 53663 T L 53677 C P 53623 C P Yes NS, NC P71707 enzyme activity 49 59861 A Null 59869 G Null 59815 G null No nc, NULL Null — 50 62758 G G 62766 A G 62712 A G Yes S, NULL Null — 51 63029 T Null 63037 C Null 62983 C null No nc, NULL Null — 52 63049 G Null 63057 C Null 63003 C null No nc, NULL Null — 53 65857 A I 65865 G V 65811 G V Yes NS, C O53607 hydrolase activity 54 69913 T I 69921 C T 69867 C T Yes NS, NC O53609 molecular_function unknown 55 70082 G P 70090 A P 70036 A P Yes S, NULL Null — 56 70257 T F 70265 G V 70211 G V Yes NS, NC O53609 molecular_function unknown 57 71758 T Null 71729 C Null 71712 C null No nc, NULL Null — 58 74119 T L 74090 C L 74073 C L Yes S, NULL Null — 59 74188 G N 74159 C K 74142 C K Yes NS, NC O53611 isocitrate dehydrogenase (NADP+) activity 60 78130 C G 78101 T E 78084 T E Yes NS, NC O53615 glycine hydroxymethyltransferase activity 61 79388 C Null 79359 G Null 79342 G null No nc, NULL Null — 62 80169 T P 80131 C P 80123 C P Yes S, NULL Null — 63 86899 G V 86862 A I 86854 A I Yes NS, C O53623 DNA binding activity 64 89235 T V 89198 G G 89190 G G Yes NS, C O53625 — 65 89570 T Null 89533 C Null 89525 C null No nc, NULL Null — 66 90964 T V 90927 C A 90919 C A Yes NS, C Q10880 oxidative phosphorylation 67 92357 T C 92320 A Null 92312 A null Yes nc, NULL Null — 68 94338 C T 94301 T M 94293 T M Yes NS, NC Q10883 oxidative phosphorylation 69 96136 A I 96099 G V 96091 G null Yes NS, C Q10884 electron transport 70 97731 C Null 97694 T Null 97686 T null No nc, NULL Null — 71 99336 T Null 99299 C Null 99291 C null Yes nc, NULL Null — 72 100624 G A 100587 A T 100579 A T Yes NS, NC Q10876 magnesium ion binding activity 73 103635 G R 103598 A C 103590 A C Yes NS, NC Q10890 integral to membrane 74 105903 T W 105865 C R 105857 C R Yes NS, NC Q10892 integral to membrane 75 106370 A P 106332 C P 106324 C P Yes S, NULL Null — 76 122650 T W 122612 C R 122604 C R Yes NS, NC Q10898 cAMP-dependent protein kinase complex 77 123556 C H 123518 T Y 123510 T Y Yes NS, C Q10898 cAMP-dependent protein kinase complex 78 123878 T Null 123840 C Null 123832 C null No nc, NULL Null — 79 126600 A S 126561 C A 126554 C A Yes NS, NC Q10900 magnesium ion binding activity 80 126840 G P 126801 A S 126794 A S Yes NS, NC Q10900 magnesium ion binding activity 81 127447 G L 127408 C L 127401 C L Yes S, NULL Null — 82 130172 A V 130133 G A 130126 G A Yes NS, C Q10900 magnesium ion binding activity 83 130237 T P 130198 C P 130191 C P Yes S, NULL Null — 84 137223 A Q 137183 G Q 137177 G Q Yes S, NULL Null — 85 138339 A R 138299 G G 138292 G G Yes NS, NC O53636 — 86 139796 C Null 139754 T Null 139747 T null No nc, NULL Null — 87 143247 C G 143205 T S 143198 T S Yes NS, NC O53639 DNA binding activity 88 146006 A A 145964 G A 145957 G A Yes S, NULL Null — 89 147495 A W 147453 C W 147446 C W Yes S, NULL Null — 90 147911 C Null 147871 A Null 147864 A null No nc, NULL Null — 91 149987 G G 149947 C G 149940 C G Yes S, NULL Null — 92 159370 A F 159177 G F 159350 G F Yes S, NULL Null — 93 160535 T K 160342 C E 160515 C E Yes NS, NC P96809 — 94 161144 T F 160951 G V 161124 G V Yes NS, NC P96810 N-acetyltransferase activity 95 162499 A R 162306 G G 162479 G G Yes NS, NC P96811 enzyme activity 96 162530 G G 162337 A D 162510 A D Yes NS, NC P96811 enzyme activity 97 165799 G G 165607 A D 165780 A D Yes NS, NC P96815 — 98 166696 A H 166504 G R 166677 G R Yes NS, NC P96816 — 99 170273 G L 170081 A F 170254 A F Yes NS, NC P96820 voltage-gated chloride channel activity 100 171097 C R 170905 A R 171078 A R Yes S, NULL Null — 101 173091 A R 172899 C R 173072 C R Yes S, NULL Null — 102 179424 T R 179232 C G 179405 C G Yes NS, NC P96828 — 103 181862 C G 181670 T D 181843 T D Yes NS, NC P96830 protein phosphatase activity 104 184917 G C 184725 A Y 184895 A null Yes NS, NC P96833 — 105 188267 T T 188075 G P 188245 G P Yes NS, NC O53642 — 106 189999 T T 189807 C A 189977 C A Yes NS, NC O86360 — 107 190284 T T 190092 C A 190262 C A Yes NS, NC O86360 — 108 192177 A L 191985 G L 192156 G L Yes S, NULL Null — 109 195552 C A 195358 T V 195529 T V Yes NS, C O07411 enzyme activity 110 195758 G A 195564 T S 195735 T S Yes NS, NC O07411 enzyme activity 111 198328 A I 198134 C I 198305 C I Yes S, NULL Null — 112 199662 G A 199468 T S 199639 T S Yes NS, NC P72013 pathogenesis 113 199800 T S 199606 C P 199777 C P Yes NS, NC P72013 pathogenesis 114 200622 C T 200428 T I 200599 T I Yes NS, NC O07414 pathogenesis 115 201759 C D 201565 G E 201736 G E Yes NS, C O07415 pathogenesis 116 206673 G P 206479 C P 206650 C P Yes S, NULL Null — 117 206676 T G 206482 G G 206653 G G Yes S, NULL Null — 118 210634 T H 210440 C R 210554 C R Yes NS, NC O07423 — 119 212446 A Null 212252 G Null 212366 G null No nc, NULL Null — 120 217393 C N 217199 T N 217313 T N Yes S, NULL Null — 121 218055 G R 217861 C P 217975 C P Yes NS, NC O07430 hydrolase activity 122 225861 T S 225666 C G 225780 C G Yes NS, NC O07437 — 123 227215 G V 227020 A I 227134 A I Yes NS, C O53645 nucleotide binding activity 124 227738 T M 227543 C T 227657 C T Yes NS, NC O53645 nucleotide binding activity 125 228053 T L 227858 C P 227972 C P Yes NS, NC O53645 nucleotide binding activity 126 228924 T R 228729 C R 228843 C R Yes S, NULL Null — 127 231783 C Null 231587 T Null 231701 T null No nc, NULL Null — 128 232188 G A 231992 C A 232106 C A Yes S, NULL Null — 129 233552 C V 233356 A V 233470 A V Yes S, NULL Null — 130 233558 C S 233362 G R 233476 G R Yes NS, NC O53648 — 131 243794 G R 243596 A H 243712 A H Yes NS, NC O53656 integral to membrane 132 244589 C A 244391 T V 244507 T V Yes NS, C O53656 integral to membrane 133 246117 C E 245919 G D 246035 G D Yes NS, C O53657 membrane 134 246365 T I 246167 A F 246283 A F Yes NS, NC O53657 membrane 135 249718 C A 249520 T V 249636 T V Yes NS, C P96391 — 136 251771 A T 251573 G A 251689 G A Yes NS, NC P96392 — 137 251865 C Null 251667 T Null 251783 T null No nc, NULL Null — 138 256378 C A 256180 G G 256296 G G Yes NS, C P96396 enzyme activity 139 259127 A Null 258900 C Null 259016 C null Yes nc, NULL Null — 140 260507 T T 260280 G P 260396 G P Yes NS, NC P96399 enzyme activity 141 262385 A N 262158 G D 262274 G D Yes NS, NC P96400 electron transport 142 265183 A D 266857 G D 266973 G D Yes S, NULL Null — 143 265653 A S 267327 G P 267443 G P Yes NS, NC P96405 metabolism 144 266601 C L 268275 G F 268391 G F Yes NS, NC P96406 S-adenosylmethionine- dependent methyltransferase activity 145 269989 T N 271663 C S 271779 C S Yes NS, C P96409 — 146 271077 C R 272751 G S 272867 G S Yes NS, NC P96409 — 147 271882 G S 273556 C S 273672 C S Yes S, NULL Null — 148 273691 T E 275365 G D 275481 G D Yes NS, C P96413 zinc ion binding activity 149 276186 T Null 277860 G Null 277976 G null No nc, NULL Null — 150 282208 C A 283882 T T 283998 T T Yes NS, NC P96419 cell adhesion 151 283942 C V 285616 T M 285732 T M Yes NS, NC P96419 cell adhesion 152 285894 T L 287568 G V 287684 G V Yes NS, C O53660 hydrolase activity 153 287276 T T 288950 C T 289066 C T Yes S, NULL Null — 154 287759 T S 289433 G A 289549 G A Yes NS, NC O53663 — 155 288778 T L 290452 C L 290568 C L Yes S, NULL Null — 156 292523 G A 294196 T E 294313 T E Yes NS, NC O53666 acyl-CoA dehydrogenase activity 157 292778 C R 294451 T K 294568 T K Yes NS, C O53666 acyl-CoA dehydrogenase activity 158 294180 C Null 295853 A Null 295970 A null No nc, NULL Null — 159 295519 T V 297192 C A 297309 C A Yes NS, C O53668 — 160 300012 T Null 301685 C Null 301802 C null No nc, NULL Null — 161 301364 T G 303037 C G 303154 C G Yes S, NULL Null — 162 305428 T G 307101 C G 307218 C G Yes S, NULL Null — 163 308090 T Null 309763 C Null 309880 C null Yes nc, NULL Null — 164 311176 A L 312849 G L 312966 G L Yes S, NULL Null — 165 312194 A S 313867 G S 313984 G S Yes S, NULL Null — 166 318505 G I 320178 A I 320294 A null Yes S, NULL Null — 167 321009 T L 322682 C L 322798 C L Yes S, NULL Null — 168 321631 G Null 323304 A Null 323420 A null No nc, NULL Null — 169 323830 C V 325503 T V 325619 T V Yes S, NULL Null — 170 327543 A L 329216 G P 329332 G P Yes NS, NC P95229 — 171 329913 A L 331586 G S 331702 G S Yes NS, NC O53681 — 172 331537 C Null 333210 G Null 333326 G null Yes nc, NULL Null — 173 331617 G Null 333290 A Null 333406 A null Yes nc, NULL Null — 174 331719 G Null 333392 C Null 333508 C null No nc, NULL Null — 175 340088 G Null 339084 A Null 339148 A null No nc, NULL Null — 176 340090 C Null 339086 T Null 339150 T null No nc, NULL Null — 177 340091 G Null 339087 A Null 339151 A null No nc, NULL Null — 178 340092 G Null 339088 C Null 339152 C null No nc, NULL Null — 179 340097 C Null 339093 G Null 339157 G null No nc, NULL Null — 180 343148 C A 342144 A E 342208 A null Yes NS, NC O53687 nuoleotide binding activity 181 344283 C A 343279 G A 343343 G A Yes S, NULL Null — 182 351491 C A 350487 G A 350551 G A Yes S, NULL Null — 183 355282 A T 354278 G A 354342 G A Yes NS, NC O86362 — 184 362163 C Null 361159 T Null 361223 T null No nc, NULL Null — 185 362818 T F 361814 C F 361878 C F Yes S, NULL Null — 186 364560 A N 363511 G S 363575 G null Yes NS, C O07226 — 187 364804 T V 363755 C V 363819 C V Yes S, NULL Null — 188 366022 T V 364973 C A 365037 C A Yes NS, C O07229 DNA binding activity 189 367778 C A 366729 T T 366793 T T Yes NS, NC O07231 tRNA ligase activity 190 368518 A F 367469 G S 367533 G S Yes NS, NC O07231 tRNA ligase activity 191 369200 T S 368166 C G 368230 C G Yes NS, NC O07231 tRNA ligase activity 192 373180 A L 372147 G L 372211 G L Yes S, NULL Null — 193 382060 G G 381028 A S 381091 A S Yes NS, NC O07239 — 194 383273 T L 382241 C P 382304 C P Yes NS, NC O07239 — 195 383519 T Null 382487 C Null 382550 C null No nc, NULL Null — 196 384021 G A 382989 A V 383052 A V Yes NS, C O07241 — 197 387090 C Null 386058 T Null 386120 T null No nc, NULL Null — 198 390159 G C 389127 A Y 389189 A Y Yes NS, NC O07247 dCTP deaminase activity 199 393291 C Q 392259 T * 392321 T * Yes NS, TP O07250 — 200 393536 G G 392504 A G 392566 A G Yes S, NULL Null — 201 394778 A Y 393746 G H 393808 G H Yes NS, C O08447 monooxygenase activity 202 395965 G S 394933 C W 394995 C W Yes NS, NC O07253 methyltransferase activity 203 398416 T Null 397384 C Null 397446 C null No nc, NULL Null — 204 399064 G G 398032 A E 398094 A G Yes NS, NC O07256 — 205 402708 A H 401676 C P 401738 C P Yes NS, NC O33266 nucleic acid binding activity 206 406818 A V 405786 C V 405848 C V Yes S, NULL Null — 207 406884 G Null 405852 C Null 405914 C null No nc, NULL Null — 208 412130 G S 411098 A N 411160 A N Yes NS, C O06293 — 209 413310 G Q 412278 T H 412340 T H Yes NS, NC O06293 — 210 423408 T L 422377 C S 422439 C S Yes NS, NC P32724 chaperone activity 211 423774 C G 422743 T G 422805 T G Yes S, NULL Null — 212 425964 A F 424930 T I 425095 T I Yes NS, NC O06304 — 213 428488 G G 427469 T G 427619 T G Yes S, NULL Null — 214 429715 T A 428696 C A 428786 C A Yes S, NULL Null — 215 430077 C D 429058 T N 429148 T N Yes NS, NC O06304 — 216 438482 C S 437463 G S 437553 G S Yes S, NULL Null — 217 439288 A T 438269 G A 438359 G A Yes NS, NC O06309 metalloendopeptidase activity 218 441762 C A 440743 T V 440833 T V Yes NS, C O06312 cation transport 219 443988 C L 442969 A I 443059 A I Yes NS, C O06314 molecular_function unknown 220 444576 A V 443557 C V 443647 C V Yes S, NULL Null — 221 446432 T S 445413 C G 445503 C G Yes NS, NC O53703 transporter activity 222 446797 T H 445778 C R 445868 C R Yes NS, NC O53703 transporter activity 223 448459 T E 447440 C G 447530 C G Yes NS, NC O53705 nucleotide binding activity 224 449922 T S 448903 C G 448993 C G Yes NS, NC O53707 — 225 451132 T S 450113 C S 450203 C S Yes S, NULL Null — 226 452456 G S 451437 A F 451527 A F Yes NS, NC O53708 electron transport 227 452844 T A 451825 C A 451915 C A Yes S, NULL Null — 228 456342 G R 455323 C P 455414 C P Yes NS, NC O53712 DNA binding activity 229 456346 C G 455327 T G 455418 T G Yes S, NULL Null — 230 467343 C R 466324 T R 466415 T R Yes S, NULL Null — 231 467402 C A 466383 A D 466474 A D Yes NS, NC O53720 DNA binding activity 232 469376 G G 468355 A E 468448 A E Yes NS, NC P95197 purine base biosynthesis 233 470348 C T 469327 T I 469420 T I Yes NS, NC P95197 purine base biosynthesis 234 472937 G A 471916 A V 472009 A V Yes NS, C P95200 electron transport 235 474708 A A 473687 G A 473780 G A Yes S, NULL Null — 236 476885 G T 475864 C T 475957 C T Yes S, NULL Null — 237 482898 G P 481878 A L 481971 A L Yes NS, NC P95211 membrane 238 485256 G A 484236 A T 485687 A T Yes NS, NC P95213 enzyme activity 239 488897 G G 487876 T G 489327 T G Yes S, NULL Null — 240 490019 T T 488998 C T 490449 C T Yes S, NULL Null — 241 490878 G V 489857 A M 491308 A M Yes NS, NC O86335 enzyme activity 242 492761 C F 491740 T F 493191 T F Yes S, NULL Null — 243 493169 C A 492148 G G 493599 G G Yes NS, C P96254 metabolism 244 495704 C R 494683 A R 496134 A R Yes S, NULL Null — 245 498127 T P 497106 C P 498557 C P Yes S, NULL Null — 246 499550 G A 498529 A A 499980 A A Yes S, NULL Null — 247 502639 T V 501618 C A 503069 C A Yes NS, C P96261 electron transport 248 506993 A T 505972 G A 507423 G A Yes NS, NC P96265 proteolysis and peptidolysis 249 507929 T E 506908 C G 508359 C G Yes NS, NC P96266 — 250 515676 G A 514655 T E 516106 T E Yes NS, NC P96271 ATP binding activity 251 518377 C G 517356 T D 518807 T D Yes NS, NC P96274 — 252 518430 G R 517409 A R 518860 A R Yes S, NULL Null — 253 519412 T T 518391 C A 519842 C A Yes NS, NC P96275 protein biosynthesis 254 520204 G G 519183 T V 520634 T V Yes NS, C P96277 — 255 520350 G A 519329 A T 520780 A T Yes NS, NC P96277 — 256 520825 A A 519804 G A 521255 G A Yes S, NULL Null — 257 522338 C C 521317 T C 522768 T C Yes S, NULL Null — 258 523100 G A 522079 A T 523530 A T Yes NS, NC P96280 ATP-dependent peptidase activity 259 528335 G I 527314 C M 528765 C M Yes NS, NC O53725 Mo-molybdopterin cofactor biosynthesis 260 529373 A Null 528352 C Null 529803 C null Yes nc, NULL Null — 261 533211 T Null 532190 C Null 533641 C null Yes S, NULL Null — 262 534258 T E 533237 C G 534688 C G Yes NS, NC O53729 — 263 534489 T D 533468 C G 534919 C G Yes NS, NC O53729 — 264 535446 A Null 534425 T Null 535876 T null No nc, NULL Null — 265 540882 G S 539861 A S 541312 A S Yes S, NULL Null — 266 540902 G L 539881 A L 541332 A L Yes S, NULL Null — 267 541571 T T 540550 C A 542001 C A Yes NS, NC O53735 membrane 268 544180 C Null 543159 T Null 544610 T null No nc, NULL Null — 269 547376 G T 546355 A T 547806 A T Yes S, NULL Null — 270 556349 T Q 555328 C R 556779 C R Yes NS, NC O53750 DNA binding activity 271 557010 G R 555989 A C 557440 A C Yes NS, NC O53750 DNA binding activity 272 557220 C D 556199 T N 557650 T N Yes NS, NC O53750 DNA binding activity 273 558318 A Null 557297 G Null 558748 G null No nc, NULL Null — 274 561876 G L 560855 C L 562305 C L Yes S, NULL Null — 275 562317 T A 561296 C A 562746 C A Yes S, NULL Null — 276 566174 A G 565153 C G 566603 C G Yes S, NULL Null — 277 566423 T R 565402 G R 566852 G R Yes S, NULL Null — 278 574240 C T 573275 G T 574725 G T Yes S, NULL Null — 279 574347 G L 573382 T I 574832 T I Yes NS, C Q11150 metabolism 280 582972 A F 581819 G L 583188 G L Yes NS, NC Q11157 electron transporter activity 281 583372 C G 582219 T G 583588 T G Yes S, NULL Null — 282 584969 T Q 583816 C Q 585186 C Q Yes S, NULL Null — 283 585322 C G 584169 T S 585539 T S Yes NS, NC Q11158 — 284 585662 T T 584509 G T 585879 G T Yes S, NULL Null — 285 591914 C D 590761 G E 592131 G E Yes NS, C Q11141 pyrroline 5-carboxylate reductase activity 286 598704 C H 597551 G D 598920 G D Yes NS, NC Q11171 membrane 287 599874 T Y 598721 G D 600090 G D Yes NS, NC Q11171 membrane 288 600514 G C 599361 C S 600730 C S Yes NS, NC Q11171 membrane 289 601019 G R 599866 A R 601235 A R Yes S, NULL Null — 290 606489 G G 605336 A E 606705 A E Yes NS, NC O33357 porphobilinogen synthase activity 291 610514 T H 609361 C H 610730 C H Yes S, NULL Null — 292 611077 A D 609924 G G 611293 G G Yes NS, NC O33362 transferase activity 293 612523 C Q 611371 T Q 612740 T Q Yes S, NULL Null — 294 622386 C S 621234 G S 622603 G S Yes S, NULL Null — 295 624971 T G 623726 G G 625179 G G Yes S, NULL Null — 296 625445 T G 624200 C G 625653 C G Yes S, NULL Null — 297 631262 G Null 630016 A Null 631469 A null No nc, NULL Null — 298 631931 T P 630685 G P 632138 G P Yes S, NULL Null — 299 634973 C V 633727 T I 635181 T I Yes NS, C O06407 — 300 641373 T Null 640127 C Null 641581 C null No nc, NULL Null — 301 644245 C R 643000 G R 644454 G R Yes S, NULL Null — 302 645682 T A 644437 C A 645891 C A Yes S, NULL Null — 303 649910 T D 648665 C D 650119 C D Yes S, NULL Null — 304 650099 C G 648854 T G 650308 T G Yes S, NULL Null — 305 654178 T G 652933 C G 654387 C G Yes S, NULL Null — 306 657229 G Null 655984 T Null 657438 T null No nc, NULL Null — 307 658821 G D 657576 A D 659030 A D Yes S, NULL Null — 308 660166 G L 658921 C F 660375 C F Yes NS, NC O53764 methyltransferase activity 309 660584 C Null 659339 T Null 660793 T null No nc, NULL Null — 310 664154 C A 662909 T A 664363 T A Yes S, NULL Null — 311 668104 G F 666860 A F 668313 A F Yes S, NULL Null — 312 669625 C K 668381 A N 669834 A N Yes NS, NC O53771 — 313 671788 A H 670543 G R 671996 G R Yes NS, NC O53773 DNA binding activity 314 673323 A P 672078 G P 673531 G P Yes S, NULL Null — 315 673880 T T 672635 C A 674088 C A Yes NS, NC O53775 subtilase activity 316 677219 G Null 675974 A Null 677427 A null Yes nc, NULL Null — 317 680416 C Null 679171 T Null 680624 T null No nc, NULL Null — 318 680740 G G 679495 A D 680948 A D Yes NS, NC O86365 nitrogen fixation 319 685069 T I 683824 C M 685275 C I Yes NS, NC O53781 — 320 685533 G Null 684288 A Null 685739 A null Yes nc, NULL Null — 321 688596 C P 687351 T L 688802 T L Yes NS, NC O07789 pathogenesis 322 690448 T M 689202 C T 690653 C T Yes NS, NC O07787 pathogenesis 323 691492 A N 690246 C T 691695 C N Yes NS, C O07787 pathogenesis 324 691694 C A 690448 A A 691888 A null Yes S, NULL Null — 325 693833 T * 692586 C Q 694036 C Q Yes NS, TP O07785 pathogenesis 326 700963 T I 699716 C V 701166 C V Yes NS, C O07776 two-component response regulator activity 327 701329 G A 700082 C P 701532 C null Yes NS, NC O07775 — 328 701386 A K 700139 G E 701589 G null Yes NS, NC O07775 — 329 702021 C P 700774 T S 702224 T S Yes NS, NC O07774 — 330 706847 C S 705600 T N 707048 T N Yes NS, C O07767 — 331 712319 T A 711072 C A 712520 C A Yes S, NULL Null — 332 713327 G G 712080 C R 713528 C null Yes NS, NC O07759 UTP-hexose-1- phosphate uridylyltransferase activity 333 713374 C A 712127 G A 713575 G null Yes S, NULL Null — 334 714556 C R 713308 T C 714756 T C Yes NS, NC P96910 galactokinase activity 335 715048 T C 713800 C R 715248 C R Yes NS, NC P96910 galactokinase activity 336 716512 G W 715264 A Null 716712 A W Yes nc, NULL Null — 337 718834 G V 717586 A V 719034 A V Yes S, NULL Null — 338 720904 T V 719656 C V 721104 C V Yes S, NULL Null — 339 721373 C A 720125 T T 721573 T T Yes NS, NC P96919 RNA binding activity 340 722454 T G 721206 C G 722654 C G Yes S, NULL Null — 341 723170 G F 721922 A F 723370 A F Yes S, NULL Null — 342 723828 A F 722581 C V 724029 C V Yes NS, NC P96920 DNA binding activity 343 726039 A L 724792 C V 726240 C V Yes NS, C P96920 DNA binding activity 344 726979 A L 725732 G P 727180 G P Yes NS, NC P96921 helicase activity 345 728566 T E 727319 C G 728767 C G Yes NS, NC P96921 helicase activity 346 730359 A G 729112 G G 730559 G G Yes S, NULL Null — 347 733788 G A 732550 A T 733997 A T Yes NS, NC P96927 cysteine-type endopeptidase activity 348 737101 G A 735863 A T 737310 A T Yes NS, NC P96932 RNA binding activity 349 737549 T P 736311 C P 737753 C P Yes S, NULL Null — 350 738155 T L 736917 G F 738359 G F Yes NS, NC P72028 methyltransferase activity 351 740056 A L 738818 C R 740260 C R Yes NS, NC P72026 methyltransferase activity 352 742977 T T 741739 C A 743181 C A Yes NS, NC P96936 — 353 745086 T L 743315 C S 745290 C S Yes NS, NC P96937 alpha-mannosidase activity 354 746998 A P 745227 G P 747202 G P Yes S, NULL Null — 355 747114 G R 745343 C P 747318 C P Yes NS, NC P96937 alpha-mannosidase activity 356 758951 G G 757180 A D 759155 A D Yes NS, NC O06776 metabolism 357 764800 C A 763029 T A 765004 T A Yes S, NULL Null — 358 770931 G P 769160 A S 771136 A null Yes NS, NC O06769 — 359 771448 C Null 769677 A Null 771653 A null No nc, NULL Null — 360 772157 A A 770386 G A 772362 G A Yes S, NULL Null — 361 774665 A L 772894 G L 774870 G L Yes S, NULL Null — 362 777869 A I 776098 G T 778074 G T Yes NS, NC O53784 membrane 363 784766 A A 782995 G A 784971 G A Yes S, NULL Null — 364 788162 G S 786391 T I 788367 T I Yes NS, NC P95032 — 365 800584 T Null 798813 C Null 800788 C null No nc, NULL Null — 366 804997 T G 803173 C G 805364 C G Yes S, NULL Null — 367 808276 T L 806452 G L 808643 G L Yes S, NULL Null — 368 808601 T * 806777 G E 808968 G E Yes NS, TP P95059 metabolism 369 811737 C Null 809913 A Null 812104 A null No nc, NULL Null — 370 812709 G Null 810885 A Null 813076 A null No nc, NULL Null — 371 816925 T R 815101 C R 817293 C R Yes S, NULL Null — 372 817058 C T 815234 T I 817426 T I Yes NS, NC P95071 structural constituent of ribosome 373 817673 G R 815849 A R 818041 A null Yes S, NULL Null — 374 822574 T H 820750 C R 822942 C R Yes NS, NC O86322 serine biosynthesis 375 823729 C P 821905 T L 824097 T L Yes NS, NC O53793 carbohydrate metabolism 376 828003 C L 826179 G L 828371 G L Yes S, NULL Null — 377 833390 G V 831564 A M 833756 A M Yes NS, NC O53802 — 378 834025 T D 832199 C D 834390 C D Yes S, NULL Null — 379 834070 G Q 832244 A Q 834435 A Q Yes S, NULL Null — 380 836836 T Null 835010 A Null 837201 A null No nc, NULL Null — 381 837652 T V 835826 C A 838017 C A Yes NS, C O53809 — 382 839308 A N 837578 G S 839769 G S Yes NS, C O53809 — 383 846049 C V 843857 T I 846000 T I Yes NS, C O53815 acyl-CoA dehydrogenase activity 384 846399 G A 844207 A V 846350 A V Yes NS, C O53815 acyl-OcA dehydrogenase activity 385 846819 C G 844627 A V 846770 A V Yes NS, C O53816 metabolism 386 850185 C Null 847993 T Null 850136 T null No nc, NULL Null — 387 850597 T K 848405 C R 850548 C R Yes NS, C O53818 — 388 853294 T A 851102 C A 853245 C A Yes S, NULL Null — 389 853752 A Null 851560 G Null 853703 G null No nc, NULL Null — 390 854796 A I 852604 G I 854747 G I Yes S, NULL Null — 391 854797 T I 852605 G I 854748 G I Yes S, NULL Null — 392 856687 A F 854496 G F 856638 G F Yes S, NULL Null — 393 864764 T V 862573 C A 864715 C A Yes NS, C P71824 metabolism 394 865821 G G 863630 T V 865772 T V Yes NS, C P71825 valine metabolism 395 869886 C A 867695 A S 869837 A S Yes NS, NC P71829 enzyme activity 396 870116 G A 867925 T D 870067 T D Yes NS, NC P71829 enzyme activity 397 870460 C A 868269 T A 870411 T A Yes S, NULL Null — 398 873460 C P 871269 A T 873411 A T Yes NS, NC P71832 enzyme activity 399 879911 A L 877718 G L 879862 G L Yes S, NULL Null — 400 879912 A G 877719 G G 879863 G G Yes S, NULL Null — 401 895718 C S 894886 T S 894797 T null Yes S, NULL Null — 402 901045 G R 900213 C R 900124 C R Yes S, NULL Null — 403 904341 G V 903509 C V 903420 C V Yes S, NULL Null — 404 905912 C G 905080 G G 904991 G G Yes S, NULL Null — 405 912091 C P 911259 T L 911170 T L Yes NS, NC O53830 two-component response regulator activity 406 913660 G L 912828 C F 912739 C F Yes NS, NC O53832 nucleotide binding activity 407 914104 G S 913272 C S 913183 C S Yes S, NULL Null — 408 916876 G P 916044 T H 915955 T H Yes NS, NC O53834 — 409 917180 A Null 916348 G Null 916259 G null No nc, NULL Null — 410 917489 G L 916657 A F 916568 A F Yes NS, NC O53835 molecular_function unknown 411 917544 T L 916712 G L 916623 G L Yes S, NULL Null — 412 918089 A C 917257 C G 917168 C G Yes NS, NC O53835 molecular_function unknown 413 919629 C Null 918797 T Null 918708 T null No nc, NULL Null — 414 920661 T R 919829 C R 919740 C R Yes S, NULL Null — 415 920753 G G 919921 A E 919832 A E Yes NS, NC O53837 — 416 921344 A Q 920512 G R 920423 G R Yes NS, NC O53837 — 417 925130 A Null 924298 G Null 924209 G null No nc, NULL Null — 418 928734 C Null 927830 T Null 927741 T null No nc, NULL Null — 419 929147 T G 928396 G G 928298 G G Yes S, NULL Null — 420 930497 T A 929746 C A 929648 C A Yes S, NULL Null — 421 931872 C Y 931121 T Y 931023 T Y Yes S, NULL Null — 422 932186 G G 931435 A D 931337 A D Yes NS, NC O53846 — 423 933001 A P 932250 C Null 932152 C null Yes nc, NULL Null — 424 933029 C W 932278 T * 932180 T * Yes NS, TP O53848 — 425 934448 T G 933697 G G 933599 G G Yes S, NULL Null — 426 934979 G Null 934228 C Null 934130 C null No nc, NULL Null — 427 934982 A Null 934231 G Null 934133 G null No nc, NULL Null — 428 935360 T Null 934609 G Null 934511 G null No nc, NULL Null — 429 938432 T F 937675 G F 937577 G V Yes S, NULL Null — 430 939001 G L 938244 A L 938146 A L Yes S, NULL Null — 431 940714 G G 939957 A D 939859 A D Yes NS, NC O53855 metabolism 432 941068 A D 940311 C A 940213 C A Yes NS, NC O53855 metabolism 433 941645 G P 940888 C A 940790 C A Yes NS, NC O53856 two-component response regulator activity 434 942600 A E 941843 C A 941745 C A Yes NS, NC O53857 ATP binding activity 435 943719 G H 942962 A Y 942864 A Y Yes NS, C O53858 copper ion binding activity 436 945051 G Null 944294 A Null 944196 A null No nc, NULL Null — 437 945480 T V 944723 C A 944625 C A Yes NS, C O53859 — 438 946102 G G 945345 T V 945247 T null Yes NS, C O53860 amino acid metabolism 439 948022 T F 947265 C F 947165 C null Yes S, NULL Null — 440 948049 C G 947292 T G 947192 T null Yes S, NULL Null — 441 948974 A F 948217 C V 948117 C V Yes NS, NC O53863 metabolism 442 949049 C G 948292 T S 948192 T S Yes NS, NC O53863 metabolism 443 951897 A Null 951140 C Null 951040 C null No nc, NULL Null — 444 953517 C Null 952760 G Null 952660 G null No nc, NULL Null — 445 958717 A L 957961 G L 957861 G L Yes S, NULL Null — 446 959147 A T 958391 G A 958291 G A Yes NS, NC O53872 enzyme activity 447 960133 G A 959377 A V 959277 A V Yes NS, C O53873 nucleic acid binding activity 448 961068 G S 960365 A L 960371 A L Yes NS, NC O53874 — 449 967989 T S 967527 C G 967533 C G Yes NS, NC O53882 — 450 970372 A L 969904 G L 969919 G L Yes S, NULL Null — 451 972368 A G 971900 G G 971915 G G Yes S, NULL Null — 452 974604 G L 974136 A L 974150 A L Yes S, NULL Null — 453 976327 C G 975859 T D 975873 T D Yes NS, NC Q10564 integral to membrane 454 997447 G A 996980 A A 996994 A A Yes S, NULL Null — 455 998183 C Null 997716 G Null 997730 G null No nc, NULL Null — 456 1001197 G A 1000730 A T 1000744 A T Yes NS, NC Q10530 enzyme activity 457 1009407 C Null 1008940 T Null 1008954 T null No nc, NULL Null — 458 1010182 T G 1009715 C G 1009729 C G Yes S, NULL Null — 459 1010422 A L 1009955 G L 1009969 G L Yes S, NULL Null — 460 1011566 T L 1011098 C P 1011113 C P Yes NS, NC O05900 — 461 1015281 G Q 1014813 T H 1014828 T H Yes NS, NC O05901 — 462 1018494 A L 1018026 G P 1018041 G P Yes NS, NC O05905 — 463 1024812 G G 1024344 A S 1024359 A S Yes NS, NC O05910 — 464 1026536 T E 1026068 G D 1026083 G D Yes NS, C O05912 — 465 1027911 C V 1027443 G V 1027458 G V Yes S, NULL Null — 466 1030402 G R 1029934 A R 1029949 A R Yes S, NULL Null — 467 1034703 G L 1034236 A L 1034251 A L Yes S, NULL Null — 468 1041172 C A 1040704 A S 1040719 A S Yes NS, NC O05870 transporter activity 469 1043636 C A 1043167 T V 1043182 T V Yes NS, C P15712 transporter activity 470 1048294 T L 1047825 C L 1047840 C L Yes S, NULL Null — 471 1054603 T T 1054134 C T 1054149 C T Yes S, NULL Null — 472 1055251 G G 1054782 C R 1054797 C R Yes NS, NC P71564 metabolism 473 1063212 C A 1062743 T V 1062758 T V Yes NS, C P71559 enzyme activity 474 1064232 A K 1063763 G R 1063778 G R Yes NS, C P71558 enzyme activity 475 1077356 T H 1076915 C R 1076930 C R Yes NS, NC P71545 — 476 1077719 C G 1077278 A W 1077293 A W Yes NS, NC P71544 — 477 1080631 A N 1080190 G D 1080205 G D Yes NS, NC P77894 magnesium ion binding activity 478 1083482 A H 1083041 C Q 1083056 C Q Yes NS, NC P71539 acyl-CoA dehydrogenase activity 479 1085532 A F 1085091 T I 1085106 T I Yes NS, NC P71538 ATP binding activity 480 1096095 T T 1095642 C A 1095671 C A Yes NS, NC O53893 — 481 1096129 G G 1095676 A G 1095705 A G Yes S, NULL Null — 482 1096774 T Q 1096321 G H 1096362 G H Yes NS, NC O53893 — 483 1097474 A S 1097021 G G 1097062 G G Yes NS, NC O53894 two-component response regulator activity 484 1098974 A H 1098521 T L 1098562 T L Yes NS, NC O53895 two-component sensor molecule activity 485 1102935 T L 1102482 G V 1102523 G V Yes NS, C O53899 nucleotide binding activity 486 1103991 T G 1103538 C G 1103579 C G Yes S, NULL Null — 487 1104263 A * 1103810 G W 1103851 G W Yes NS, TP O53900 membrane 488 1105141 G V 1104688 T F 1104729 T F Yes NS, NC O53900 membrane 489 1105524 G G 1105071 A G 1105112 A G Yes S, NULL Null — 490 1105735 A I 1105282 G V 1105323 G V Yes NS, C O86370 — 491 1105969 G D 1105516 T Y 1105557 T Y Yes NS, NC O86370 — 492 1108391 C A 1107938 A S 1107979 A S Yes NS, NC O05573 — 493 1109614 G I 1109161 C M 1109202 C M Yes NS, NC O05575 enzyme activity 494 1111407 G G 1110954 T C 1110995 T C Yes NS, NC O05577 Mo-molybdopterin cofactor biosynthesis 495 1113109 G G 1112656 A D 1112697 A D Yes NS, NC O05579 — 496 1113741 C Q 1113288 G E 1113329 G E Yes NS, NC O05579 — 497 1120048 G L 1119595 C V 1119635 C V Yes NS, C O05586 mannosyltransferase activity 498 1124048 G S 1123595 A L 1123641 A L Yes NS, NC O05591 biosynthesis 499 1124238 G S 1123785 A N 1123831 A S Yes NS, C O05592 — 500 1125767 T S 1125314 C P 1125360 C P Yes NS, NC O05592 — 501 1129386 A E 1128933 G G 1128979 G G Yes NS, NC O05594 — 502 1129611 T V 1129158 C A 1129204 C A Yes NS, C O05594 — 503 1131752 A N 1131298 G S 1131344 G null Yes NS, C O05597 — 504 1137772 G Q 1137323 C E 1137369 C E Yes NS, NC P96382 UDP-N- acetylglucosamine pyrophosphorylase activity 505 1138029 C G 1137580 T E 1137626 T E Yes NS, NC P96382 UDP-N- acetylglucosamine pyrophosphorylase activity 506 1139461 T L 1139012 C L 1139058 C L Yes S, NULL Null — 507 1144279 C P 1143830 A T 1143876 A T Yes NS, NC P96378 — 508 1145032 G G 1144583 A R 1144629 A R Yes NS, NC P96377 phosphopyruvate hydratase complex 509 1148706 G Null 1148257 A Null 1148303 A null Yes nc, NULL Null — 510 1149575 T L 1149126 C L 1149172 C L Yes S, NULL Null — 511 1151250 T D 1150801 C G 1150847 C G Yes NS, NC P96372 two-component sensor molecule activity 512 1152153 T Null 1151704 C Null 1151750 C null Yes nc, NULL Null — 513 1161217 A L 1160768 T Q 1160814 T Q Yes NS, NC P96364 — 514 1164196 A Null 1163747 G Null 1163793 G null Yes nc, NULL Null — 515 1164719 T Null 1164270 C Null 1164316 C null Yes nc, NULL Null — 516 1165018 G Null 1164569 A Null 1164615 A null No nc, NULL Null — 517 1165561 T N 1165112 C D 1165158 C null Yes NS, NC P96360 — 518 1166468 A C 1166018 C G 1166065 C G Yes NS, NC P96358 serine-type endopeptidase activity 519 1166960 T T 1166510 C A 1166557 C A Yes NS, NC P96358 serine-type endopeptidase activity 520 1168430 G G 1167980 T W 1168027 T W Yes NS, NC P96356 — 521 1169896 A T 1169445 G A 1169493 G A Yes NS, NC P96354 peroxidase activity 522 1170414 A G 1169963 G G 1170011 G G Yes S, NULL Null — 523 1171297 A Null 1170846 G Null 1170894 G null Yes nc, NULL Null — 524 1175230 A Null 1174780 G Null 1174828 G null No nc, NULL Null — 525 1177201 C Null 1176751 T Null 1176799 T null Yes nc, NULL Null — 526 1179589 G Null 1179139 T Null 1179187 T null No nc, NULL Null — 527 1189705 T M 1189243 C V 1189291 C V Yes NS, NC O53415 — 528 1193177 C W 1191815 A L 1192055 A L Yes NS, NC O53416 — 529 1193221 C E 1191859 T E 1192099 T E Yes S, NULL Null — 530 1199501 G Null 1198139 A Null 1198376 A null No nc, NULL Null — 531 1199502 A Null 1198140 C Null 1198377 C null No nc, NULL Null — 532 1199636 A G 1198274 G G 1198511 G G Yes S, NULL Null — 533 1205184 C T 1203822 T I 1204059 T I Yes NS, NC O53426 — 534 1206868 A N 1205506 G N 1205743 G N Yes S, NULL Null — 535 1212729 C R 1211367 A S 1211604 A S Yes NS, NC O53434 metabolism 536 1214512 T G 1213168 C G 1213326 C null Yes S, NULL Null — 537 1221942 T Null 1220568 G Null 1220117 G null No nc, NULL Null — 538 1226570 T S 1225196 C P 1224745 C P Yes NS, NC O53444 carbohydrate metabolism 539 1227449 A L 1226075 G P 1225624 G P Yes NS, NC O53445 — 540 1230847 G D 1229473 T E 1229022 T E Yes NS, C O53449 integral to membrane 541 1232149 A I 1230776 G T 1230325 G T Yes NS, NC O53450 DNA binding activity 542 1236028 A D 1234655 G D 1234205 G D Yes S, NULL Null — 543 1236817 C S 1235444 T S 1234994 T S Yes S, NULL Null — 544 1239854 A I 1238481 G V 1238031 G V Yes NS, C O53459 GTP binding activity 545 1241612 C P 1240239 T S 1239789 T S Yes NS, NC O06567 — 546 1244718 G A 1243345 C G 1242895 C G Yes NS, C O06572 guanylate cyclase activity 547 1245764 G V 1244391 C V 1243941 C V Yes S, NULL Null — 548 1249753 G G 1248380 A S 1247930 A null Yes NS, NC O06577 — 549 1250307 C P 1248934 G P 1248483 G P Yes S, NULL Null — 550 1251711 G A 1250338 A A 1249887 A A Yes S, NULL Null — 551 1251728 G P 1250355 T T 1249904 T T Yes NS, NC O06579 ATP binding activity 552 1255933 G G 1254560 A D 1254109 A D Yes NS, NC O06582 — 553 1255953 C L 1254580 T F 1254129 T F Yes NS, NC O06582 — 554 1257383 T R 1256010 G R 1255559 G R Yes S, NULL Null — 555 1259222 T M 1257849 C T 1257398 C T Yes NS, NC O06583 — 556 1261908 T L 1260535 C L 1260084 C L Yes S, NULL Null — 557 1282061 C G 1280687 T D 1280179 T D Yes NS, NC O06551 methyltransferase activity 558 1282113 T T 1280739 C A 1280231 C A Yes NS, NC O06551 methyltransferase activity 559 1283143 C P 1281769 T S 1281261 T S Yes NS, NC O06553 — 560 1288484 C Null 1287110 T Null 1286600 T null No nc, NULL Null — 561 1290071 C L 1288697 G V 1288187 G V Yes NS, C O06559 electron transport 562 1291161 G G 1289787 A D 1289277 A D Yes NS, NC O06559 electron transport 563 1295376 T V 1294002 C A 1293492 C A Yes NS, C O06562 electron transport 564 1295770 T D 1294396 C D 1293886 C D Yes S, NULL Null — 565 1303656 G H 1302281 T Q 1301771 T Q Yes NS, NC O50428 — 566 1304272 G Null 1302897 A Null 1302387 A null No nc, NULL Null — 567 1307530 C S 1306279 A I 1305769 A I Yes NS, NC O50431 electron transport 568 1309207 T N 1307956 G T 1307446 G T Yes NS, C O50431 electron transport 569 1311565 T V 1310314 C A 1309804 C A Yes NS, C O50434 transaminase activity 570 1318177 C A 1316925 A D 1316414 A D Yes NS, NC O50437 alcohol dehydrogenase activity 571 1325815 A R 1324563 G R 1324052 G R Yes S, NULL Null — 572 1335064 T L 1333812 C L 1333301 C L Yes S, NULL Null — 573 1340081 C Null 1338829 A Null 1338318 A null Yes nc, NULL Null — 574 1341302 T L 1340050 G R 1339539 G R Yes NS, NC O05298 — 575 1341343 G V 1340091 A M 1339580 A M Yes NS, NC O05298 — 576 1341420 T A 1340168 C A 1339657 C A Yes S, NULL Null — 577 1341887 T Null 1340638 C Null 1340127 C null No nc, NULL Null — 578 1341914 G S 1340665 A S 1340154 A S Yes S, NULL Null — 579 1342025 C I 1340776 T I 1340265 T I Yes S, NULL Null — 580 1342028 G S 1340779 C S 1340268 C S Yes S, NULL Null — 581 1342031 C G 1340782 T G 1340271 T G Yes S, NULL Null — 582 1342077 A T 1340828 G A 1340317 G A Yes NS, NC O05299 — 583 1342287 A D 1341038 C A 1340527 C A Yes NS, NC O05300 — 584 1342456 T A 1341207 C A 1340696 C A Yes S, NULL Null — 585 1343724 A A 1342475 G A 1341964 G A Yes S, NULL Null — 586 1345988 G Y 1344739 A Y 1344228 A Y Yes S, NULL Null — 587 1348420 T L 1347171 C L 1346660 C L Yes S, NULL Null — 588 1352419 G Null 1351170 A Null 1350659 A null No nc, NULL Null — 589 1356596 T I 1355347 C V 1354836 C V Yes NS, C O05313 biosynthesis 590 1357184 T F 1355935 C F 1355424 C F Yes S, NULL Null — 591 1360182 A S 1358938 C A 1358427 C A Yes NS, NC O05316 DNA binding activity 592 1362617 T T 1361373 C A 1360862 C A Yes NS, NC O05318 — 593 1367980 C L 1366734 T F 1366224 T F Yes NS, NC O06291 serine-type endopeptidase activity 594 1368452 A N 1367206 G S 1366696 G S Yes NS, C O06291 serine-type endopeptidase activity 595 1368728 G G 1367482 T W 1366972 T W Yes NS, NC O33220 protein targeting 596 1370191 G A 1368945 A V 1368435 A V Yes NS, C O33222 — 597 1372850 C Null 1371604 A Null 1371094 A null Yes nc, NULL Null — 598 1375153 G P 1373907 A S 1373397 A S Yes NS, NC O86313 transcription factor activity 599 1377868 T D 1376622 C G 1376112 C G Yes NS, NC O86316 — 600 1377935 C D 1376689 T N 1376179 T N Yes NS, NC O86316 — 601 1378384 G E 1377138 A E 1376628 A E Yes S, NULL Null — 602 1383703 C R 1382457 T H 1381947 T H Yes NS, NC O50455 cobalt ion transport 603 1388166 T G 1386920 C G 1386410 C G Yes S, NULL Null — 604 1388824 A K 1387578 C Q 1387068 C Q Yes NS, NC O50459 — 605 1391333 T A 1390087 C A 1389576 C A Yes S, NULL Null — 606 1392007 T M 1390761 C V 1390250 C V Yes NS, NC O50463 metabolism 607 1394247 G Null 1393001 T Null 1392490 T null Yes nc, NULL Null — 608 1394944 T T 1393698 C A 1393187 C A Yes NS, NC O50464 — 609 1396254 G G 1395008 A R 1394497 A R Yes NS, NC O50465 transporter activity 610 1398445 G N 1397199 A N 1396688 A N Yes S, NULL Null — 611 1401640 G V 1400394 A M 1399883 A M Yes NS, NC Q11039 nucleic acid binding activity 612 1408298 C R 1410060 G P 1409548 G P Yes NS, NC Q11066 — 613 1410739 T C 1412501 C R 1411989 C R Yes NS, NC Q11055 guanylate cyclase activity 614 1412796 T R 1414558 C R 1414046 C R Yes S, NULL Null — 615 1412800 T N 1414562 A I 1414050 A I Yes NS, NC Q11053 protein kinase activity 616 1412889 T P 1414651 C P 1414139 C P Yes S, NULL Null — 617 1413243 G A 1415095 C A 1414583 C A Yes S, NULL Null — 618 1415700 C Null 1417552 G Null 1417040 G null Yes nc, NULL Null — 619 1417495 T T 1419347 C A 1418835 C A Yes NS, NC Q11049 membrane 620 1421972 T A 1423824 C A 1423312 C A Yes S, NULL Null — 621 1422845 C P 1424697 T L 1424185 T L Yes NS, NC Q11045 membrane 622 1423465 A Null 1425317 G Null 1424805 G null No nc, NULL Null — 623 1423787 A S 1425639 T T 1425127 T T Yes NS, C Q11043 hydrolase activity 624 1425622 T F 1427474 C F 1426962 C F Yes S, NULL Null — 625 1435584 A R 1437436 C R 1436924 C R Yes S, NULL Null — 626 1437785 T L 1439637 G V 1439125 G V Yes NS, C Q10600 sulfate assimilation 627 1438084 T R 1439936 C R 1439424 C R Yes S, NULL Null — 628 1440727 G Null 1442732 C Null 1442220 C null No nc, NULL Null — 629 1452860 T N 1454809 C N 1454352 C N Yes S, NULL Null — 630 1456125 G G 1458074 T G 1457617 T G Yes S, NULL Null — 631 1456193 A Q 1458142 C P 1457685 C P Yes NS, NC Q10618 molecular_function unknown 632 1457413 G G 1459362 T V 1458905 T V Yes NS, C Q10606 magnesium ion binding activity 633 1458715 T V 1460664 C V 1460207 C V Yes S, NULL Null — 634 1460269 C V 1462218 G V 1461761 G V Yes S, NULL Null — 635 1465744 T V 1467693 C A 1467236 C A Yes NS, C Q10620 integral to membrane 636 1465784 A G 1467733 G G 1467276 G G Yes S, NULL Null — 637 1469253 T F 1471215 C F 1470758 C F Yes S, NULL Null — 638 1476347 T L 1478310 C L 1477853 C L Yes S, NULL Null — 639 1476918 T * 1478881 C W 1478424 C W Yes NS, TP Q10630 DNA binding activity 640 1477120 C V 1479083 T I 1478626 T I Yes NS, C Q10630 DNA binding activity 641 1487043 C A 1489006 T T 1490222 T T Yes NS, NC Q10637 — 642 1488940 G P 1490903 A S 1492119 A S Yes NS, NC Q10625 643 1488946 A S 1490909 G P 1492125 G P Yes NS, NC Q10625 644 1490229 C G 1492192 T D 1493408 T D Yes NS, NC Q10625 645 1490640 T A 1492603 C A 1493819 C A Yes S, NULL Null — 646 1494193 G G 1496156 A D 1497372 A D Yes NS, NC Q10639 enzyme activity 647 1494324 T F 1496287 G V 1497503 G V Yes NS, NC Q10639 enzyme activity 648 1494999 T S 1496962 G A 1498178 G A Yes NS, NC Q10639 enzyme activity 649 1497326 T G 1499289 C G 1500505 C G Yes S, NULL Null — 650 1497523 T K 1499486 C E 1500702 C E Yes NS, NC Q10641 — 651 1499260 G R 1501223 T R 1502439 T R Yes S, NULL Null — 652 1500014 A T 1501977 G T 1503193 G T Yes S, NULL Null — 653 1503229 C G 1505192 T G 1506408 T G Yes S, NULL Null — 654 1504008 A R 1505971 G R 1507187 G R Yes S, NULL Null — 655 1505078 A S 1507041 G G 1508257 G G Yes NS, NC Q10628 tRNA binding activity 656 1506717 G A 1508680 T E 1509896 T E Yes NS, NC Q11013 integral to membrane 657 1521210 C A 1523173 A A 1524390 A A Yes S, NULL Null — 658 1521826 G P 1523789 A L 1525006 A L Yes NS, NC Q11025 enzyme activity 659 1524738 T V 1526701 G G 1527918 G G Yes NS, C Q11028 DNA binding activity 660 1525971 C A 1527934 A D 1529151 A D Yes NS, NC Q11028 DNA binding activity 661 1528766 A R 1530729 G G 1531946 G G Yes NS, NC Q11029 guanylate cyclase activity 662 1530691 T A 1532654 G A 1533871 G A Yes S, NULL Null — 663 1530694 T P 1532657 C P 1533874 C P Yes S, NULL Null — 664 1530695 G P 1532658 T P 1533875 T P Yes S, NULL Null — 665 1530763 T S 1532726 C S 1533943 C S Yes S, NULL Null — 666 1530890 T N 1532853 C S 1534070 C S Yes NS, C Q11031 — 667 1530894 T T 1532857 C A 1534074 C A Yes NS, NC Q11031 — 668 1530957 T I 1532920 G L 1534137 G L Yes NS, C Q11031 — 669 1531501 C G 1533464 T G 1534681 T G Yes S, NULL Null — 670 1531505 A V 1533468 G V 1534685 G V Yes S, NULL Null — 671 1531506 C V 1533469 T V 1534686 T V Yes S, NULL Null — 672 1531581 G Q 1533544 T K 1534761 T K Yes NS, NC Q11031 — 673 1531582 A A 1533545 C A 1534762 C A Yes S, NULL Null — 674 1531585 C A 1533548 G A 1534765 G A Yes S, NULL Null — 675 1532338 C G 1534301 A V 1535518 A V Yes NS, C Q11032 integral to membrane 676 1532964 T N 1534927 G T 1536144 G T Yes NS, C Q11033 integral to membrane 677 1534974 T T 1536937 C A 1538155 C A Yes NS, NC Q11034 two-component sensor molecule activity 678 1535961 T K 1537924 C E 1539142 C E Yes NS, NC Q11035 — 679 1537543 A Null 1539506 G Null 1540724 G null No nc, NULL Null — 680 1538176 C V 1540139 T I 1541357 T I Yes NS, C Q11037 — 681 1540933 T C 1544253 C C 1544113 C C Yes S, NULL Null — 682 1543382 T A 1546701 C A 1546561 C A Yes S, NULL Null — 683 1544766 A R 1548085 G G 1547945 G G Yes NS, NC P71803 — 684 1544828 A P 1548147 G P 1548007 G P Yes S, NULL Null — 685 1545475 C P 1548794 G R 1548654 G R Yes NS, NC P71803 — 686 1546533 C P 1549852 G R 1549712 G R Yes NS, NC P71804 — 687 1549309 T H 1552628 C R 1552488 C R Yes NS, NC P71806 — 688 1551431 T F 1554750 G V 1554610 G V Yes NS, NC P71809 dihydroorotase activity 689 1553002 G G 1556321 C A 1556181 C A Yes NS, C P71811 enzyme activity 690 1556241 A E 1559560 C A 1559420 C A Yes NS, NC Not — annotated 691 1556275 T H 1559594 C H 1559454 C H Yes S, NULL Null — 692 1558090 A Null 1561409 G Null 1561269 G null No nc, NULL Null — 693 1558582 C S 1561901 A S 1561761 A S Yes S, NULL Null — 694 1558728 C A 1562047 T V 1561907 T V Yes NS, C P71657 — 695 1563681 G A 1567000 A T 1566860 A T Yes NS, NC P77899 magnesium ion binding activity 696 1569266 T H 1572957 C R 1572817 C null Yes NS, NC P71664 integral to membrane 697 1570275 T Null 1573966 C Null 1573825 C null No nc, NULL Null — 698 1570513 C G 1574204 T D 1574063 T D Yes NS, NC P71665 — 699 1578358 C Null 1582049 T Null 1581905 T null No nc, NULL Null — 700 1580686 C L 1584377 A I 1584233 A I Yes NS, C P71675 RNA binding activity 701 1581590 C N 1585281 A K 1585137 A K Yes NS, NC P71677 enzyme activity 702 1581711 A T 1585402 G A 1585258 G A Yes NS, NC P71677 enzyme activity 703 1585618 G Null 1589309 T Null 1589165 T null No nc, NULL Null — 704 1589763 T Null 1593454 C Null 1593310 C null No nc, NULL Null — 705 1593041 T R 1596732 C R 1596588 C R Yes S, NULL Null — 706 1593444 T V 1597135 C A 1596991 C A Yes NS, C P71691 — 707 1596992 T L 1600683 C P 1600539 C P Yes NS, NC P71694 molecular_function unknown 708 1604583 C T 1608274 A N 1608132 A N Yes NS, C O06827 — 709 1605752 C Q 1609443 A K 1609301 A K Yes NS, NC O06827 — 710 1607590 C Null 1611281 T Null 1611139 T null No nc, NULL Null — 711 1609080 T T 1612750 C A 1612635 C A Yes NS, NC O06823 — 712 1614744 A G 1618414 G G 1618299 G null Yes S, NULL Null — 713 1614952 T N 1618622 G T 1618507 G null Yes NS, C O06818 structural molecule activity 714 1615306 C G 1618976 T D 1618860 T null Yes NS, NC O06818 structural molecule activity 715 1627846 G G 1631524 A G 1631407 A G Yes S, NULL Null — 716 1628460 G H 1632138 T N 1632021 T N Yes NS, NC O06810 — 717 1629691 G N 1633342 A N 1633252 A N Yes S, NULL Null — 718 1631814 A T 1635228 G A 1635345 G A Yes NS, NC O06809 heme biosynthesis 719 1636164 G L 1639416 A L 1639521 A L Yes S, NULL Null — 720 1636389 C R 1639641 T R 1639746 T R Yes S, NULL Null — 721 1637188 T G 1640440 C G 1640545 C G Yes S, NULL Null — 722 1643728 T V 1646980 C A 1647138 C A Yes NS, C O53151 transcription factor activity 723 1643863 C G 1647115 T G 1647273 T G Yes S, NULL Null — 724 1656740 T S 1659992 C P 1660150 C P Yes NS, NC O53163 enzyme activity 725 1657398 T Null 1660650 G Null 1660808 G null No nc, NULL Null — 726 1657399 T Null 1660651 A Null 1660809 A null No nc, NULL Null — 727 1658616 A Q 1661868 G Q 1662026 G Q Yes S, NULL Null — 728 1659304 C P 1662556 T Null 1662714 T S Yes nc, NULL Null — 729 1659465 C A 1662717 G A 1662875 G A Yes S, NULL Null — 730 1668404 T R 1671656 C R 1671814 C R Yes S, NULL Null — 731 1669135 C Null 1672387 T Null 1672545 T null No nc, NULL Null — 732 1678674 T V 1681926 C V 1682084 C V Yes S, NULL Null — 733 1681725 C S 1684977 T S 1685135 T S Yes S, NULL Null — 734 1683015 T Null 1686267 C Null 1686425 C null No nc, NULL Null — 735 1685046 C F 1688298 T F 1688456 T F Yes S, NULL Null — 736 1687091 G Null 1690343 A Null 1690501 A null Yes S, NULL Null — 737 1690478 T C 1693731 C C 1693889 C C Yes S, NULL Null — 738 1690944 T K 1694197 C E 1694355 C null Yes NS, NC CAB02017 — 739 1691292 C E 1694545 A * 1694703 A null Yes NS, TP CAB02018 — 740 1692419 A Y 1695672 G Y 1695830 G Y Yes S, NULL Null — 741 1694454 A R 1710439 C S 1710596 C S Yes NS, NC Q50590 integral to membrane 742 1694605 C L 1710590 A M 1710747 A M Yes NS, NC Q50590 integral to membrane 743 1696535 T I 1712520 G S 1712677 G S Yes NS, NC Q50586 enzyme activity 744 1698303 T * 1714288 G S 1714445 G S Yes NS, TP Q50585 membrane 745 1698786 T N 1714771 C S 1714928 C S Yes NS, C Q50585 membrane 746 1700485 G P 1716470 A S 1716627 A S Yes NS, NC Q50585 membrane 747 1701016 C A 1717001 T T 1717158 T T Yes NS, NC Q50585 membrane 748 1703404 T F 1719389 C F 1719546 C F Yes S, NULL Null — 749 1708108 G L 1724093 A F 1724250 A null Yes NS, NC O53901 enzyme activity 750 1710829 T T 1726814 G P 1726970 G null Yes NS, NC O53901 enzyme activity 751 1712677 T Null 1728662 C Null 1728818 C null Yes nc, NULL Null — 752 1715811 A A 1731796 G A 1731952 G A Yes S, NULL Null — 753 1723307 G A 1739292 C P 1739447 C P Yes NS, NC Q10765 tRNA ligase activity 754 1734934 A A 1750919 C A 1751074 C A Yes S, NULL Null — 755 1737144 G A 1753129 A V 1753284 A V Yes NS, C Q10778 integral to membrane 756 1737486 C Null 1753471 G Null 1753626 G null Yes nc, NULL Null — 757 1738210 A G 1754193 G G 1754349 G G Yes S, NULL Null — 758 1738587 C S 1754570 T L 1754726 T L Yes NS, NC Q10776 enzyme activity 759 1744942 C T 1760921 T T 1761077 T T Yes S, NULL Null — 760 1752792 T T 1766618 C A 1766774 C A Yes NS, NC Q10769 hydrolase activity 761 1760533 A Null 1775165 G Null 1775321 G null No nc, NULL Null — 762 1779600 A A 1794232 G A 1785141 G A Yes S, NULL Null — 763 1782943 G D 1797575 A N 1788484 A N Yes NS, NC O06594 nicotinate-nucleotide pyrophosphorylase (carboxylating) activity 764 1785887 G Q 1800519 A Q 1791428 A Q Yes S, NULL Null — 765 1789614 A E 1804246 G E 1795155 G E Yes S, NULL Null — 766 1789681 C H 1804313 T Y 1795222 T Y Yes NS, C O53907 inositol/ phosphatidylinositol phosphatase activity 767 1790156 T L 1804788 C P 1795697 C P Yes NS, NC O53907 inositol/ phosphatidylinositol phosphatase activity 768 1790580 T L 1805212 C P 1796121 C P Yes NS, NC O53908 histidine biosynthesis 769 1798626 C V 1813258 T V 1804167 T V Yes S, NULL Null — 770 1802214 T D 1816846 G E 1807755 G E Yes NS, C O06134 magnesium ion binding activity 771 1808750 C T 1823382 G T 1814291 G T Yes S, NULL Null — 772 1811420 C A 1826052 T T 1816961 T T Yes NS, NC O06141 — 773 1813171 T V 1827803 C V 1818712 C V Yes S, NULL Null — 774 1813366 A Null 1827998 G Null 1818907 G null No nc, NULL Null — 775 1813755 T R 1828387 C R 1819296 C R Yes S, NULL Null — 776 1815661 A F 1830293 G F 1821202 G F Yes S, NULL Null — 777 1820225 A T 1834857 G A 1825766 G A Yes NS, NC O06147 RNA binding activity 778 1822223 T Null 1836855 G Null 1827764 G null No nc, NULL Null — 779 1824626 G L 1839258 T L 1830167 T L Yes S, NULL Null — 780 1825125 C R 1839757 G G 1830666 G G Yes NS, NC O06151 transporter activity 781 1828921 A N 1843553 G N 1834462 G N Yes S, NULL Null — 782 1834571 C G 1849203 T D 1840112 T D Yes NS, NC P94974 magnesium ion binding activity 783 1834975 C R 1849607 T R 1840516 T R Yes S, NULL Null — 784 1844924 A D 1859557 C A 1850466 C A Yes NS, NC P94984 magnesium ion binding activity 785 1845757 T V 1860390 C A 1851299 C A Yes NS, C P94985 tRNA binding activity 786 1850233 A V 1864866 G A 1855775 G A Yes NS, C P94986 — 787 1858345 G R 1872957 A R 1863865 A R Yes S, NULL Null — 788 1862697 T W 1877309 C R 1868217 C R Yes NS, NC P94996 enzyme activity 789 1863620 A T 1878232 G T 1869140 G T Yes S, NULL Null — 790 1864215 C P 1878827 T S 1869735 T S Yes NS, NC P94996 enzyme activity 791 1867321 T Y 1881933 G D 1872841 G D Yes NS, NC O65933 enzyme activity 792 1867566 T A 1882178 C A 1873086 C A Yes S, NULL Null — 793 1869512 T V 1884124 C A 1875032 C A Yes NS, C O65933 enzyme activity 794 1869897 A V 1884509 G V 1875417 G V Yes S, NULL Null — 795 1870867 G G 1885479 C R 1876387 C R Yes NS, NC O65933 enzyme activity 796 1871495 G C 1886107 A Y 1877015 A Y Yes NS, NC O65933 enzyme activity 797 1873514 A T 1888126 G A 1879034 G A Yes NS, NC O06586 enzyme activity 798 1874459 C P 1889071 G A 1879979 G A Yes NS, NC O06586 enzyme activity 799 1878859 A T 1893471 G T 1884379 G T Yes S, NULL Null — 800 1885417 T Null 1900019 C Null 1890823 C null Yes nc, NULL Null — 801 1886196 G A 1900798 A V 1891602 A V Yes NS, C O53922 transcription factor activity 802 1888569 T I 1903171 C I 1893975 C I Yes S, NULL Null — 803 1890513 G G 1905115 C A 1895919 C A Yes NS, C O33182 — 804 1891732 G Null 1906334 A Null 1897138 A null No nc, NULL Null — 805 1897364 A F 1912022 C V 1902826 C V Yes NS, NC O33188 drug transporter activity 806 1897922 A A 1912580 G A 1903384 G A Yes S, NULL Null — 807 1899910 C A 1914568 A A 1905372 A A Yes S, NULL Null — 808 1905462 T P 1920118 G P 1910922 G P Yes S, NULL Null — 809 1910301 C G 1924957 T G 1915761 T G Yes S, NULL Null — 810 1911052 G L 1925708 C F 1916512 C F Yes NS, NC O33199 — 811 1911527 A T 1926183 G A 1916987 G A Yes NS, NC O33199 — 812 1915691 T A 1930348 C A 1921152 C A Yes S, NULL Null — 813 1916811 A Null 1931468 G Null 1922272 G null No nc, NULL Null — 814 1917059 C V 1931716 G L 1922520 G L Yes NS, C O33204 — 815 1921036 G A 1935693 T S 1926497 T S Yes NS, NC O33206 sulfate porter activity 816 1921535 A Q 1936192 G R 1926996 G R Yes NS, NC O33206 sulfate porter activity 817 1921866 A T 1936523 G A 1927327 G null Yes NS, NC O33207 — 818 1928563 A Null 1943220 G Null 1934024 G null Yes S, NULL Null — 819 1933291 A M 1947949 G V 1938753 G V Yes NS, NC P71980 — 820 1934421 T R 1949079 C R 1939883 C R Yes S, NULL Null — 821 1937104 A Null 1951762 G Null 1942565 G null No nc, NULL Null — 822 1937372 C P 1952030 G A 1942833 G A Yes NS, NC P71984 sugar porter activity 823 1938167 T Y 1952825 C H 1943628 C H Yes NS, C P71984 sugar porter activity 824 1941920 A T 1956521 C T 1947381 C T Yes S, NULL Null — 825 1942743 C Null 1957344 T Null 1948204 T null Yes nc, NULL Null — 826 1946179 C A 1960780 T T 1951640 T A Yes NS, NC P71992 — 827 1948447 C R 1963048 T R 1953908 T R Yes S, NULL Null — 828 1949354 C G 1963955 T D 1954815 T D Yes NS, NC P71994 electron transport 829 1949427 G H 1964028 C D 1954888 C D Yes NS, NC P71994 electron transport 830 1950831 G Null 1965432 A Null 1956292 A null No nc, NULL Null — 831 1953513 C T 1968114 A K 1958974 A K Yes NS, NC P71999 — 832 1953569 T Null 1968170 G Null 1959030 G null No nc, NULL Null — 833 1954568 A D 1969168 T V 1960028 T V Yes NS, NC P72001 protein kinase activity 834 1956427 T Q 1971027 C R 1961887 C R Yes NS, NC O06787 — 835 1956859 T Null 1971459 G Null 1962319 G null Yes S, NULL Null — 836 1957123 C R 1971723 G R 1962583 G R Yes S, NULL Null — 837 1957247 G S 1971847 A F 1962707 A F Yes NS, NC P72002 isopentenyl- diphosphate delta- isomerase activity 838 1958508 A T 1973108 G A 1963968 G A Yes NS, NC P72003 protein kinase activity 839 1961358 T S 1975958 G S 1966818 G S Yes S, NULL Null — 840 1965950 C T 1980550 T M 1971410 T M Yes NS, NC O65936 monooxygenase activity 841 1981202 G G 1990359 A G 1988183 A null Yes S, NULL Null — 842 1982624 G G 1991781 A G 1989605 A null Yes S, NULL Null — 843 1985405 T T 1994564 C T 1992387 C T Yes S, NULL Null — 844 1989704 G R 1999262 A Null 1996686 A null Yes nc, NULL Null — 845 1991672 C H 2001230 A N 1998654 A null Yes NS, NC O06801 — 846 1993549 T L 2003089 C L 2000511 C L Yes S, NULL Null — 847 1997652 A F 2007192 G F 2004614 G F Yes S, NULL Null — 848 2001072 A Null 2010612 G Null 2008034 G null No nc, NULL Null — 849 2002085 G Q 2011625 C H 2009047 C H Yes NS, NC O33180 monooxygenase activity 850 2002894 C R 2012434 G T 2009856 G T Yes NS, NC O33181 — 851 2004047 T L 2013587 C L 2011009 C L Yes S, NULL Null — 852 2007749 C R 2017289 T R 2014711 T R Yes S, NULL Null — 853 2008319 A H 2017859 G R 2015281 G R Yes NS, NC O53933 — 854 2009694 G P 2019234 T P 2016656 T P Yes S, NULL Null — 855 2011784 G A 2021324 A A 2018746 A A Yes S, NULL Null — 856 2012022 A M 2021562 G V 2018984 G V Yes NS, NC O53935 nucleotide binding activity 857 2017231 A Null 2026774 G Null 2024196 G null Yes nc, NULL Null — 858 2018064 G A 2027607 T S 2025029 T S Yes NS, NC O53939 — 859 2019447 T S 2028990 C P 2026412 C P Yes NS, NC O53940 — 860 2019644 G P 2029187 A P 2026609 A P Yes S, NULL Null — 861 2020481 T P 2030024 C P 2027446 C P Yes S, NULL Null — 862 2020767 T Null 2030310 C Null 2027732 C null No nc, NULL Null — 863 2020942 T G 2030485 C G 2027907 C null Yes S, NULL Null — 864 2020943 C Q 2030486 A Q 2027908 A null Yes S, NULL Null — 865 2020944 A Q 2030487 T Q 2027909 T null Yes S, NULL Null — 866 2020976 C Q 2030519 T * 2027941 T null Yes NS, TP Not — annotated 867 2021631 T P 2031174 G P 2028596 G P Yes S, NULL Null — 868 2022570 G Null 2032113 A Null 2029535 A null No nc, NULL Null — 869 2023460 G A 2033003 A T 2030425 A T Yes NS, NC O53944 — 870 2023476 A D 2033019 G G 2030441 G G Yes NS, NC O53944 — 871 2030339 G W 2039882 T C 2037304 T C Yes NS, NC O53949 — 872 2030664 G V 2040207 T F 2037629 T F Yes NS, NC O53949 — 873 2031415 C A 2040958 T V 2038380 T V Yes NS, C O53949 — 874 2037036 A * 2046579 G Q 2044001 G Q Yes NS, TP O53952 — 875 2037314 C Null 2046857 T Null 2044279 T null Yes nc, NULL Null — 876 2039950 T P 2049493 C P 2046915 C P Yes S, NULL Null — 877 2040516 G S 2050059 A S 2047481 A S Yes S, NULL Null — 878 2041277 C A 2050820 G G 2048242 G G Yes NS, C O53957 — 879 2042298 T * 2051841 C Q 2049263 C Q Yes NS, TP O53958 proton transport 880 2043142 C S 2052685 G * 2050107 G * Yes NS, TP O53958 proton transport 881 2044762 A T 2054305 G T 2051727 G T Yes S, NULL Null — 882 2048737 G K 2058280 A K 2055702 A K Yes S, NULL Null — 883 2052442 T S 2061976 C G 2059405 C G Yes NS, NC Q50615 integral to membrane 884 2053144 G Null 2062678 A Null 2060017 A null Yes nc, NULL Null — 885 2053386 C V 2062920 T I 2060259 T I Yes NS, C Q50614 nucleotide binding activity 886 2054840 G A 2064374 A V 2061713 A V Yes NS, C Q50614 nucleotide binding activity 887 2055511 A P 2065045 G P 2062384 G P Yes S, NULL Null — 888 2062654 C A 2072188 A E 2069527 A E Yes NS, NC Q50607 glycine cleavage system complex 889 2064683 T C 2074217 C R 2071556 C R Yes NS, NC Q50604 — 890 2065441 C Y 2075087 T Y 2072314 T Y Yes S, NULL Null — 891 2066872 C A 2076518 T V 2073745 T V Yes NS, C Q50601 glycine cleavage system 892 2067570 G A 2077216 A T 2074443 A T Yes NS, NC Q50601 glycine cleavage system 893 2068670 T V 2078316 C V 2075543 C V Yes S, NULL Null — 894 2070996 C A 2080642 T V 2077869 T V Yes NS, C Q50599 enzyme activity 895 2073217 T H 2082863 C R 2080091 C R Yes NS, NC Q50597 integral to membrane 896 2074580 A C 2084226 G R 2081454 G R Yes NS, NC Q50597 integral to membrane 897 2080993 G S 2090774 A L 2088002 A L Yes NS, NC Q50592 integral to membrane 898 2082905 A G 2092686 G G 2089914 G G Yes S, NULL Null — 899 2083932 C K 2093713 T Null 2090941 T null Yes nc, NULL Null — 900 2086536 A Y 2096324 C D 2093546 C D Yes NS, NC P95163 — 901 2087337 T N 2097126 C N 2094348 C N Yes S, NULL Null — 902 2087353 C L 2097142 G V 2094364 G V Yes NS, C P95162 enzyme activity 903 2090002 T L 2099791 A M 2097013 A M Yes NS, NC P50050 nickel ion binding activity 904 2092402 A W 2102191 G R 2099413 G R Yes NS, NC P95160 electron transport 905 2094478 T H 2104268 C R 2101490 C R Yes NS, NC P95158 metabolism 906 2094633 T A 2104423 C A 2101645 C A Yes S, NULL Null — 907 2097719 T M 2107509 C T 2104731 C T Yes NS, NC P95155 nucleotide binding activity 908 2099098 C Null 2108888 A Null 2106110 A null No nc, NULL Null — 909 2099682 T Null 2109472 C Null 2106694 C null No nc, NULL Null — 910 2100574 C T 2110363 A T 2107586 A T Yes S, NULL Null — 911 2103397 C Q 2113186 G E 2110409 G E Yes NS, NC P95149 DNA binding activity 912 2110986 T L 2120775 C Null 2117998 C null Yes nc, NULL Null — 913 2111005 A L 2120794 T * 2118017 T * Yes NS, TP P95145 base-excision repair 914 2112834 G A 2122623 A V 2119846 A V Yes NS, C P95143 electron transport 915 2113185 G A 2122974 C G 2120197 C G Yes NS, C P95143 electron transport 916 2113487 G G 2123276 T G 2120499 T G Yes S, NULL Null — 917 2113686 A N 2123475 G D 2120698 G D Yes NS, NC O07756 — 918 2116072 T Null 2125861 C Null 2123084 C null No nc, NULL Null — 919 2118582 G T 2128370 A T 2125593 A T Yes S, NULL Null — 920 2119054 A T 2128842 G A 2126065 G A Yes NS, NC O07752 glutamate-ammonia ligase activity 921 2119491 A A 2129279 C A 2126502 C A Yes S, NULL Null — 922 2120739 G Null 2130527 A Null 2127750 A null No nc, NULL Null — 923 2128138 A G 2137901 G G 2135149 G G Yes S, NULL Null — 924 2134872 A D 2144635 G D 2141883 G D Yes S, NULL Null — 925 2136113 G P 2145876 A L 2143124 A L Yes NS, NC O07733 — 926 2137405 T Q 2147123 C R 2144416 C R Yes NS, NC O07732 guanylate cyclase activity 927 2141458 T D 2151176 C D 2148469 C D Yes S, NULL Null — 928 2141625 T M 2151343 C T 2148636 C T Yes NS, NC O07728 — 929 2141958 T T 2151676 G P 2148969 G P Yes NS, NC O07727 monooxygenase activity 930 2145004 A L 2154722 C R 2152015 C R Yes NS, NC Q08129 catalase activity 931 2145783 A T 2155501 G T 2152794 G T Yes S, NULL Null — 932 2146305 T P 2156023 G P 2153316 G P Yes S, NULL Null — 933 2147148 T G 2156866 G G 2154159 G G Yes S, NULL Null — 934 2147202 T T 2156920 A T 2154213 A T Yes S, NULL Null — 935 2148389 C G 2158107 T D 2155400 T D Yes NS, NC O07721 NADPH: quinone reductase activity 936 2153341 A L 2163058 G L 2160351 G L Yes S, NULL Null — 937 2159560 G S 2167924 A L 2165280 A L Yes NS, NC O53960 — 938 2159645 G R 2168009 T S 2165365 T S Yes NS, NC O53960 — 939 2159953 A I 2168317 G T 2165673 G T Yes NS, NC O53960 — 940 2163647 C I 2172010 G M 2169366 G M Yes NS, NC O53962 metabolism 941 2166221 A R 2174584 C R 2171940 C R Yes S, NULL Null — 942 2167025 A D 2175388 G G 2172744 G G Yes NS, NC P95290 — 943 2167348 A N 2175711 G D 2173067 G D Yes NS, NC P95290 — 944 2168708 C Null 2177071 T Null 2174427 T null No nc, NULL Null — 945 2180277 T C 2188640 C C 2185973 C C Yes S, NULL Null — 946 2188349 C L 2196713 G V 2194046 G V Yes NS, C P95269 — 947 2188810 A T 2197174 G T 2194507 G T Yes S, NULL Null — 948 2189303 T T 2197667 C A 2195000 C A Yes NS, NC P95268 — 949 2190686 G R 2199050 C G 2196383 C G Yes NS, NC P95266 — 950 2191050 G L 2199414 A F 2196747 A F Yes NS, NC P95265 — 951 2192930 C R 2201294 T H 2198627 T null Yes NS, NC P95260 — 952 2200251 G G 2221333 A D 2218667 A D Yes NS, NC O53979 S-adenosylmethionine- dependent methyltransferase activity 953 2201224 C G 2222306 T D 2219640 T D Yes NS, NC Q10875 amino acid-polyamine transporter activity 954 2204091 C R 2225173 A L 2222507 A L Yes NS, NC Q10840 ribonucleoside- diphosphate reductase activity 955 2205817 A T 2226899 G A 2224233 G A Yes NS, NC Q10873 integral to membrane 956 2208717 G P 2229799 C P 2227133 C P Yes S, NULL Null — 957 2210402 G Null 2231484 A Null 2228818 A null No nc, NULL Null — 958 2220658 G P 2241740 A P 2239074 A P Yes S, NULL Null — 959 2221950 G R 2243032 T S 2240366 T S Yes NS, NC Q10859 enzyme activity 960 2223259 T R 2244341 G R 2241675 G R Yes S, NULL Null — 961 2225876 C V 2246958 G V 2244292 G V Yes S, NULL Null — 962 2226085 A H 2247167 G R 2244501 G R Yes NS, NC Q10856 — 963 2231155 A S 2252237 G G 2249571 G G Yes NS, NC Q10850 carbohydrate metabolism 964 2232015 C A 2253097 A A 2250431 A A Yes S, NULL Null — 965 2234651 C P 2255733 T L 2253067 T L Yes NS, NC Q10850 carbohydrate metabolism 966 2237132 G D 2258214 A N 2255548 A N Yes NS, NC Q10848 — 967 2239016 T Null 2260098 C Null 2257432 C null No nc, NULL Null — 968 2240157 G E 2261239 A E 2258573 A E Yes S, NULL Null — 969 2240609 C Null 2261691 G Null 2259025 G null No nc, NULL Null — 970 2244542 G G 2265624 A D 2262958 A D Yes NS, NC O53464 — 971 2246892 T R 2267974 G R 2265308 G R Yes S, NULL Null — 972 2247313 T L 2268395 C Null 2265729 C L Yes nc, NULL Null — 973 2253136 C V 2269218 A F 2271552 A F Yes NS, NC O53470 ATP binding activity 974 2253292 A C 2269374 G R 2271708 G R Yes NS, NC O53470 ATP binding activity 975 2255734 G Null 2271818 A Null 2274152 A null No nc, NULL Null — 976 2258377 C V 2274461 A L 2276795 A L Yes NS, C O53473 ATP binding activity 977 2263994 T L 2280079 C P 2282413 C P Yes NS, NC O53476 — 978 2266289 T V 2282374 C V 2284708 C V Yes S, NULL Null — 979 2266290 T V 2282375 C V 2284709 C V Yes S, NULL Null — 980 2271395 A V 2287480 G A 2289814 G A Yes NS, C O53485 transporter activity 981 2272986 C D 2289071 G H 2291405 G H Yes NS, NC Q50575 enzyme activity 982 2275230 C P 2291315 T S 2293649 T S Yes NS, NC O53489 — 983 2282106 T S 2298191 C G 2300525 C G Yes NS, NC O53489 enzyme activity 984 2285002 C L 2301087 T L 2303421 T L Yes S, NULL Null — 985 2304443 G A 2320528 A V 2322862 A V Yes NS, C O53498 biosynthesis 986 2312457 C M 2328541 T I 2330875 T I Yes NS, NC Q10672 porphyrin biosynthesis 987 2312508 A G 2328592 G G 2330926 G G Yes S, NULL Null — 988 2312541 T A 2328625 C A 2330959 C A Yes S, NULL Null — 989 2313380 T P 2329464 C P 2331798 C P Yes S, NULL Null — 990 2317013 T H 2335125 C H 2337459 C H Yes S, NULL Null — 991 2317887 T L 2335999 C P 2338333 C P Yes NS, NC Q10687 — 992 2319259 C A 2337371 T V 2339705 T V Yes NS, C Q10688 membrane 993 2322578 T L 2340687 C L 2343015 C L Yes S, NULL Null — 994 2322919 A T 2341028 G A 2343356 G A Yes NS, NC Q10691 integral to membrane 995 2329583 T I 2347738 C T 2350008 C T Yes NS, NC Q10699 DNA binding activity 996 2332029 G R 2350184 A R 2352454 A R Yes S, NULL Null — 997 2333365 A M 2351520 G T 2353790 G T Yes NS, NC Q10701 nucleic acid binding activity 998 2335359 A V 2353514 G A 2355783 G A Yes NS, C Q10704 — 999 2344034 T S 2362191 G A 2364459 G A Yes NS, NC O53499 nucleic acid binding activity 1000 2349668 C G 2369184 G R 2370093 G R Yes NS, NC O33244 endopeptidase activity 1001 2353673 C P 2373246 A T 2374098 A T Yes NS, NC O33248 — 1002 2353887 T L 2373460 C S 2374312 C S Yes NS, NC O33248 — 1003 2354188 T Y 2373761 C Y 2374613 C Y Yes S, NULL Null — 1004 2356850 G Null 2376423 A Null 2377275 A null No nc, NULL Null — 1005 2360168 G Null 2379741 C Null 2380593 C null Yes nc, NULL Null — 1006 2364212 C V 2383812 T I 2382390 T I Yes NS, C O33259 dihydropteroate synthase activity 1007 2365161 C R 2384761 A R 2383339 A R Yes S, NULL Null — 1008 2369039 A D 2388639 G G 2387216 G null Yes NS, NC O33261 amino acid-polyamine transporter activity 1009 2369143 A S 2388743 G G 2387320 G G Yes NS, NC O33261 amino acid-polyamine transporter activity 1010 2370697 G Null 2390297 A Null 2388874 A null No nc, NULL Null — 1011 2373913 C R 2393513 T R 2392090 T R Yes S, NULL Null — 1012 2377026 C V 2396626 A L 2395203 A L Yes NS, C O06239 undecaprenol kinase activity 1013 2384213 C L 2403697 G L 2402390 G L Yes S, NULL Null — 1014 2393645 G P 2413129 A L 2411822 A L Yes NS, NC O06224 cytokinesis 1015 2393760 A L 2413244 C V 2411937 C V Yes NS, C O06224 cytokinesis 1016 2395865 A V 2415349 C V 2414042 C V Yes S, NULL Null — 1017 2399656 G V 2419140 A V 2417833 A V Yes S, NULL Null — 1018 2402330 G A 2421814 A V 2420507 A V Yes NS, C O06217 — 1019 2405256 G Null 2424862 A Null 2423555 A null No nc, NULL Null — 1020 2405346 C Null 2424952 A Null 2423645 A null No nc, NULL Null — 1021 2405863 C R 2425469 T R 2424162 T R Yes S, NULL Null — 1022 2408026 G A 2427632 A V 2426325 A V Yes NS, C O06213 — 1023 2413856 G Null 2434820 A Null 2432155 A null No nc, NULL Null — 1024 2416293 T S 2437257 G A 2434592 G A Yes NS, NC O53508 — 1025 2416871 A L 2437835 G P 2435170 G P Yes NS, NC O53509 — 1026 2417128 G A 2438092 T S 2435427 T S Yes NS, NC O53510 protein kinase activity 1027 2418638 T K 2439602 G T 2436937 G T Yes NS, NC O53511 DNA binding activity 1028 2421783 T T 2442747 G P 2440082 G P Yes NS, NC O53514 — 1029 2423986 C G 2444950 A G 2442285 A G Yes S, NULL Null — 1030 2426460 T I 2447424 G I 2444759 G I Yes S, NULL Null — 1031 2426573 G Null 2447537 A Null 2444872 A null No nc, NULL Null — 1032 2427491 T S 2448456 C S 2445791 C S Yes S, NULL Null — 1033 2428328 A E 2449293 G G 2446628 G G Yes NS, NC O53521 enzyme activity 1034 2433965 A T 2454930 G T 2452265 G T Yes S, NULL Null — 1035 2433967 G T 2454932 A T 2452267 A T Yes S, NULL Null — 1036 2438267 C I 2459232 G M 2456567 G M Yes NS, NC Q10387 electron transport 1037 2440692 A S 2461543 C A 2458821 C A Yes NS, NC Q10389 integral to membrane 1038 2447668 T V 2468519 C V 2465797 C V Yes S, NULL Null — 1039 2449344 G C 2470195 A C 2467473 A C Yes S, NULL Null — 1040 2449738 C Null 2470589 A Null 2467867 A null Yes S, NULL Null — 1041 2452103 C S 2472954 T L 2470232 T L Yes NS, NC Q10397 porphyrin biosynthesis 1042 2454263 A F 2475114 G F 2472392 G F Yes S, NULL Null — 1043 2455035 G A 2475886 T E 2473164 T E Yes NS, NC Q10399 enzyme activity 1044 2458114 G L 2478965 C F 2476243 C F Yes NS, NC Q10401 aminopeptidase activity 1045 2463948 G G 2484799 A D 2482077 A D Yes NS, NC Q10404 enzyme activity 1046 2465601 C L 2486452 T F 2483730 T F Yes NS, NC Q10405 integral to membrane 1047 2468463 G Null 2489314 A Null 2486590 A null No nc, NULL Null — 1048 2474596 C Null 2495447 T Null 2492723 T null No nc, NULL Null — 1049 2474647 C L 2495498 T L 2492774 T L Yes S, NULL Null — 1050 2478070 A D 2498921 G G 2496197 G G Yes NS, NC Q10510 — 1051 2480295 C A 2501146 T A 2498422 T A Yes S, NULL Null — 1052 2480652 C L 2501502 T F 2498778 T F Yes NS, NC Q10511 — 1053 2481905 T Q 2502755 C R 2500031 C null Yes NS, NC Q10513 kinesin complex 1054 2488510 A I 2509360 G T 2506634 G T Yes NS, NC Q10518 vitamin B12 biosynthesis 1055 2488792 A G 2509642 G G 2506916 G G Yes S, NULL Null — 1056 2490860 T K 2511710 G T 2508984 G T Yes NS, NC Q10522 integral to membrane 1057 2492611 C R 2513461 G G 2510735 G G Yes NS, NC Q10504 pyruvate dehydrogenase (lipoamide) activity 1058 2494787 T V 2515637 G V 2512911 G V Yes S, NULL Null — 1059 2497280 T T 2518130 C T 2515404 C T Yes S, NULL Null — 1060 2501788 A E 2522726 C D 2519999 C D Yes NS, C Q10526 — 1061 2504215 G A 2525150 T D 2522412 T D Yes NS, NC Q10528 DNA binding activity 1062 2507835 A V 2528771 G A 2526031 G A Yes NS, C O53528 lysine permease activity 1063 2508361 A Null 2529297 G Null 2526557 G null Yes nc, NULL Null — 1064 2508860 C G 2529796 G A 2527056 G A Yes NS, C O53530 — 1065 2509390 C R 2530326 A R 2527586 A R Yes S, NULL Null — 1066 2516165 C P 2537209 G P 2534414 G P Yes S, NULL Null — 1067 2518574 A V 2539618 G V 2536823 G V Yes S, NULL Null — 1068 2520531 G Null 2541575 A Null 2538780 A null No nc, NULL Null — 1069 2524106 T L 2545150 C P 2542355 C P Yes NS, NC Q50693 membrane 1070 2525002 G L 2546046 C L 2543251 C L Yes S, NULL Null — 1071 2525661 C M 2546705 T I 2543910 T M Yes NS, NC Q50689 — 1072 2528547 G P 2549591 A L 2546796 A L Yes NS, NC Q50687 glycerol metabolism 1073 2533496 T Null 2555898 G Null 2551745 G null No nc, NULL Null — 1074 2536766 A * 2559168 G Q 2555015 G Q Yes NS, TP Q50679 protein disulfide oxidoreductase activity 1075 2537259 G Null 2559661 C Null 2555508 C null No nc, NULL Null — 1076 2540378 C A 2562781 T V 2558628 T V Yes NS, C Q50675 membrane 1077 2541551 C A 2563956 A E 2559803 A E Yes NS, NC Q59570 thiosulfate sulfurtransferase activity 1078 2544362 G Null 2566766 A Null 2562613 A null No nc, NULL Null — 1079 2550055 A H 2572458 G H 2568305 G H Yes S, NULL Null — 1080 2553846 A D 2576249 G G 2572096 G G Yes NS, NC Q50660 molecular_function unknown 1081 2554841 G V 2577244 A V 2573091 A V Yes S, NULL Null — 1082 2555589 A W 2577992 G R 2573839 G R Yes NS, NC Q50658 enzyme activity 1083 2558141 T V 2580544 G G 2576391 G G Yes NS, C Q50657 — 1084 2558704 A R 2581107 C R 2576954 C R Yes S, NULL Null — 1085 2560796 A K 2583199 G Null 2579046 G E Yes nc, NULL Null — 1086 2569172 G V 2591575 C L 2587422 C L Yes NS, C P71894 transporter activity 1087 2573528 T T 2595931 C A 2591777 C A Yes NS, NC P71889 — 1088 2579779 C A 2602182 G A 2598028 G A Yes S, NULL Null — 1089 2582470 C L 2604873 A L 2600719 A null Yes S, NULL Null — 1090 2582888 T D 2605291 G E 2601137 G E Yes NS, C P71880 malic enzyme activity 1091 2583687 C L 2606090 A I 2601936 A I Yes NS, C P71880 malic enzyme activity 1092 2586084 C Null 2608486 T Null 2604332 T null Yes nc, NULL Null — 1093 2589179 T H 2611581 C H 2607427 C H Yes S, NULL Null — 1094 2589896 T R 2612298 G R 2608144 G R Yes S, NULL Null — 1095 2592420 T V 2614821 C A 2610667 C A Yes NS, C P95235 membrane 1096 2594770 A Null 2617171 G Null 2613017 G null Yes S, NULL Null — 1097 2596868 C Null 2619269 T Null 2615115 T null No nc, NULL Null — 1098 2603521 C A 2625922 T A 2621768 T A Yes S, NULL Null — 1099 2609911 G R 2641838 A H 2639170 A H Yes NS, NC O05839 transcription factor activity 1100 2611180 A F 2643107 G F 2640439 G F Yes S, NULL Null — 1101 2614613 A A 2646540 G A 2643872 G A Yes S, NULL Null — 1102 2626747 A V 2658674 G A 2656006 G A Yes NS, C O05819 enzyme activity 1103 2627613 C G 2659540 T G 2656872 T G Yes S, NULL Null — 1104 2643121 T Q 2675048 C R 2672380 C R Yes NS, NC P71717 enzyme activity 1105 2650664 T T 2682591 C A 2679923 C A Yes NS, NC P71756 magnesium ion binding activity 1106 2652240 G T 2684167 A I 2681499 A I Yes NS, NC P71754 — 1107 2656797 C A 2688724 T A 2686056 T A Yes S, NULL Null — 1108 2657264 A Q 2689191 G R 2686523 G R Yes NS, NC P71750 gamma-glutamyl transferase activity 1109 2659785 C P 2691711 T S 2689043 T S Yes NS, NC P71749 — 1110 2660947 A N 2692873 G S 2690205 G S Yes NS, C P71748 oxygen transporter activity 1111 2661446 C A 2693375 T A 2690707 T A Yes S, NULL Null — 1112 2661841 G S 2693770 A N 2691102 A N Yes NS, C P71748 oxygen transporter activity 1113 2663078 T H 2695007 C R 2692339 C R Yes NS, NC P71746 transporter activity 1114 2668981 G L 2700910 C V 2698242 C V Yes NS, C P71740 — 1115 2671087 T G 2703016 G G 2700348 G G Yes S, NULL Null — 1116 2671898 T A 2703827 C A 2701157 C A Yes S, NULL Null — 1117 2677979 G A 2709793 A A 2706644 A A Yes S, NULL Null — 1118 2681098 A L 2712911 C R 2709762 C R Yes NS, NC P71728 DNA binding activity 1119 2683310 C A 2715123 T T 2711974 T T Yes NS, NC P71727 — 1120 2684991 C R 2716804 T R 2713655 T R Yes S, NULL Null — 1121 2685491 A V 2717304 G A 2714155 G A Yes NS, C P71724 enzyme activity 1122 2686456 T S 2718269 C G 2715120 C G Yes NS, NC O86328 nicotinate-nucleotide adenylyltransferase activity 1123 2687242 A Null 2719055 G Null 2715906 G null No nc, NULL Null — 1124 2689080 A Y 2720893 G H 2717744 R ? Yes NS, C P71924 DNA binding activity 1125 2689137 C A 2720950 T T 2717801 Y ? Yes NS, NC P71924 DNA binding activity 1126 2689139 A I 2720952 G T 2717803 R ? Yes NS, NC P71924 DNA binding activity 1127 2691689 C L 2723504 T L 2720355 T L Yes S, NULL Null — 1128 2692030 G L 2723845 A F 2720696 A F Yes NS, NC P71922 nucleotide binding activity 1129 2693966 T V 2725801 C Null 2722652 C V Yes nc, NULL Null — 1130 2702213 T V 2734048 C A 2730899 C A Yes NS, C P71913 ribokinase activity 1131 2705180 A Null 2737015 G Null 2733866 G null Yes nc, NULL Null — 1132 2708856 C Null 2740691 T Null 2737539 T null Yes nc, NULL Null — 1133 2709921 T L 2741756 G L 2738604 G L Yes S, NULL Null — 1134 2719463 A T 2751298 G T 2748146 G T Yes S, NULL Null — 1135 2720611 G D 2752446 A N 2749294 A N Yes NS, NC O53178 — 1136 2721171 T Null 2753006 C Null 2749854 C null No nc, NULL Null — 1137 2728310 T R 2760145 C R 2756992 C R Yes S, NULL Null — 1138 2729181 A I 2761016 G M 2757863 G M Yes NS, NC O53186 transporter activity 1139 2733102 A L 2764937 G P 2761784 G P Yes NS, NC O53189 cytokinesis 1140 2736005 C Q 2767840 T Q 2764687 T Q Yes S, NULL Null — 1141 2740904 A S 2772739 C A 2769586 C A Yes NS, NC O53196 nucleic acid binding activity 1142 2741117 C G 2772952 T S 2769799 T S Yes NS, NC O53196 nucleic acid binding activity 1143 2742343 C S 2774178 G W 2771025 G W Yes NS, NC O53198 alpha-amylase activity 1144 2743386 T Null 2775221 C Null 2772068 C null No nc, NULL Null — 1145 2745044 A V 2776879 G A 2773726 G A Yes NS, C O53201 — 1146 2751087 C T 2782925 T T 2779772 T T Yes S, NULL Null — 1147 2754350 C S 2787546 T N 2783035 T N Yes NS, C O53207 glycerol-3-phosphate O- acyltransferase activity 1148 2757260 C G 2790456 A C 2785945 A C Yes NS, NC O53208 metabolism 1149 2757900 T D 2791096 C G 2786585 C G Yes NS, NC O53209 molecular_function unknown 1150 2758277 G A 2791473 A A 2786962 A A Yes S, NULL Null — 1151 2762360 T T 2795557 C T 2791046 C T Yes S, NULL Null — 1152 2763122 A V 2796320 G A 2791809 G A Yes NS, C O53212 — 1153 2763158 G T 2796356 C S 2791845 C S Yes NS, C O53212 — 1154 2771624 A H 2804833 G H 2800322 G H Yes S, NULL Null — 1155 2774283 A D 2807484 C A 2802973 C A Yes NS, NC O53217 thymidylate synthase activity 1156 2776115 A W 2809316 G R 2804805 G R Yes NS, NC O06159 protein binding activity 1157 2777179 T S 2810380 C G 2805869 C G Yes NS, NC O06160 — 1158 2779539 G G 2812740 A G 2808229 A G Yes S, NULL Null — 1159 2784243 T L 2817444 G F 2812933 G F Yes NS, NC O06165 biotin carboxylase activity 1160 2785043 T S 2818244 C G 2813733 C G Yes NS, NC O06165 biotin carboxylase activity 1161 2789771 T P 2822972 C P 2818461 C P Yes S, NULL Null — 1162 2792263 A K 2825464 G K 2820953 G K Yes S, NULL Null — 1163 2798279 G G 2831480 A G 2826969 A G Yes S, NULL Null — 1164 2802192 T Null 2835393 C Null 2830882 C null No nc, NULL Null — 1165 2803099 C A 2836300 G A 2831789 G A Yes S, NULL Null — 1166 2803100 C A 2836301 G A 2831790 G A Yes S, NULL Null — 1167 2804844 A M 2838045 G V 2833534 G V Yes NS, NC O53226 — 1168 2807819 G R 2841020 A C 2836509 A C Yes NS, NC P95029 enzyme activity 1169 2814078 G D 2847279 A D 2842768 A D Yes S, NULL Null — 1170 2818088 A V 2851289 G V 2846777 G V Yes S, NULL Null — 1171 2818694 G Q 2851895 C E 2847383 C E Yes NS, NC P95025 — 1172 2819952 A E 2853153 G G 2848641 G G Yes NS, NC P95024 nucleic acid binding activity 1173 2824432 A D 2857633 G D 2853121 G D Yes S, NULL Null — 1174 2825466 T D 2858667 G A 2854156 G A Yes NS, NC P95020 RNA binding activity 1175 2837839 T Null 2870384 C Null 2866530 C null No nc, NULL Null — 1176 2843260 G N 2875806 C K 2871952 C K Yes NS, NC O07438 nucleic acid binding activity 1177 2846432 T D 2878978 C G 2875124 C G Yes NS, NC Q50739 nucleotide binding activity 1178 2849417 C T 2881964 T I 2878109 T I Yes NS, NC Q50737 — 1179 2853851 A S 2886398 G G 2882543 G G Yes NS, NC Q50732 — 1180 2854021 G E 2886568 A E 2882713 A E Yes S, NULL Null — 1181 2854631 T S 2887178 G A 2883323 G A Yes NS, NC Q50732 — 1182 2858117 T L 2890666 C L 2886811 C L Yes S, NULL Null — 1183 2863708 A V 2896258 G A 2892403 G A Yes NS, C Q50649 nucleic acid binding activity 1184 2865290 C Null 2897840 G Null 2893985 G null No nc, NULL Null — 1185 2865319 G Null 2897869 A Null 2894014 A null No nc, NULL Null — 1186 2866213 T A 2898763 C A 2894908 C A Yes S, NULL Null — 1187 2868616 A * 2901166 G W 2897311 G W Yes NS, TP Q50644 hydrolase activity 1188 2871372 A T 2903922 G A 2900067 G A Yes NS, NC Q50642 enzyme activity 1189 2871964 A Q 2904514 G R 2900659 G R Yes NS, NC Q50642 enzyme activity 1190 2874457 T F 2907007 G V 2903152 G V Yes NS, NC Q50639 peptidyl-prolyl cis-trans isomerase activity 1191 2879964 A T 2912514 G T 2908659 G T Yes S, NULL Null — 1192 2880160 G P 2912710 T T 2908855 T T Yes NS, NC Q50635 protein targeting 1193 2880535 T T 2913085 C A 2909230 C A Yes NS, NC Q50635 protein targeting 1194 2881707 C S 2914257 T N 2910402 T N Yes NS, C Q50634 protein targeting 1195 2886244 A Y 2918794 T F 2914939 T F Yes NS, C Q50631 enzyme activity 1196 2887118 A L 2919668 G L 2915813 G L Yes S, NULL Null — 1197 2888634 A T 2921184 G A 2917329 G A Yes NS, NC Q50631 enzyme activity 1198 2890241 A S 2922791 G G 2918936 G G Yes NS, NC Q50630 — 1199 2890386 A D 2922936 G G 2919081 G G Yes NS, NC Q50630 — 1200 2890432 C G 2922982 T G 2919127 T G Yes S, NULL Null — 1201 2893419 C R 2925960 T C 2922105 T C Yes NS, NC Q50625 — 1202 2894748 A A 2927289 G A 2923434 G A Yes S, NULL Null — 1203 2894968 T I 2927509 G S 2923654 G S Yes NS, NC Q50622 integral to membrane 1204 2896114 A L 2928655 G L 2924800 G L Yes S, NULL Null — 1205 2900347 G L 2932888 A F 2929033 A F Yes NS, NC O06209 acyl-CoA metabolism 1206 2903343 T S 2935884 C P 2932029 C P Yes NS, NC O06206 — 1207 2911002 A H 2943543 G Null 2939688 G null Yes nc, NULL Null — 1208 2913009 A I 2945541 G V 2941686 G V Yes NS, C O06198 — 1209 2913792 C Null 2946324 T Null 2942469 T null No nc, NULL Null — 1210 2920364 A H 2952899 G H 2949044 G H Yes S, NULL Null — 1211 2920770 T Null 2953305 G Null 2949450 G null No nc, NULL Null — 1212 2922696 T L 2955231 C S 2951376 C S Yes NS, NC O06184 — 1213 2922723 G R 2955258 C P 2951403 C P Yes NS, NC O06184 — 1214 2926786 G Null 2959321 A Null 2955467 A null No nc, NULL Null — 1215 2929067 G G 2961602 C G 2957748 C G Yes S, NULL Null — 1216 2935735 C A 2968270 T V 2964416 T V Yes NS, C P71942 protein tyrosine phosphatase activity 1217 2935930 C Null 2968465 G Null 2964611 G null Yes nc, NULL Null — 1218 2938515 A R 2982032 G R 2976820 G R Yes S, NULL Null — 1219 2941411 C A 2984929 G G 2979718 G G Yes NS, C P71965 — 1220 2941695 A K 2985213 G E 2980002 G E Yes NS, NC P71965 — 1221 2945109 G D 2988627 C H 2983416 C H Yes NS, NC P71969 — 1222 2948228 G S 2991691 C S 2986535 C S Yes S, NULL Null — 1223 2950721 C L 2994184 T L 2989028 T L Yes S, NULL Null — 1224 2950791 C G 2994254 G A 2989098 G A Yes NS, C O53231 uroporphyrinogen decarboxylase activity 1225 2953961 T V 2997322 C A 2992268 C A Yes NS, C O07183 nucleic acid binding activity 1226 2956998 C S 3000359 T L 2995305 T L Yes NS, NC O07185 — 1227 2959751 G G 3003112 C A 2998058 C A Yes NS, C O07187 transport 1228 2959795 T C 3003156 G G 2998102 G G Yes NS, NC O07187 transport 1229 2963534 A Y 3006895 G Y 3001840 G Y Yes S, NULL Null — 1230 2963874 G R 3007235 A * 3002180 A * Yes NS, TP O07192 amino acid-polyamine transporter activity 1231 2967056 G V 3010417 A I 3005362 A I Yes NS, C O07194 transport 1232 2968202 T S 3011563 G R 3006508 G R Yes NS, NC O07196 nucleic acid binding activity 1233 2969755 T N 3013116 C D 3008061 C D Yes NS, NC O07198 — 1234 2978578 G S 3021939 C T 3016884 C T Yes NS, C O07210 — 1235 2979168 A A 3022529 G A 3017474 G A Yes S, NULL Null — 1236 2979744 T V 3023105 G V 3018050 G V Yes S, NULL Null — 1237 2984242 G W 3027603 C S 3022542 C S Yes NS, NC O07213 — 1238 2984434 C A 3027795 T V 3022734 T V Yes NS, C O07213 — 1239 2984591 A L 3027952 G L 3022891 G L Yes S, NULL Null — 1240 2987804 G H 3031165 A Y 3026104 A Y Yes NS, C O07218 cell wall catabolism 1241 2988773 C A 3032134 T V 3027073 T V Yes NS, C Q50765 DNA binding activity 1242 2993548 G T 3036909 A I 3031848 A I Yes NS, NC O33229 acyl-CoA dehydrogenase activity 1243 2993831 C A 3037192 G P 3032131 G P Yes NS, NC O33229 acyl-CoA dehydrogenase activity 1244 2998193 C Null 3041554 T Null 3036491 T null No nc, NULL Null — 1245 2998315 A V 3041676 G A 3036613 G A Yes NS, C O33234 — 1246 2998989 C L 3042350 G F 3037287 G F Yes NS, NC O33234 — 1247 3001500 T V 3044861 C V 3039798 C V Yes S, NULL Null — 1248 3011613 A G 3055059 C G 3049784 C G Yes S, NULL Null — 1249 3011639 A D 3055085 G G 3049810 G G Yes NS, NC O33284 — 1250 3012496 G L 3055919 A L 3050644 A L Yes S, NULL Null — 1251 3014181 G Q 3057604 T K 3052329 T K Yes NS, NC P31511 — 1252 3015844 G E 3059267 A E 3053992 A null Yes S, NULL Null — 1253 3026379 C V 3069802 G V 3064527 G V Yes S, NULL Null — 1254 3029501 A * 3072924 G Q 3067649 G Q Yes NS, TP O33304 — 1255 3033865 C R 3077288 G P 3072013 G P Yes NS, NC O33310 — 1256 3035400 A S 3078823 G P 3073548 G P Yes NS, NC O33311 — 1257 3036408 A A 3079831 G A 3074556 G A Yes S, NULL Null — 1258 3036451 G S 3079874 A F 3074599 A F Yes NS, NC O33312 — 1259 3038305 A I 3081728 G T 3076453 G T Yes NS, NC P72024 dihydrodipicolinate reductase activity 1260 3038502 T E 3081925 G D 3076650 G D Yes NS, C P72024 dihydrodipicolinate reductase activity 1261 3043278 T I 3086725 C M 3081450 C M Yes NS, NC O33321 DNA binding activity 1262 3045174 G V 3088622 A V 3083347 A V Yes S, NULL Null — 1263 3049237 G Null 3092685 A Null 3087410 A null No nc, NULL Null — 1264 3053917 C A 3097365 A D 3092089 A D Yes NS, NC O33330 transcription factor activity 1265 3054660 A G 3098108 G G 3092832 G G Yes S, NULL Null — 1266 3055488 C Null 3098936 G Null 3093660 G null No nc, NULL Null — 1267 3058474 C A 3101922 T T 3096643 T T Yes NS, NC O33334 recombinase activity 1268 3058662 A V 3102110 G A 3096831 G A Yes NS, C O33334 recombinase activity 1269 3060738 G C 3104186 A C 3098907 A C Yes S, NULL Null — 1270 3061693 A F 3105141 C C 3099862 C C Yes NS, NC P71655 — 1271 3063629 A A 3107077 G A 3101798 G A Yes S, NULL Null — 1272 3066230 C D 3109675 T D 3104396 T D Yes S, NULL Null — 1273 3069429 A V 3112874 G A 3107595 G A Yes NS, C P71647 — 1274 3069475 T T 3112920 C A 3107641 C A Yes NS, NC P71647 — 1275 3072095 C P 3115540 A T 3110261 A T Yes NS, NC P71642 — 1276 3074999 G V 3118446 A I 3113166 A I Yes NS, C P71638 — 1277 3081797 A * 3125232 G Q 3119439 G Q Yes NS, TP P71635 — 1278 3084028 G R 3127463 T R 3121670 T R Yes S, NULL Null — 1279 3089119 G P 3132545 T H 3126761 T H Yes NS, NC P71628 — 1280 3089527 T E 3132953 G A 3127169 G A Yes NS, NC P71627 — 1281 3089534 G L 3132960 A L 3127176 A L Yes S, NULL Null — 1282 3089536 T Q 3132962 G Q 3127178 G Q Yes S, NULL Null — 1283 3089537 G Q 3132963 T Q 3127179 T Q Yes S, NULL Null — 1284 3089546 G L 3132972 C V 3127188 C V Yes NS, C P71627 — 1285 3089625 G C 3133051 C C 3127267 C C Yes S, NULL Null — 1286 3089626 C C 3133052 G C 3127268 G C Yes S, NULL Null — 1287 3091410 A R 3134836 G R 3129052 G R Yes S, NULL Null — 1288 3092467 G G 3135893 A G 3130109 A G Yes S, NULL Null — 1289 3092732 G A 3136158 T E 3130374 T E Yes NS, NC P71624 — 1290 3093808 C Null 3137234 T Null 3131450 T null No nc, NULL Null — 1291 3094520 T C 3137946 C R 3132162 C R Yes NS, NC P71621 enzyme activity 1292 3096227 G P 3139653 C A 3133869 C A Yes NS, NC P71619 transporter activity 1293 3096535 A L 3139961 G P 3134175 G L Yes NS, NC P71619 transporter activity 1294 3096724 A I 3140150 C S 3134364 C I Yes NS, NC P71619 transporter activity 1295 3098942 T L 3142369 C L 3136583 C L Yes S, NULL Null — 1296 3099150 A L 3142577 G P 3136791 G P Yes NS, NC P71616 transporter activity 1297 3103523 C E 3146950 T E 3141164 T E Yes S, NULL Null — 1298 3108827 T T 3152254 C A 3146468 C A Yes NS, NC O05814 tRNA ligase activity 1299 3108991 C R 3152418 T H 3146632 T H Yes NS, NC O05814 tRNA ligase activity 1300 3111157 C R 3154584 T R 3148798 T R Yes S, NULL Null — 1301 3111158 C R 3154585 G R 3148799 G R Yes S, NULL Null — 1302 3114301 G C 3157782 C W 3151996 C W Yes NS, NC O05810 ATP binding activity 1303 3115235 T S 3158716 C G 3152930 C G Yes NS, NC O05809 nucleotide binding activity 1304 3115753 T Q 3159234 C R 3153448 C R Yes NS, NC O05809 nucleotide binding activity 1305 3119320 C N 3162801 A K 3157013 A K Yes NS, NC O05806 — 1306 3121306 T D 3164787 C D 3158999 C D Yes S, NULL Null — 1307 3127009 G P 3170490 C P 3164702 C P Yes S, NULL Null — 1308 3131012 G R 3174493 A C 3168651 A C Yes NS, NC O33344 — 1309 3131107 G P 3174588 C R 3168746 C R Yes NS, NC O33344 — 1310 3133059 A I 3176540 G I 3170698 G I Yes S, NULL Null — 1311 3135930 G A 3179411 T D 3173569 T D Yes NS, NC O33350 isoprenoid biosynthesis 1312 3137504 A F 3180985 C V 3175143 C V Yes NS, NC O33351 metalloendopeptidase activity 1313 3141276 T Null 3184757 G Null 3178914 G null Yes nc, NULL Null — 1314 3144308 C R 3187789 T W 3181946 T R Yes NS, NC Q10802 integral to membrane 1315 3145285 G H 3188766 A Y 3182923 A Y Yes NS, C Q10803 membrane 1316 3145758 G A 3189239 A A 3183396 A A Yes S, NULL Null — 1317 3146096 C Null 3189577 T Null 3183734 T null No nc, NULL Null — 1318 3146180 C K 3189661 T K 3183818 T K Yes S, NULL Null — 1319 3149728 T Null 3193210 C Null 3187366 C null No nc, NULL Null — 1320 3150908 A I 3194389 T K 3188545 T K Yes NS, NC Q10809 — 1321 3152247 C V 3195728 T V 3189884 T V Yes S, NULL Null — 1322 3154848 A M 3198329 G T 3192485 G T Yes NS, NC Q10788 translation elongation factor activity 1323 3156820 G V 3200301 A V 3194457 A V Yes S, NULL Null — 1324 3162781 C G 3206262 T E 3200418 T E Yes NS, NC Q10817 DNA mediated transformation 1325 3163766 T L 3207247 A L 3201403 A L Yes S, NULL Null — 1326 3169156 T H 3212637 C R 3206793 C R Yes NS, NC Q10793 RNA binding activity 1327 3169605 T N 3213086 C D 3207242 C D Yes NS, NC Q10789 proteolysis and peptidolysis 1328 3179819 T E 3223300 C E 3217456 C E Yes S, NULL Null — 1329 3185717 A W 3229198 G R 3223352 G R Yes NS, NC Q10961 enzyme activity 1330 3186529 C R 3230010 A L 3224164 A L Yes NS, NC Q10961 enzyme activity 1331 3187380 A D 3230861 G D 3225015 G D Yes S, NULL Null — 1332 3192343 C G 3235712 G R 3230035 G R Yes NS, NC Q10970 ATP-binding cassette (ABC) transporter activity 1333 3193344 C R 3236713 A L 3231036 A L Yes NS, NC Q10970 ATP-binding cassette (ABC) transporter activity 1334 3199928 C Null 3243352 T Null 3237675 T null No nc, NULL Null — 1335 3200987 G V 3244411 A M 3238734 A M Yes NS, NC Q10976 enzyme activity 1336 3203120 C T 3246544 A N 3240867 A N Yes NS, C Q10977 enzyme activity 1337 3204152 A Q 3247576 G R 3241899 G R Yes NS, NC Q10977 enzyme activity 1338 3211268 T A 3254692 C A 3249015 C A Yes S, NULL Null — 1339 3211453 T L 3254877 G R 3249200 G R Yes NS, NC Q10978 enzyme activity 1340 3217579 A G 3261003 C G 3255326 C G Yes S, NULL Null — 1341 3219201 A I 3262625 G M 3256948 G M Yes NS, NC P96203 enzyme activity 1342 3222603 G S 3266027 A S 3260350 A S Yes S, NULL Null — 1343 3224288 C A 3267712 A E 3262035 A E Yes NS, NC P96203 enzyme activity 1344 3227610 G D 3271034 A N 3265357 A N Yes NS, NC P96204 enzyme activity 1345 3229711 G D 3273135 C H 3267458 C H Yes NS, NC P96205 nucleotide binding activity 1346 3230432 T L 3273856 C L 3268179 C L Yes S, NULL Null — 1347 3238652 A C 3282076 T S 3276399 T S Yes NS, NC P96291 enzyme activity 1348 3239912 T I 3283336 G S 3277659 G S Yes NS, NC P96290 enzyme activity 1349 3240065 G R 3283489 A Q 3277812 A Q Yes NS, NC P96290 enzyme activity 1350 3240165 C G 3283589 G G 3277912 G G Yes S, NULL Null — 1351 3242680 A V 3286104 C V 3280427 C V Yes S, NULL Null — 1352 3243139 T A 3286563 C A 3280886 C A Yes S, NULL Null — 1353 3248962 A V 3292272 G A 3286595 G A Yes NS, C P96285 alcohol dehydrogenase activity 1354 3249193 C G 3292503 A V 3286826 A V Yes NS, C P96285 alcohol dehydrogenase activity 1355 3250170 A A 3293480 G A 3287803 G A Yes S, NULL Null — 1356 3253409 G R 3296718 C G 3291041 C G Yes NS, NC P96284 enzyme activity 1357 3257940 T T 3301249 C A 3295572 C A Yes NS, NC P95141 enzyme activity 1358 3259371 T Null 3302680 C Null 3297003 C null Yes nc, NULL Null — 1359 3265154 T H 3308463 C R 3302785 C R Yes NS, NC P95137 — 1360 3265769 A E 3309078 G E 3303400 G E Yes S, NULL Null — 1361 3266065 C T 3309374 T I 3303696 T I Yes NS, NC P95136 — 1362 3267563 A Null 3310872 G Null 3305194 G null Yes S, NULL Null — 1363 3267807 C D 3311116 G D 3305438 G D Yes S, NULL Null — 1364 3269417 T V 3312725 C V 3307047 C V Yes S, NULL Null — 1365 3271101 G A 3314409 A A 3308731 A A Yes S, NULL Null — 1366 3277243 A S 3320551 G S 3314873 G S Yes S, NULL Null — 1367 3283243 C H 3326551 A N 3320873 A N Yes NS, NC P95124 — 1368 3291984 C G 3335294 T D 3329616 T D Yes NS, NC P95116 recombinase activity 1369 3292201 C A 3335511 T T 3329833 T T Yes NS, NC P95116 recombinase activity 1370 3292395 C R 3335705 G P 3330027 G P Yes NS, NC P95116 recombinase activity 1371 3301607 T E 3345044 G D 3339424 G D Yes NS, C O53237 3-isopropylmalate dehydratase activity 1372 3303630 T E 3347067 G A 3341447 G A Yes NS, NC O53239 — 1373 3304818 A T 3348255 G A 3342635 G A Yes NS, NC O53240 — 1374 3309535 G L 3352916 A F 3347295 A F Yes NS, NC P95313 3-isopropylmalate dehydrogenase activity 1375 3312033 A S 3355414 T C 3349793 T C Yes NS, NC O53244 — 1376 3313133 C P 3356514 T P 3350893 T P Yes S, NULL Null — 1377 3321979 A D 3365361 G G 3359739 G G Yes NS, NC O53253 — 1378 3326484 T Null 3369866 G Null 3364244 G null No nc, NULL Null — 1379 3327875 C V 3371257 T I 3365635 T I Yes NS, C O53258 amidase activity 1380 3327980 T T 3371362 C A 3365740 C A Yes NS, NC O53258 amidase activity 1381 3328016 A L 3371398 G L 3365776 G L Yes S, NULL Null — 1382 3333886 C V 3377268 G L 3371647 G L Yes NS, C P31500 — 1383 3338640 T G 3382077 C G 3377816 C G Yes S, NULL Null — 1384 3339158 T T 3382595 C A 3378334 C A Yes NS, NC P96354 peroxidase activity 1385 3343458 C Null 3386895 T Null 3382634 T null Yes nc, NULL Null — 1386 3343463 G Null 3386900 A Null 3382639 A null Yes nc, NULL Null — 1387 3343657 A V 3387094 G A 3382833 G A Yes NS, C O53275 electron transporter activity 1388 3345242 C V 3388679 T V 3384418 T V Yes S, NULL Null — 1389 3353514 C R 3396951 T Q 3392690 T Q Yes NS, NC O53283 — 1390 3354831 G A 3398268 T D 3394007 T D Yes NS, NC O53284 — 1391 3359515 A S 3402952 C A 3398691 C A Yes NS, NC O53289 phosphoserine phosphatase activity 1392 3362817 A Null 3406254 G Null 3401993 G null No nc, NULL Null — 1393 3366744 A R 3410181 G R 3405920 G R Yes S, NULL Null — 1394 3371878 G Null 3415329 A Null 3411054 A null Yes nc, NULL Null — 1395 3376988 T Y 3420439 C Y 3416164 C Y Yes S, NULL Null — 1396 3377371 G G 3420822 A D 3416547 A D Yes NS, NC P95099 monooxygenase activity 1397 3384993 T C 3428443 G G 3424236 G G Yes NS, NC P95095 cellular response to starvation 1398 3385588 C P 3429038 T L 3424831 T L Yes NS, NC P95095 cellular response to starvation 1399 3386152 A Null 3429602 G Null 3425395 G null Yes nc, NULL Null — 1400 3392209 G Null 3435659 C Null 3431452 C null Yes nc, NULL Null — 1401 3394933 A I 3438383 G I 3434176 G I Yes S, NULL Null — 1402 3397089 G G 3440539 A G 3436332 A G Yes S, NULL Null — 1403 3401113 A L 3444563 G L 3440356 G L Yes S, NULL Null — 1404 3401886 A V 3445336 G A 3441129 G A Yes NS, C P95078 protein kinase activity 1405 3404010 A C 3447460 G R 3443253 G R Yes NS, NC Q06861 DNA binding activity 1406 3405330 A I 3448780 G V 3444573 G V Yes NS, C O53300 — 1407 3409943 G A 3453393 A T 3449186 A T Yes NS, NC O53304 molecular_function unknown 1408 3410810 G V 3454260 C L 3450053 C L Yes NS, C O53304 molecular_function unknown 1409 3414061 C Null 3457511 G Null 3453304 G null No nc, NULL Null — 1410 3417571 C M 3461021 T I 3456814 T I Yes NS, NC O05771 — 1411 3421176 G G 3464626 A E 3460424 A E Yes NS, NC O05775 hydrolase activity 1412 3423466 G A 3466916 C G 3462714 C G Yes NS, C P77909 enzyme activity 1413 3423862 C E 3467312 G D 3463110 G D Yes NS, C O05776 — 1414 3424012 G A 3467462 C A 3463260 C A Yes S, NULL Null — 1415 3426715 C S 3470165 T N 3465963 T N Yes NS, C P96293 cytokinesis 1416 3430975 A I 3474424 G V 3470223 G V Yes NS, C O05783 ferredoxin-NADP reductase activity 1417 3431707 G D 3475156 A N 3470955 A N Yes NS, NC O05783 ferredoxin-NADP reductase activity 1418 3434037 G V 3477486 A I 3473285 A I Yes NS, C O05785 — 1419 3434151 T Null 3477600 C Null 3473399 C null No nc, NULL Null — 1420 3435166 G A 3478615 A T 3474414 A T Yes NS, NC O05786 enzyme activity 1421 3436346 A G 3479795 G G 3475594 G G Yes S, NULL Null — 1422 3436653 C C 3480103 G W 3475902 G W Yes NS, NC O05790 metabolism 1423 3437192 G R 3480642 T L 3476441 T L Yes NS, NC O05790 metabolism 1424 3437336 C P 3480786 T S 3476585 T S Yes NS, NC O05791 zinc ion binding activity 1425 3438022 A T 3481472 G A 3477271 G A Yes NS, NC P96354 peroxidase activity 1426 3438540 A G 3481990 G G 3477789 G G Yes S, NULL Null — 1427 3442328 T S 3488553 G R 3484352 G R Yes NS, NC O07033 — 1428 3442459 A Q 3488684 G R 3484483 G R Yes NS, NC O07034 — 1429 3443112 G Null 3489337 C Null 3485136 C null No nc, NULL Null — 1430 3445311 A V 3491536 G A 3487335 G A Yes NS, C O05798 — 1431 3446202 G C 3492427 T F 3488226 T F Yes NS, NC O05800 — 1432 3447457 C G 3493682 A V 3489481 A null Yes NS, C Not — annotated 1433 3452190 G T 3498415 A I 3494214 A I Yes NS, NC P95194 ATP binding activity 1434 3456796 T Null 3501684 C Null 3497171 C null Yes S, NULL Null — 1435 3459632 A N 3504520 G S 3500007 G S Yes NS, C P95188 lyase activity 1436 3460073 C S 3504961 T F 3500448 T F Yes NS, NC P95188 lyase activity 1437 3460112 T L 3505000 C P 3500487 C P Yes NS, NC P95188 lyase activity 1438 3460114 C P 3505002 A T 3500489 A T Yes NS, NC P95188 lyase activity 1439 3464200 C Null 3509088 G Null 3504575 G null No nc, NULL Null — 1440 3464257 C Q 3509145 A H 3504632 A H Yes NS, NC P95184 — 1441 3465229 G Q 3510117 T K 3505604 T K Yes NS, NC P95182 — 1442 3466696 G Null 3511584 T Null 3507071 T null No nc, NULL Null — 1443 3467191 C G 3512079 A G 3507566 A G Yes S, NULL Null — 1444 3468833 T N 3513721 C N 3509208 C N Yes S, NULL Null — 1445 3470134 T G 3515022 C G 3510509 C G Yes S, NULL Null — 1446 3472676 T N 3517564 C N 3513051 C N Yes S, NULL Null — 1447 3476153 G A 3521041 A T 3516528 A T Yes NS, NC P95173 electron transporter activity 1448 3478232 A Y 3523120 T F 3518607 T F Yes NS, C O86350 oxidative phosphorylation 1449 3480424 A D 3525312 G G 3520799 G G Yes NS, NC O53307 oxidative phosphorylation 1450 3480666 A I 3525554 G V 3521041 G V Yes NS, C O53307 oxidative phosphorylation 1451 3482095 T A 3526983 A A 3522470 A A Yes S, NULL Null — 1452 3483661 T E 3528549 G D 3524036 G D Yes NS, C O53309 — 1453 3488207 G L 3530952 C V 3528588 C V Yes NS, C O53311 iron ion binding activity 1454 3489142 T E 3531888 G D 3529524 G D Yes NS, C O53313 transporter activity 1455 3491098 C G 3533844 T E 3531480 T E Yes NS, NC O53314 — 1456 3492231 G V 3534977 C V 3532613 C V Yes S, NULL Null — 1457 3493545 C R 3536291 T W 3533927 T W Yes NS, NC O53318 — 1458 3497395 A M 3540141 G T 3537777 G T Yes NS, NC O53321 enzyme activity 1459 3499414 C A 3542160 T V 3539796 T V Yes NS, C O53324 metabolism 1460 3500015 C L 3542761 G L 3540397 G L Yes S, NULL Null — 1461 3510233 G A 3555696 A V 3550616 A V Yes NS, C O53336 — 1462 3515180 T Q 3560642 C R 3555549 C R Yes NS, NC O53339 molecular_function unknown 1463 3519984 A E 3565446 G E 3560353 G E Yes S, NULL Null — 1464 3522549 A R 3568001 C R 3562908 C R Yes S, NULL Null — 1465 3526379 G P 3571831 T Q 3566738 T Q Yes NS, NC O53345 magnesium ion binding activity 1466 3528181 C D 3573633 T N 3568540 T N Yes NS, NC O53346 potassium channel activity 1467 3532503 G A 3577955 A V 3572862 A V Yes NS, C O53348 DNA binding activity 1468 3538731 T N 3584187 C D 3579093 C null Yes NS, NC O05859 proteolysis and peptidolysis 1469 3542388 C A 3587844 T V 3582750 T V Yes NS, C O05855 nucleic acid binding activity 1470 3544683 C A 3590139 T V 3585045 T V Yes NS, C O05854 — 1471 3545177 C Null 3590633 G Null 3585539 G null No nc, NULL Null — 1472 3545178 G Null 3590634 C Null 3585540 C null No nc, NULL Null — 1473 3549450 A Q 3594848 G Q 3589751 G Q Yes S, NULL Null — 1474 3550026 A R 3595424 G R 3590327 G R Yes S, NULL Null — 1475 3551995 T N 3597393 C D 3592296 C D Yes NS, NC O05846 ATP binding activity 1476 3556127 T T 3601524 C A 3596428 C A Yes NS, NC O05841 N-acetyltransferase activity 1477 3558424 A H 3603821 G R 3598725 G R Yes NS, NC P22487 3-phosphoshikimate 1- carboxyvinyltransferase activity 1478 3561226 A L 3606623 G L 3601527 G L Yes S, NULL Null — 1479 3562541 A C 3607938 G R 3602842 G R Yes NS, NC O05875 electron transporter activity 1480 3563125 A V 3608522 G V 3603426 G V Yes S, NULL Null — 1481 3566088 C G 3611484 G G 3606388 G G Yes S, NULL Null — 1482 3569604 T H 3615000 C R 3609903 C R Yes NS, NC O05884 enzyme activity 1483 3577972 G P 3623368 C P 3618271 C P Yes S, NULL Null — 1484 3578330 A L 3623726 G S 3618629 G S Yes NS, NC O05889 — 1485 3578950 A A 3624346 C A 3619249 C A Yes S, NULL Null — 1486 3579086 C G 3624482 T D 3619385 T D Yes NS, NC O05889 — 1487 3579193 T V 3624589 C V 3619492 C V Yes S, NULL Null — 1488 3579310 T L 3624706 C L 3619609 C L Yes S, NULL Null — 1489 3583683 T I 3629079 C V 3623982 C V Yes NS, C O08364 adenosylhomocysteinase activity 1490 3592693 A L 3638089 G S 3632992 G S Yes NS, NC O86374 carbohydrate metabolism 1491 3601629 G P 3647037 A S 3641940 A S Yes NS, NC P96871 dTDP-4- dehydrorhamnose reductase activity 1492 3609075 G S 3654483 A N 3649386 A N Yes NS, C P96877 metabolism 1493 3609941 T F 3655349 C F 3650252 C F Yes S, NULL Null — 1494 3612854 G R 3658262 C G 3653165 C G Yes NS, NC P96880 phospho- ribosylaminoimidazole carboxylase activity 1495 3615280 T L 3660688 C S 3655591 C S Yes NS, NC P96882 — 1496 3615970 T N 3661378 C D 3656280 C D Yes NS, NC P96884 biotin-apoprotein ligase activity 1497 3617992 C A 3663400 T V 3658302 T V Yes NS, C P96885 biotin carboxylase activity 1498 3619140 T S 3664611 G A 3659450 G A Yes NS, NC P96887 — 1499 3619961 A D 3665432 G G 3660271 G G Yes NS, NC P96888 thiosulfate sulfurtransferase activity 1500 3621718 T H 3667189 C H 3662028 C H Yes S, NULL Null — 1501 3622087 C G 3667558 T G 3662397 T G Yes S, NULL Null — 1502 3624565 T A 3670036 C A 3664875 C A Yes S, NULL Null — 1503 3626758 A V 3672229 G A 3667068 G A Yes NS, C P96896 DNA binding activity 1504 3628943 T C 3674414 G G 3669253 G G Yes NS, NC P96898 metabolism 1505 3633454 A M 3678925 G V 3673764 G V Yes NS, NC P96901 nucleotide binding activity 1506 3633751 A N 3679222 G D 3674061 G D Yes NS, NC P96901 nucleotide binding activity 1507 3634474 G E 3679945 A K 3674784 A K Yes NS, NC P96901 nucleotide binding activity 1508 3636073 C R 3681544 A R 3676383 A R Yes S, NULL Null — 1509 3639879 T S 3685350 C G 3680189 C G Yes NS, NC O65931 enzyme activity 1510 3641272 T N 3686743 C D 3681582 C D Yes NS, NC O07166 pseudouridylate synthase activity 1511 3644541 G S 3690012 A L 3684851 A L Yes NS, NC O53355 cytoplasm 1512 3645379 C A 3690850 T T 3685689 T T Yes NS, NC O53355 cytoplasm 1513 3648206 C A 3693677 A A 3688572 A A Yes S, NULL Null — 1514 3650706 G G 3696177 A S 3691072 A S Yes NS, NC O53360 carbohydrate metabolism 1515 3652233 G A 3697704 A T 3692599 A T Yes NS, NC O53361 hydrolase activity 1516 3654880 G Null 3700351 A Null 3695243 A null No nc, NULL Null — 1517 3657068 A W 3702539 G R 3697430 G R Yes NS, NC O53366 pyrimidine base metabolism 1518 3659623 A V 3705094 G V 3699985 G V Yes S, NULL Null — 1519 3660007 A E 3705478 G E 3700369 G E Yes S, NULL Null — 1520 3661401 G E 3706872 C D 3701763 C D Yes NS, C O53371 electron transporter activity 1521 3662101 C Null 3707572 G Null 3702463 G null No nc, NULL Null — 1522 3662102 G Null 3707573 C Null 3702464 C null No nc, NULL Null — 1523 3663410 A A 3708884 G A 3703775 G A Yes S, NULL Null — 1524 3671821 T L 3714568 C L 3712186 C L Yes S, NULL Null — 1525 3672930 T D 3715677 C D 3713295 C D Yes S, NULL Null — 1526 3673148 A V 3715895 G V 3713513 G V Yes S, NULL Null — 1527 3687716 G T 3730462 A I 3728072 A null Yes NS, NC O53393 carboxypeptidase A activity 1528 3693443 G A 3740060 T E 3732216 T E Yes NS, NC O53395 — 1529 3693692 A V 3740309 C G 3732465 C G Yes NS, C O53395 — 1530 3696063 A T 3742525 G T 3734759 G T Yes S, NULL Null — 1531 3697083 G Null 3743545 A Null 3735779 A null No nc, NULL Null — 1532 3699350 T N 3745812 C D 3738047 C null Yes NS, NC O50378 — 1533 3700460 C W 3746922 T W 3739156 T null Yes S, NULL Null — 1534 3701886 G A 3748349 C G 3740583 C null Yes NS, C O50378 — 1535 3703453 A S 3749916 G P 3742150 G null Yes NS, NC O50378 — 1536 3703940 C G 3750403 G G 3742637 G null Yes S, NULL Null — 1537 3703950 T Y 3750413 A F 3742647 A null Yes NS, C O50378 — 1538 3703954 C G 3750417 T S 3742651 T null Yes NS, NC O50378 — 1539 3704386 G L 3750849 A L 3743083 A null Yes S, NULL Null — 1540 3704564 G G 3751027 A G 3743261 A null Yes S, NULL Null — 1541 3704570 G N 3751033 A N 3743267 A null Yes S, NULL Null — 1542 3706162 T I 3752625 G L 3744859 G null Yes NS, C O50378 — 1543 3706947 G Null 3753410 T Null 3745645 T null Yes nc, NULL Null — 1544 3708970 A Null 3755439 G Null 3747674 G null No nc, NULL Null — 1545 3711573 T S 3758042 C S 3750277 C null Yes S, NULL Null — 1546 3715389 A V 3761859 G A 3754086 G null Yes NS, C O50379 — 1547 3717907 C D 3764377 T N 3756604 T null Yes NS, NC O50379 — 1548 3719141 C A 3765611 G A 3757838 G null Yes S, NULL Null — 1549 3719324 T Null 3765794 G Null 3758021 G null Yes S, NULL Null — 1550 3719936 G G 3766406 C G 3758633 C null Yes S, NULL Null — 1551 3720790 G Null 3767260 A Null 3759487 A null No nc, NULL Null — 1552 3722971 C A 3769441 T V 3761668 T V Yes NS, C O50383 — 1553 3724114 G P 3770584 T Q 3762811 T Q Yes NS, NC O50385 enzyme activity 1554 3724214 T Null 3770684 C Null 3762911 C null No nc, NULL Null — 1555 3724771 A L 3771241 G L 3763468 G L Yes S, NULL Null — 1556 3724938 G R 3771408 T R 3763635 T R Yes S, NULL Null — 1557 3725154 C I 3771624 A I 3763851 A I Yes S, NULL Null — 1558 3726142 A Null 3772612 G Null 3764839 G null No nc, NULL Null — 1559 3729791 T R 3776261 G R 3768488 G R Yes S, NULL Null — 1560 3733435 A S 3779791 G G 3772027 G G Yes NS, NC O50396 — 1561 3736194 A S 3782550 G S 3774786 G S Yes S, NULL Null — 1562 3736445 T R 3782801 G R 3775037 G R Yes S, NULL Null — 1563 3739586 G G 3785942 A R 3778178 A R Yes NS, NC O50400 molecular_function unknown 1564 3739673 G V 3786029 A I 3778265 A I Yes NS, C O50400 molecular_function unknown 1565 3742005 G G 3788361 T * 3780597 T null Yes NS, TP O50402 enzyme activity 1566 3746351 T T 3792708 C T 3784944 C T Yes S, NULL Null — 1567 3747920 T Y 3794277 C C 3786513 C null Yes NS, NC O50408 — 1568 3752240 G Null 3799953 A Null 3790831 A null No nc, NULL Null — 1569 3755845 C A 3803582 G G 3794460 G G Yes NS, C O50415 — 1570 3756614 A L 3804273 G P 3795151 G P Yes NS, NC Q11198 metabolism 1571 3760440 C S 3808099 T N 3798977 T N Yes NS, C Q11195 methyltransferase activity 1572 3763664 T M 3811323 C V 3802201 C V Yes NS, NC Q50730 integral to membrane 1573 3763966 A V 3811625 G A 3802503 G A Yes NS, C Q50730 integral to membrane 1574 3766395 A I 3814054 G I 3804932 G I Yes S, NULL Null — 1575 3772351 A H 3820010 G R 3810888 G R Yes NS, NC Q50724 carbohydrate metabolism 1576 3773467 C Null 3820835 G Null 3811715 G null Yes S, NULL Null — 1577 3774060 A C 3821428 G R 3812308 G R Yes NS, NC Q50723 — 1578 3777374 A L 3824742 G L 3815622 G L Yes S, NULL Null — 1579 3783323 G A 3830691 A A 3821571 A A Yes S, NULL Null — 1580 3795810 T H 3848104 C R 3834058 C R Yes NS, NC O06247 DNA binding activity 1581 3799589 C A 3851883 A S 3837836 A S Yes NS, NC O06250 molecular_function unknown 1582 3799590 C A 3851884 T A 3837837 T A Yes S, NULL Null — 1583 3801054 T T 3853348 C A 3839301 C A Yes NS, NC O06251 — 1584 3804863 C P 3857157 T L 3843110 T L Yes NS, NC O06254 — 1585 3805949 T Null 3858243 C Null 3844196 C null No nc, NULL Null — 1586 3812465 T S 3864760 C G 3850712 C G Yes NS, NC O06264 nucleotide binding activity 1587 3816846 A D 3869141 C A 3855093 C A Yes NS, NC O33354 transporter activity 1588 3817926 T I 3870221 C I 3856173 C I Yes S, NULL Null — 1589 3818947 C G 3871242 T G 3857194 T G Yes S, NULL Null — 1590 3823086 A I 3875382 G V 3861333 G V Yes NS, C O06321 — 1591 3824956 T A 3877252 C A 3863203 C A Yes S, NULL Null — 1592 3826984 A N 3879284 C K 3865235 C K Yes NS, NC O06326 RNA binding activity 1593 3831379 C V 3883679 G V 3869630 G V Yes S, NULL Null — 1594 3831382 G G 3883682 T G 3869633 T G Yes S, NULL Null — 1595 3831386 A T 3883686 G A 3869637 G A Yes NS, NC O06331 — 1596 3831403 C L 3883703 T L 3869654 T L Yes S, NULL Null — 1597 3831407 A T 3883707 G A 3869658 G A Yes NS, NC O06331 — 1598 3831541 C G 3883841 T G 3869792 T G Yes S, NULL Null — 1599 3831611 A I 3883911 G V 3869862 G V Yes NS, C O06331 — 1600 3832059 G E 3884359 A K 3870310 A K Yes NS, NC Q50655 — 1601 3832094 T I 3884394 C I 3870345 C I Yes S, NULL Null — 1602 3832393 G G 3884693 C A 3870644 C A Yes NS, C Q50655 — 1603 3832444 A D 3884744 G G 3870695 G G Yes NS, NC Q50655 — 1604 3832483 G R 3884783 A H 3870734 A H Yes NS, NC Q50655 — 1605 3832818 A N 3885118 G N 3880312 G N Yes S, NULL Null — 1606 3835237 T E 3887537 C G 3882731 C G Yes NS, NC O06335 — 1607 3836573 C W 3888873 G C 3884067 G C Yes NS, NC O06336 nutrient reservoir activity 1608 3839628 A V 3893286 G A 3887122 G A Yes NS, C O06339 transporter activity 1609 3839818 A F 3893476 G L 3887312 G L Yes NS, NC O06339 transporter activity 1610 3840507 T V 3894165 C A 3888001 C A Yes NS, C O06340 — 1611 3842065 A Null 3895723 C Null 3889559 C null Yes S, NULL Null — 1612 3842157 A Null 3895815 G Null 3889651 G null Yes S, NULL Null — 1613 3844494 A N 3898865 C T 3892701 C T Yes NS, C O06342 enzyme activity 1614 3850113 A E 3904486 G E 3898322 G E Yes S, NULL Null — 1615 3853581 A R 3907954 G G 3901790 G G Yes NS, NC O06351 — 1616 3854858 C L 3909231 G V 3903067 G V Yes NS, C O06353 alpha 1617 3858259 C G 3912632 T D 3906467 T D Yes NS, NC O53539 pathogenesis 1618 3865062 A P 3919435 G P 3913270 G P Yes S, NULL Null — 1619 3867127 G A 3921500 C A 3915336 C A Yes S, NULL Null — 1620 3868459 C D 3922832 T D 3916668 T D Yes S, NULL Null — 1621 3869973 T V 3924346 C A 3918182 C A Yes NS, C O53550 acyl-CoA dehydrogenase activity 1622 3870019 A Q 3924392 G Q 3918228 G Q Yes S, NULL Null — 1623 3874389 G G 3928888 A D 3922733 A D Yes NS, NC O53552 — 1624 3875932 A G 3930377 C G 3924213 C G Yes S, NULL Null — 1625 3876018 G G 3930463 A D 3924299 A D Yes NS, NC O53552 — 1626 3908574 C Null 3965355 T Null 3957501 T null No nc, NULL Null — 1627 3910673 C L 3967454 T L 3959600 T L Yes S, NULL Null — 1628 3911467 T S 3968248 C S 3960394 C S Yes S, NULL Null — 1629 3911833 A T 3968614 G T 3960760 G T Yes S, NULL Null — 1630 3921125 A L 3977906 G L 3970052 G L Yes S, NULL Null — 1631 3927536 A H 3984317 G H 3976463 G H Yes S, NULL Null — 1632 3930860 C V 3987641 T M 3979787 T M Yes NS, NC P71853 metabolism 1633 3933129 T S 3989910 G A 3982056 G A Yes NS, NC P71850 metabolism 1634 3938113 G R 3994894 A W 3987040 A null Yes NS, NC P96837 — 1635 3939862 C G 3996643 G G 3988788 G G Yes S, NULL Null — 1636 3942989 A V 3999770 G A 3991914 G V Yes NS, C P96841 metabolism 1637 3946062 A N 4002843 C T 3994987 C T Yes NS, C P96843 enzyme activity 1638 3947819 G R 4004600 A Q 3996744 A Q Yes NS, NC P96845 structural constituent of ribosome 1639 3948329 C S 4005110 G W 3997254 G W Yes NS, NC P96845 structural constituent of ribosome 1640 3951962 G T 4008744 A I 4000886 A I Yes NS, NC P96849 electron transport 1641 3952885 C R 4009667 T Q 4001809 T Q Yes NS, NC P96850 enzyme activity 1642 3955434 C D 4012216 T N 4004358 T N Yes NS, NC P96852 — 1643 3961924 A N 4018706 G D 4010848 G D Yes NS, NC P96858 — 1644 3964308 T S 4021090 G A 4013232 G A Yes NS, NC P96860 arsenite transporter activity 1645 3964705 G A 4021486 T E 4013628 T E Yes NS, NC P96861 RNA binding activity 1646 3964973 T R 4021754 G R 4013896 G R Yes S, NULL Null — 1647 3965078 T M 4021859 C V 4014001 C V Yes NS, NC P96861 RNA binding activity 1648 3967982 C A 4024763 T T 4016905 T T Yes NS, NC P96864 isoprenoid biosynthesis 1649 3971967 G A 4028749 A T 4020891 A T Yes NS, NC O53571 DNA binding activity 1650 3972140 T D 4028922 G E 4021064 G E Yes NS, C O53571 DNA binding activity 1651 3973474 G T 4030256 A I 4022398 A I Yes NS, NC O53573 carbonate dehydratase activity 1652 3978123 G S 4034905 A N 4027047 A N Yes NS, C O06155 — 1653 3978196 A Q 4034978 G Q 4027120 G Q Yes S, NULL Null — 1654 3981644 G L 4038400 A L 4030533 A L Yes S, NULL Null — 1655 3989459 A Null 4046215 G Null 4038347 G null Yes nc, NULL Null — 1656 3990280 C G 4047036 A V 4039168 A V Yes NS, C O06278 — 1657 3990684 C G 4047440 A G 4039572 A G Yes S, NULL Null — 1658 3991234 A G 4047990 G G 4040122 G G Yes S, NULL Null — 1659 3997767 G G 4054634 A G 4046877 A G Yes S, NULL Null — 1660 3997999 T K 4054866 C K 4047109 C K Yes S, NULL Null — 1661 3999048 G A 4055915 A V 4048158 A V Yes NS, C O06267 — 1662 3999546 A Null 4056413 C Null 4048656 C null No nc, NULL Null — 1663 3999563 G Null 4056430 A Null 4048673 A null No nc, NULL Null — 1664 3999617 C Null 4056484 T Null 4048727 T null Yes nc, NULL Null — 1665 4004281 A V 4067041 G A 4059284 G A Yes NS, C O06380 serine carboxypeptidase activity 1666 4004389 A V 4067149 G A 4059392 G A Yes NS, C O06380 serine carboxypeptidase activity 1667 4006348 T Null 4069108 C Null 4061351 C null No nc, NULL Null — 1668 4007724 T Null 4070484 G Null 4062727 G null No nc, NULL Null — 1669 4013888 T I 4076648 C I 4068891 C null Yes S, NULL Null — 1670 4015529 G N 4078289 T K 4070532 T K Yes NS, NC O06368 — 1671 4016100 T E 4078860 C G 4071103 C G Yes NS, NC O06367 — 1672 4017100 G Null 4079860 C Null 4072103 C null No nc, NULL Null — 1673 4020748 T I 4083508 C I 4075752 C I Yes S, NULL Null — 1674 4024907 T V 4087667 C V 4079911 C V Yes S, NULL Null — 1675 4026295 C P 4089055 T L 4081299 T L Yes NS, NC O06359 nucleic acid binding activity 1676 4027898 T H 4090658 C H 4082902 C H Yes S, NULL Null — 1677 4032641 C E 4095292 T E 4087553 T E Yes S, NULL Null — 1678 4033932 A A 4096583 G A 4088843 G A Yes S, NULL Null — 1679 4036406 A L 4099057 G P 4091317 G null Yes NS, NC O69628 — 1680 4037111 C P 4099761 T S 4092021 T S Yes NS, NC O69629 metabolism 1681 4039283 T T 4101933 C A 4094193 C A Yes NS, NC O69630 — 1682 4043080 C G 4105730 T E 4097990 T E Yes NS, NC O69634 transporter activity 1683 4043104 T Q 4105754 C R 4098014 C R Yes NS, NC O69634 transporter activity 1684 4044421 C R 4107071 T Q 4099331 T Q Yes NS, NC O69634 transporter activity 1685 4045320 A E 4107970 G G 4100230 G G Yes NS, NC O69635 enzyme activity 1686 4049776 C V 4112426 T I 4104686 T I Yes NS, C O69639 serine-type endopeptidase activity 1687 4054029 C L 4116679 T L 4108939 T L Yes S, NULL Null — 1688 4054508 A Null 4117158 C Null 4109418 C null No nc, NULL Null — 1689 4056593 C D 4119243 T D 4111501 T D Yes S, NULL Null — 1690 4058330 G Null 4120980 A Null 4113238 A null No nc, NULL Null — 1691 4059022 T Null 4121672 C Null 4113930 C null No nc, NULL Null — 1692 4065667 G Q 4128317 C E 4120575 C E Yes NS, NC O69653 monooxygenase activity 1693 4066936 A Null 4129586 C Null 4121844 C null Yes S, NULL Null — 1694 4068058 C L 4130708 G V 4122966 G V Yes NS, C O69657 — 1695 4072777 T T 4135427 C T 4127684 C T Yes S, NULL Null — 1696 4073901 A L 4136551 G L 4128808 G L Yes S, NULL Null — 1697 4075724 G A 4138374 A V 4130631 A V Yes NS, C O69664 glycerol kinase activity 1698 4076324 G A 4138974 C G 4131231 C G Yes NS, C O69664 glycerol kinase activity 1699 4077491 T R 4140140 C G 4132397 C G Yes NS, NC O69665 — 1700 4077846 C R 4140495 A R 4132752 A R Yes S, NULL Null — 1701 4078038 C I 4140687 G M 4132944 G M Yes NS, NC O69666 — 1702 4078538 G R 4141187 C P 4133444 C P Yes NS, NC O69666 — 1703 4083085 G Y 4145734 A Y 4137991 A Y Yes S, NULL Null — 1704 4091572 A H 4154221 C P 4146478 C P Yes NS, NC P96420 enzyme activity 1705 4092200 T V 4154849 G V 4147106 G V Yes S, NULL Null — 1706 4093758 G A 4156236 A V 4148493 A V Yes NS, C O69678 DNA-directed DNA polymerase activity 1707 4094022 T D 4156500 C G 4148757 C G Yes NS, NC O69678 DNA-directed DNA polymerase activity 1708 4095038 A S 4157575 G G 4149891 G G Yes NS, NC O69679 ATP binding activity 1709 4095492 C T 4158029 A K 4150345 A K Yes NS, NC O69679 ATP binding activity 1710 4095821 G P 4158358 A P 4150674 A P Yes S, NULL Null — 1711 4101540 A Q 4164077 G Q 4156393 G Q Yes S, NULL Null — 1712 4107289 A V 4169827 G V 4162142 G V Yes S, NULL Null — 1713 4108573 C P 4171110 T P 4163425 T P Yes S, NULL Null — 1714 4109633 C S 4172170 A R 4164485 A R Yes NS, NC O69693 alcohol dehydrogenase activity 1715 4110670 A M 4173207 G V 4165522 G V Yes NS, NC O69694 — 1716 4113722 A R 4176259 G G 4168574 G G Yes NS, NC O69695 enzyme activity 1717 4116252 A I 4178789 G V 4171104 G V Yes NS, C O69696 S-adenosylmethionine- dependent methyltransferase activity 1718 4116549 T S 4179086 C P 4171401 C P Yes NS, NC O69696 S-adenosylmethionine- dependent methyltransferase activity 1719 4118314 C G 4180851 G G 4173166 G G Yes S, NULL Null — 1720 4118737 A F 4181274 G F 4173589 G F Yes S, NULL Null — 1721 4121062 T A 4183599 C A 4175914 C A Yes S, NULL Null — 1722 4126515 A R 4189052 C R 4181367 C R Yes S, NULL Null — 1723 4127210 A C 4190913 G R 4183228 G R Yes NS, NC O69707 molecular_function unknown 1724 4131476 A C 4195179 G C 4187494 G C Yes S, NULL Null — 1725 4132036 T A 4195739 C A 4188054 C A Yes S, NULL Null — 1726 4133484 G Null 4197186 A Null 4189502 A null Yes nc, NULL Null — 1727 4133850 A D 4197552 G G 4189868 G null Yes NS, NC O69715 — 1728 4136514 G T 4200217 A M 4192532 A M Yes NS, NC O69720 — 1729 4138677 C V 4202380 A V 4194695 A V Yes S, NULL Null — 1730 4141141 A V 4204844 G A 4197159 G A Yes NS, C O69725 — 1731 4144138 G H 4207841 A Y 4200156 A Y Yes NS, C O69728 — 1732 4144689 C G 4208392 A V 4200707 A V Yes NS, C O69728 — 1733 4147170 C R 4210873 T H 4203188 T H Yes NS, NC O69729 two-component sensor molecule activity 1734 4148468 C Null 4212171 T Null 4204486 T null No nc, NULL Null — 1735 4151295 A Null 4214998 C Null 4207313 C null No nc, NULL Null — 1736 4151778 C A 4215481 G P 4207796 G P Yes NS, NC P72037 — 1737 4152549 G R 4216252 C Null 4208567 C R Yes nc, NULL Null — 1738 4153851 G A 4217554 A T 4209869 A T Yes NS, NC P72039 histidine biosynthesis 1739 4158142 T A 4221844 C A 4214159 C A Yes S, NULL Null — 1740 4165765 C Y 4229467 T Y 4221782 T Y Yes S, NULL Null — 1741 4167728 G A 4231430 A A 4223746 A A Yes S, NULL Null — 1742 4168622 G R 4232324 A R 4224640 A R Yes S, NULL Null — 1743 4169929 A N 4233631 G N 4225947 G N Yes S, NULL Null — 1744 4172445 T G 4236147 C G 4228463 C G Yes S, NULL Null — 1745 4176574 A L 4240276 G L 4232591 G L Yes S, NULL Null — 1746 4176966 T I 4240668 C T 4232983 C T Yes NS, NC P72059 cell wall 1747 4179265 T T 4242967 C T 4235282 C T Yes S, NULL Null — 1748 4180515 T L 4244217 C L 4236532 C L Yes S, NULL Null — 1749 4182846 G S 4246548 A N 4238863 A N Yes NS, C P72030 cell wall 1750 4183159 T V 4246861 C V 4239176 C V Yes S, NULL Null — 1751 4183941 C A 4247643 A E 4239958 A E Yes NS, NC P72030 cell wall 1752 4187131 T I 4250833 C T 4243148 C T Yes NS, NC P72062 hydrolase activity 1753 4187592 C G 4251294 G G 4243609 G G Yes S, NULL Null — 1754 4195852 C G 4259576 G A 4251901 G A Yes NS, C O53579 enzyme activity 1755 4197772 A V 4261496 G A 4253821 G A Yes NS, C O53580 enzyme activity 1756 4199552 G Null 4263276 A Null 4255601 A null No nc, NULL Null — 1757 4201999 C G 4265723 G G 4258048 G G Yes S, NULL Null — 1758 4204131 C V 4267855 T I 4260180 T I Yes NS, C O53582 — 1759 4205624 A A 4269348 G A 4261673 G A Yes S, NULL Null — 1760 4205660 G D 4269384 T E 4261709 T E Yes NS, C O53583 membrane 1761 4205879 G R 4269603 A R 4261928 A R Yes S, NULL Null — 1762 4209847 G Null 4273571 T Null 4265896 T null No nc, NULL Null — 1763 4214379 A Null 4278103 G Null 4270428 G null Yes nc, NULL Null — 1764 4214597 C Null 4278321 G Null 4270646 G null No nc, NULL Null — 1765 4215241 G T 4278965 A M 4271290 A M Yes NS, NC O07810 molecular_function unknown 1766 4217784 A L 4281508 G L 4273833 G L Yes S, NULL Null — 1767 4220711 A I 4284435 G T 4276760 G T Yes NS, NC O07803 molecular_function unknown 1768 4222561 A N 4286285 G D 4278610 G D Yes NS, NC O07802 — 1769 4222603 A T 4286327 G A 4278652 G A Yes NS, NC O07802 — 1770 4223157 A Y 4286881 G C 4279206 G C Yes NS, NC O07801 — 1771 4223301 C T 4287025 A N 4279350 A N Yes NS, C O07801 — 1772 4223437 G G 4287161 A G 4279486 A G Yes S, NULL Null — 1773 4223634 T V 4287358 C A 4279683 C A Yes NS, C O07801 — 1774 4226226 G A 4289950 A V 4282275 A V Yes NS, C O07800 membrane 1775 4226837 T A 4290561 G A 4282886 G A Yes S, NULL Null — 1776 4227100 G R 4290824 C G 4283149 C G Yes NS, NC O07800 membrane 1777 4228368 A A 4292092 C A 4284417 C A Yes S, NULL Null — 1778 4238583 C L 4302307 A L 4294632 A L Yes S, NULL Null — 1779 4241120 A D 4304844 C E 4297169 C E Yes NS, C O07794 — 1780 4241350 A T 4305074 G T 4297399 G T Yes S, NULL Null — 1781 4247232 A Null 4310955 G Null 4303280 G null No nc, NULL Null — 1782 4249402 T S 4313125 C P 4305450 C P Yes NS, NC P96239 — 1783 4252596 T H 4316319 C R 4308644 C R Yes NS, NC P96235 — 1784 4252840 G R 4316563 C G 4308888 C G Yes NS, NC P96235 — 1785 4254698 G Null 4318421 T Null 4310746 T null Yes nc, NULL Null — 1786 4257590 C T 4321314 T I 4313640 T I Yes NS, NC P17670 superoxide dismutase activity 1787 4259178 A I 4322902 G V 4315228 G V Yes NS, C P96229 molecular_function unknown 1788 4259279 A A 4323003 G A 4315329 G A Yes S, NULL Null — 1789 4266055 A Null 4329779 G Null 4322105 G null Yes nc, NULL Null — 1790 4266511 T H 4330235 C R 4322561 C R Yes NS, NC P96219 monooxygenase activity 1791 4270698 C E 4334422 G Q 4326748 G Q Yes NS, NC P96218 glutamate biosynthesis 1792 4272870 A Null 4336594 C Null 4328920 C null No nc, NULL Null — 1793 4273741 C A 4337465 T V 4329791 T V Yes NS, C P96217 — 1794 4280361 T V 4344038 C A 4336363 C A Yes NS, C O69733 nucleotide binding activity 1795 4293145 A K 4356822 G E 4349146 G E Yes NS, NC O69742 — 1796 4293741 A G 4357418 G G 4349742 G G Yes S, NULL Null — 1797 4294795 A P 4358472 C P 4350796 C P Yes S, NULL Null — 1798 4300168 A L 4363800 G L 4356106 G L Yes S, NULL Null — 1799 4301014 C A 4364646 T T 4356952 T T Yes NS, NC O05461 subtilase activity 1800 4304014 G Y 4367646 A Y 4359952 A Y Yes S, NULL Null — 1801 4304489 G P 4368121 A L 4360427 A L Yes NS, NC O05459 — 1802 4307013 C G 4370645 T D 4362949 T D Yes NS, NC O05457 — 1803 4308186 C A 4374225 T T 4366529 T T Yes NS, NC O05453 — 1804 4310990 C S 4377030 G S 4369334 G S Yes S, NULL Null — 1805 4313166 T R 4379205 C R 4371509 C R Yes S, NULL Null — 1806 4314838 C G 4380877 T D 4373181 T D Yes NS, NC O05449 — 1807 4316253 C V 4382293 T I 4374597 T I Yes NS, C O05448 — 1808 4316561 C G 4382601 T D 4374905 T D Yes NS, NC O05448 — 1809 4316925 T Null 4382965 C Null 4375269 C null No nc, NULL Null — 1810 4317617 G Q 4383652 A * 4375961 A * Yes NS, TP O05447 — 1811 4317969 G Null 4384004 C Null 4376313 C null No nc, NULL Null — 1812 4319148 G P 4385184 A S 4377493 A S Yes NS, NC O05446 — 1813 4320218 C A 4386254 G P 4378563 G P Yes NS, NC O05445 — 1814 4320714 C W 4386750 A L 4379059 A L Yes NS, NC O05444 — 1815 4324427 C V 4390463 T M 4382772 T M Yes NS, NC O05441 — 1816 4324820 T * 4390856 C W 4383165 C W Yes NS, TP O05440 — 1817 4327799 T L 4393835 C L 4386144 C L Yes S, NULL Null — 1818 4328171 C R 4394207 G G 4386516 G R Yes NS, NC O05436 — 1819 4328226 C A 4394262 G G 4386571 G A Yes NS, C O05436 — 1820 4329348 G S 4395384 A N 4387692 A N Yes NS, C O05436 — 1821 4329765 T V 4395801 C A 4388109 C A Yes NS, C O05436 — 1822 4331996 C A 4398032 T V 4390340 T V Yes NS, C O05435 pathogenesis 1823 4334624 T S 4400660 C S 4392968 G A Yes S, NULL Null — 1824 4335857 G G 4401894 A D 4394201 A D Yes NS, NC P52214 thioredoxin reductase (NADPH) activity 1825 4339065 C R 4405102 T R 4397409 T R Yes S, NULL Null — 1826 4341548 C A 4407585 T A 4399892 T A Yes S, NULL Null — 1827 4342530 A W 4408567 G R 4400874 G R Yes NS, NC O53598 nucleic acid binding activity 1828 26940 G Null 26959 C Null Null Null Null No Null, NC Null Null 1829 34028 C Null 34044 T Null Null Null Null No Null, NC Null Null Table I: List of single nucleotide polymorphisms in Mycobacaterium tuberculosis / M. bovis BCG Polymorphism ID: The ID by which the polymorphism can be identified SNP Position: Position of the SNP in the respective genome Base: The nucleotide occurring in the region of the polymorphism in the respective genome AA: The aminoacid occurring in the region of the polymorphism in the respective genome ORF: Indicates whether the polymorphism occurs in an open reading frame (yes) or not (no) SNP type: Indicates the kind of SNP-S: synonymous SNP which codes for the same amino acid as the reference sequence; NS: non-synonymous SNP which codes for an aminoacid different from the reference sequence: C: conservative SNP coding for an aminoacid of the same family as the reference sequence: NC: nonconservative SNP coding for an aminoacid from a different family as the reference sequence GO ID: The ID for the sequence in the gene ontology database Putative function: The putative function of the gene in which the SNP occurs.
[0244]
TABLE II
List of insertion/deletions in M. tuberculosis / M. bovis BCG
BCG
BCG
H37Rv
H37Rv
CDC
CDC
Polymorphism ID
Start
End
start
end
start
end
ORF
GO ID
Putative Function
1830
13233
13234
13233
13235
13233
13235
YES
P71580
integral to
membrane
1831
24719
24720
24720
24739
13233
13235
YES
P71590
—
1832
28917
28918
28936
28938
13233
13235
YES
P71594
—
1833
30962
30967
30982
30983
13233
13235
YES
P71596
—
1834
42578
42588
42594
42595
13233
13235
YES
P71697
—
1835
71576
71614
71584
71585
13233
13235
YES
Null
—
1836
79584
79594
79555
79556
13233
13235
YES
O53616
RNA binding
activity
1837
82490
82491
82452
82454
13233
13235
YES
O53618
nucleotide binding
activity
1838
125870
125872
125832
125833
13233
13235
YES
Q10900
magnesium ion
binding activity
1839
131213
131215
131174
131175
13233
13235
YES
Null
—
1840
138784
138786
138744
138745
13233
13235
YES
O53637
peroxidase activity
1841
139598
139600
139557
139558
13233
13235
YES
O53637
peroxidase activity
1842
147495
147496
147453
147455
13233
13235
YES
O07170
translation
elongation factor
activity
1843
147853
147854
147812
147814
13233
13235
YES
Null
—
1844
150079
150080
150039
150067
13233
13235
YES
O07174
—
1845
150906
151077
150893
150894
13233
13235
YES
O07174
—
1846
162346
162347
162153
162155
13233
13235
YES
P96811
enzyme activity
1847
162451
162453
162259
162260
13233
13235
YES
P96811
enzyme activity
1848
162694
162695
162501
162503
13233
13235
YES
P96811
enzyme activity
1849
194495
194498
194303
194304
13233
13235
YES
O07410
transcription factor
activity
1850
208509
208510
208315
208322
13233
13235
YES
O07420
—
1851
223943
223945
223749
223750
13233
13235
YES
O07436
—
1852
230770
230772
230575
230576
13233
13235
YES
Null
—
1853
234690
234693
234494
234495
13233
13235
YES
O53648
—
1854
257984
258014
257786
257787
13233
13235
YES
P96397
acyl-CoA
dehydrogenase
activity
1855
264979
264980
264752
266645
13233
13235
YES
P96403, P96405
—
1856
265066
265068
266741
266742
13233
13235
YES
P96405
metabolism
1857
291957
291959
293631
293632
13233
13235
YES
Null
—
1858
331998
331999
333671
333673
13233
13235
YES
P56877
—
1859
332977
335748
334651
334652
13233
13235
YES
P56877
—
1860
336706
336707
335600
335657
13233
13235
YES
P56877
—
1861
336884
336885
335844
335863
13233
13235
YES
P56877
—
1862
338180
338181
337158
337168
13233
13235
YES
O53684
—
1863
339540
339541
338527
338537
13233
13235
YES
O53684
—
1864
363810
363856
362806
362807
13233
13235
YES
O07224
intracellular
1865
369162
369163
368113
368129
13233
13235
YES
O07231
tRNA ligase activity
1866
370799
370800
369765
369767
13233
13235
YES
O07231
tRNA ligase activity
1867
374314
374315
373281
373283
13233
13235
YES
O07232
—
1868
416214
416215
415182
415184
13233
13235
YES
O06296
—
1869
425351
425353
424320
424321
13233
13235
YES
O06303
—
1870
425821
425824
424789
424790
13233
13235
YES
O06304
—
1871
428391
428392
427357
427373
13233
13235
YES
O06304
—
1872
482549
482550
481528
481530
13233
13235
YES
P95211
membrane
1873
488117
488119
487097
487098
13233
13235
YES
O86335
enzyme activity
1874
570941
570942
569920
569961
13233
13235
YES
Q11146
molecular_function
unknown
1875
578459
578500
577494
577495
13233
13235
YES
Null
—
1876
581835
581956
580812
580813
13233
13235
YES
Q11156
two-component
response regulator
activity
1877
612063
612064
610910
610912
13233
13235
YES
Null
—
1878
624447
624522
623295
623296
13233
13235
YES
O06398
—
1879
624655
624665
623419
623420
13233
13235
YES
O06398
—
1880
625594
625596
624349
624350
13233
13235
YES
O06398
—
1881
641609
641610
640363
640365
13233
13235
YES
O06415
—
1882
664431
664432
663186
663188
13233
13235
YES
O53767
ribonucleoside-
diphosphate
reductase activity
1883
669950
669952
668706
668707
13233
13235
YES
O53772
monooxygenase
activity
1884
690039
690041
688794
688795
13233
13235
YES
O07788
pathogenesis
1885
693138
693140
691892
691893
13233
13235
YES
O07786
pathogenesis
1886
713437
713439
712190
712191
13233
13235
YES
O07759, O07758
—
1887
723680
723681
722432
722434
13233
13235
YES
P96920
DNA binding
activity
1888
731330
731331
730083
730093
13233
13235
YES
P96923
—
1889
743870
744394
742632
742633
13233
13235
YES
Null
—
1890
800911
800912
799140
799142
13233
13235
YES
P95044
—
1891
804268
804309
802498
802499
13233
13235
YES
Null
—
1892
832699
832702
830875
830876
13233
13235
YES
O53802
—
1893
838696
838697
836870
836919
13233
13235
YES
O53809
—
1894
839071
839072
837293
837342
13233
13235
YES
O53809
—
1895
839638
839767
837908
837909
13233
13235
YES
O53809
—
1896
841026
841185
839098
839099
13233
13235
YES
O53810
—
1897
841398
841494
839302
839303
13233
13235
YES
O53810
—
1898
841688
841689
839487
839497
13233
13235
YES
O53810
—
1899
856450
856451
854258
854260
13233
13235
YES
Null
—
1900
877025
877028
874834
874835
13233
13235
YES
P71834, P71835
—
1901
881931
881932
879738
879740
13233
13235
YES
P71838
integral to
membrane
1902
890037
890038
887845
887847
13233
13235
YES
O07268
cytoplasm
1903
927816
927891
926984
926985
13233
13235
YES
O53844
—
1904
928822
928823
927918
927928
13233
13235
YES
O53845
calcium ion binding
activity
1905
928975
928976
928080
928215
13233
13235
YES
O53845
calcium ion binding
activity
1906
936197
936204
935446
935447
13233
13235
YES
O53850
cell wall
1907
953566
953567
952809
952811
13233
13235
YES
Null
—
1908
961024
961025
960268
960309
13233
13235
YES
Null
—
1909
963656
963657
962953
962955
13233
13235
YES
O53876
Mo-molybdopterin
cofactor
biosynthesis
1910
965541
965542
964839
965070
13233
13235
YES
O53879
—
1911
968900
968910
968438
968439
13233
13235
YES
O53884
—
1912
969448
969449
968977
968981
13233
13235
YES
O53884
—
1913
977362
977363
976894
976896
13233
13235
YES
Q10540
integral to
membrane
1914
1010671
1010673
1010204
1010205
13233
13235
YES
O05900
—
1915
1032449
1032450
1031981
1031983
13233
13235
YES
O05917
—
1916
1039551
1039553
1039084
1039085
13233
13235
YES
O05871
protein kinase
activity
1917
1041920
1041922
1041452
1041453
13233
13235
YES
P95302
nucleotide binding
activity
1918
1064550
1064551
1064081
1064110
13233
13235
YES
Null
—
1919
1087886
1087887
1087445
1087447
13233
13235
YES
O86319
acyl-CoA
dehydrogenase
activity
1920
1090629
1090631
1090189
1090190
13233
13235
YES
Null
—
1921
1131681
1131683
1131228
1131229
13233
13235
YES
O05597
—
1922
1135355
1135356
1134901
1134907
13233
13235
YES
P96384
membrane
1923
1165969
1165971
1165520
1165521
13233
13235
YES
Null
—
1924
1169165
1169167
1168715
1168716
13233
13235
YES
O86321
—
1925
1173288
1173289
1172837
1172839
13233
13235
YES
Null
—
1926
1189124
1189125
1188674
1188678
13233
13235
YES
O53415
—
1927
1189603
1189622
1189156
1189157
13233
13235
YES
O53415
—
1928
1189661
1189662
1189196
1189200
13233
13235
YES
O53415
—
1929
1191462
1191463
1191000
1191010
13233
13235
YES
O53416
—
1930
1191817
1192525
1191364
1191365
13233
13235
YES
O53416
—
1931
1192629
1192812
1191459
1191460
13233
13235
YES
O53416
—
1932
1214392
1214393
1213030
1213049
13233
13235
YES
O53435
—
1933
1214589
1214590
1213245
1213255
13233
13235
YES
O53435
—
1934
1214840
1214844
1213505
1213506
13233
13235
YES
O53435
—
1935
1215028
1215074
1213690
1213691
13233
13235
YES
O53435
—
1936
1219617
1219618
1218234
1218244
13233
13235
YES
O53439
—
1937
1231791
1231792
1230417
1230419
13233
13235
YES
O53449
integral to
membrane
1938
1274621
1274623
1273248
1273249
13233
13235
YES
O06545
membrane
1939
1300681
1300683
1299307
1299308
13233
13235
YES
O50424
—
1940
1306903
1306904
1305528
1305643
13233
13235
YES
Null
—
1941
1314587
1314589
1313336
1313337
13233
13235
YES
Null
—
1942
1341420
1341421
1340168
1340182
13233
13235
YES
O05298
—
1943
1358664
1358665
1357415
1357421
13233
13235
YES
O05315
—
1944
1367083
1367086
1365839
1365840
13233
13235
YES
O06291
serine-type
endopeptidase
activity
1945
1404177
1404178
1402931
1405929
13233
13235
YES
Q11063, Q11061
—
1946
1407255
1407256
1409016
1409018
13233
13235
YES
Q11058
monooxygenase
activity
1947
1439690
1439691
1441542
1441686
13233
13235
YES
Q10614
enzyme activity
1948
1441478
1441519
1443483
1443484
13233
13235
YES
Q10616
integral to
membrane
1949
1466163
1466164
1468112
1468115
13233
13235
YES
Q10620
integral to
membrane
1950
1475063
1475064
1477025
1477027
13233
13235
YES
Null
—
1951
1539986
1539987
1541949
1543298
13233
13235
YES
Null
—
1952
1540483
1540485
1543804
1543805
13233
13235
YES
P71799
—
1953
1543150
1543152
1546470
1546471
13233
13235
YES
P71801
sulfotransferase
activity
1954
1569167
1569168
1572486
1572849
13233
13235
YES
P71664
integral to
membrane
1955
1608954
1608976
1612645
1612646
13233
13235
YES
O06823
—
1956
1627336
1627337
1630987
1631015
13233
13235
YES
O06810
—
1957
1628863
1628891
1632541
1632542
13233
13235
YES
O06810
—
1958
1632753
1632882
1636167
1636168
13233
13235
YES
O06808
—
1959
1632905
1632909
1636181
1636182
13233
13235
YES
O06808
—
1960
1633457
1633467
1636730
1636731
13233
13235
YES
O06808
—
1961
1689986
1689987
1693238
1693240
13233
13235
YES
P71783
—
1962
1737536
1737538
1753521
1753522
13233
13235
YES
Q10777
enzyme activity
1963
1738035
1738037
1754019
1754020
13233
13235
YES
Q10777, Q10776
—
1964
1744186
1744191
1760169
1760170
13233
13235
YES
Q10761
succinate
dehydrogenase
activity
1965
1745810
1747954
1761789
1761790
13233
13235
YES
Q10773
membrane
1966
1754245
1754246
1768071
1768868
13233
13235
YES
Q10768
alpha-amylase
activity
1967
1765829
1765830
1780461
1780463
13233
13235
YES
O06615
—
1968
1765952
1765954
1780585
1780586
13233
13235
YES
O06615
—
1969
1837548
1837549
1852180
1852182
13233
13235
YES
Null
—
1970
1850305
1850327
1864938
1864939
13233
13235
YES
P94986
—
1971
1879687
1879698
1894299
1894300
13233
13235
YES
O53916
nucleotide binding
activity
1972
1892915
1892916
1907517
1907558
13233
13235
YES
Null
—
1973
1900884
1900887
1915542
1915543
13233
13235
YES
O33192
—
1974
1914068
1914069
1928724
1928726
13233
13235
YES
Null
—
1975
1930724
1930725
1945381
1945383
13233
13235
YES
P71976
—
1976
1941012
1941053
1955670
1955671
13233
13235
YES
Null
—
1977
1953648
1953650
1968249
1968250
13233
13235
YES
O33271
—
1978
1967611
1967752
1982211
1982212
13233
13235
YES
O65937
—
1979
1968448
1968449
1982898
1982967
13233
13235
YES
O65937
—
1980
1968664
1968665
1983192
1983261
13233
13235
YES
O65937
—
1981
1983171
1983172
1992328
1992330
13233
13235
YES
O06794
—
1982
1985312
1985313
1994470
1994472
13233
13235
YES
O06795
molecular_function
unknown
1983
1992126
1992145
2001684
2001685
13233
13235
YES
O06801
—
1984
2016682
2016683
2026222
2026231
13233
13235
YES
O86373
—
1985
2051905
2051915
2061448
2061449
13233
13235
YES
Q50615
integral to
membrane
1986
2064977
2064978
2074511
2074614
13233
13235
YES
Null
—
1987
2079195
2079196
2088841
2088979
13233
13235
YES
Q50594
integral to
membrane
1988
2080613
2080626
2090406
2090407
13233
13235
YES
Q50593
integral to
membrane
1989
2084192
2084193
2093973
2093975
13233
13235
YES
P95165
phosphogluconate
dehydrogenase
(decarboxylating)
activity
1990
2085136
2085137
2094918
2094925
13233
13235
YES
P95165
phosphogluconate
dehydrogenase
(decarboxylating)
activity
1991
2087040
2087041
2096828
2096830
13233
13235
YES
Null
—
1992
2093386
2093387
2103175
2103177
13233
13235
YES
Null
—
1993
2099733
2099735
2109523
2109524
13233
13235
YES
Null
—
1994
2116913
2116915
2126702
2126703
13233
13235
YES
O07753
transporter activity
1995
2123684
2123700
2133472
2133473
13233
13235
YES
O07748
—
1996
2127747
2127758
2137520
2137521
13233
13235
YES
O07744
—
1997
2133043
2133044
2142806
2142808
13233
13235
YES
O07737
alcohol
dehydrogenase
activity
1998
2133758
2133760
2143522
2143523
13233
13235
YES
O07737
alcohol
dehydrogenase
activity
1999
2136332
2136378
2146095
2146096
13233
13235
YES
O07733
—
2000
2151627
2151629
2161345
2161346
13233
13235
YES
O07718
enzyme activity
2001
2153548
2153549
2163265
2163278
13233
13235
YES
O07716
enzyme activity
2002
2153668
2154142
2163397
2163398
13233
13235
YES
O07716
enzyme activity
2003
2154541
2154542
2163787
2163847
13233
13235
YES
O07716
enzyme activity
2004
2156236
2156602
2165551
2165552
13233
13235
YES
O07716
enzyme activity
2005
2160449
2160451
2168813
2168814
13233
13235
YES
O53960
—
2006
2184230
2184231
2192593
2192595
13233
13235
YES
P95275
electron transport
2007
2199225
2199227
2207589
2207590
13233
13235
YES
Null
—
2008
2254439
2254440
2270521
2270531
13233
13235
YES
Null
—
2009
2260638
2260639
2276722
2276724
13233
13235
YES
O53475
nucleoside
metabolism
2010
2312077
2312079
2328162
2328163
13233
13235
YES
Q10680
vitamin B12
biosynthesis
2011
2313772
2313774
2329856
2329857
13233
13235
YES
Q10671
porphyrin
biosynthesis
2012
2313988
2313989
2330071
2332091
13233
13235
YES
Q10671, Q10683
—
2013
2320088
2320092
2338200
2338201
13233
13235
YES
Q10689
integral to
membrane
2014
2324539
2324551
2342648
2342649
13233
13235
YES
Q10692
—
2015
2329456
2329457
2347554
2347595
13233
13235
YES
Q10699
DNA binding
activity
2016
2339127
2339128
2357282
2357286
13233
13235
YES
Q10707
—
2017
2339871
2339873
2358029
2358030
13233
13235
YES
Q10707, Q9ZAE2
—
2018
2347255
2347256
2365412
2366761
13233
13235
YES
Null
—
2019
2349048
2349049
2368563
2368565
13233
13235
YES
Null
—
2020
2352985
2352986
2372501
2372542
13233
13235
YES
O33247
molecular_function
unknown
2021
2361585
2361586
2381158
2381186
13233
13235
YES
O33258
—
2022
2378768
2378769
2398368
2398377
13233
13235
YES
O06237
—
2023
2382325
2382432
2401925
2401926
13233
13235
YES
Null
—
2024
2402489
2402494
2421973
2421974
13233
13235
YES
O06217
—
2025
2404055
2404056
2423535
2423634
13233
13235
YES
O06215
—
2026
2404228
2404229
2423816
2423835
13233
13235
YES
O06215
—
2027
2410508
2410509
2430114
2431463
13233
13235
YES
Null
—
2028
2427464
2427465
2448428
2448430
13233
13235
YES
O53521
enzyme activity
2029
2440537
2440642
2461502
2461503
13233
13235
YES
Q10389
integral to
membrane
2030
2480295
2480297
2501146
2501147
13233
13235
YES
Q10511
—
2031
2502267
2502271
2523205
2523206
13233
13235
YES
Null
—
2032
2504789
2504790
2525724
2525726
13233
13235
YES
O53525
electron transport
2033
2511025
2511026
2531961
2532058
13233
13235
YES
Null
—
2034
2513519
2513520
2534561
2534564
13233
13235
YES
O53536
nitrogen
metabolism
2035
2528967
2528968
2550011
2551360
13233
13235
YES
Q50687
glycerol
metabolism
2036
2540310
2540311
2562712
2562714
13233
13235
YES
Q50675
membrane
2037
2540853
2540854
2563256
2563259
13233
13235
YES
Q59570
thiosulfate
sulfurtransferase
activity
2038
2541962
2541964
2564367
2564368
13233
13235
YES
Q50673
enzyme activity
2039
2544362
2544364
2566766
2566767
13233
13235
YES
Null
—
2040
2584392
2584410
2606795
2606796
13233
13235
YES
P71879
transporter activity
2041
2592156
2592158
2614558
2614559
13233
13235
YES
Null
—
2042
2607119
2607120
2639043
2639047
13233
13235
YES
P95249
—
2043
2658273
2658275
2690200
2690201
13233
13235
YES
P71749
—
2044
2661152
2661153
2693078
2693088
13233
13235
YES
P71748
oxygen transporter
activity
2045
2672954
2672976
2704883
2704884
13233
13235
YES
P71736
—
2046
2673694
2673779
2705602
2705603
13233
13235
YES
Null
—
2047
2679611
2679613
2711425
2711426
13233
13235
YES
P71729
—
2048
2689758
2689759
2721571
2721574
13233
13235
YES
P71924
DNA binding
activity
2049
2692384
2692385
2724199
2724220
13233
13235
YES
Null
—
2050
2748934
2748935
2780769
2780773
13233
13235
YES
O53203
—
2051
2752776
2752777
2784614
2785963
13233
13235
YES
Null
—
2052
2762072
2762073
2795268
2795270
13233
13235
YES
Null
—
2053
2762938
2762939
2796135
2796137
13233
13235
YES
O53212
—
2054
2763778
2763780
2796976
2796977
13233
13235
YES
O53212
—
2055
2768766
2768767
2801963
2801967
13233
13235
YES
O53215
RNA-3′-phosphate
cyclase activity
2056
2769956
2769957
2803156
2803166
13233
13235
YES
O53215
RNA-3′-phosphate
cyclase activity
2057
2771738
2771747
2804947
2804948
13233
13235
YES
O53215
RNA-3′-phosphate
cyclase activity
2058
2834003
2834650
2867204
2867205
13233
13235
YES
P95009
—
2059
2839452
2839453
2871997
2871999
13233
13235
YES
P95001
shikimate 5-
dehydrogenase
activity
2060
2849054
2849055
2881600
2881602
13233
13235
YES
Q50737
—
2061
2855417
2855418
2887964
2887967
13233
13235
YES
Q50732
—
2062
2863468
2863469
2896017
2896019
13233
13235
YES
Q50649
nucleic acid binding
activity
2063
2890583
2890593
2923133
2923134
13233
13235
YES
Q50630
—
2064
2911188
2911198
2943729
2943730
13233
13235
YES
O06199
—
2065
2915441
2915442
2947973
2947977
13233
13235
YES
O06191
—
2066
2925032
2925033
2957567
2957569
13233
13235
YES
P71930
molecular_function
unknown
2067
2925801
2925803
2958337
2958338
13233
13235
YES
P71930
molecular_function
unknown
2068
2938901
2938902
2982418
2982420
13233
13235
YES
Null
—
2069
2947177
2947218
2990695
2990696
13233
13235
YES
Null
—
2070
2952702
2952795
2996165
2996166
13233
13235
YES
O86317
—
2071
3010580
3010581
3053941
3053943
13233
13235
YES
O33284
—
2072
3011358
3011359
3054720
3054795
13233
13235
YES
O33284
—
2073
3012343
3012367
3055789
3055790
13233
13235
YES
O33285
—
2074
3042938
3042939
3086361
3086386
13233
13235
YES
O33321
DNA binding
activity
2075
3043634
3043635
3087081
3087083
13233
13235
YES
P30234
alanine
dehydrogenase
activity
2076
3064422
3064426
3107870
3107871
13233
13235
YES
P71652
—
2077
3073960
3073961
3117405
3117408
13233
13235
YES
P71639
DNA binding
activity
2078
3075770
3075771
3119217
3119800
13233
13235
YES
Null
—
2079
3075914
3076356
3119953
3119954
13233
13235
YES
Null
—
2080
3076439
3076501
3120027
3120028
13233
13235
YES
Null
—
2081
3078601
3078745
3122118
3122119
13233
13235
YES
Null
—
2082
3078967
3078968
3122331
3122394
13233
13235
YES
Null
—
2083
3088034
3088044
3131469
3131470
13233
13235
YES
P71629
molecular_function
unknown
2084
3098539
3098540
3141965
3141967
13233
13235
YES
P71617
transporter activity
2085
3112605
3112606
3156032
3156073
13233
13235
YES
Null
—
2086
3146666
3146667
3190147
3190149
13233
13235
YES
Q10806, Q10806
—
2087
3150757
3150759
3194239
3194240
13233
13235
YES
Q10809
—
2088
3196190
3196191
3239559
3239600
13233
13235
YES
Null
—
2089
3248018
3248123
3291442
3291443
13233
13235
YES
Null
—
2090
3253069
3253071
3296379
3296380
13233
13235
YES
P96284
enzyme activity
2091
3267820
3267822
3311129
3311130
13233
13235
YES
P95134
metabolism
2092
3288055
3288056
3331363
3331366
13233
13235
YES
P95120
aspartic-type
endopeptidase
activity
2093
3293332
3293333
3336642
3336751
13233
13235
YES
Null
—
2094
3294465
3294466
3337893
3337903
13233
13235
YES
P95114
cell wall
2095
3307774
3307815
3351211
3351212
13233
13235
YES
Null
—
2096
3313357
3313358
3356738
3356740
13233
13235
YES
Null
—
2097
3336999
3337085
3380437
3380438
13233
13235
YES
O53268, O53268
—
2098
3371757
3371758
3415194
3415209
13233
13235
YES
Null
—
2099
3381643
3381645
3425094
3425095
13233
13235
YES
P95097
acyl-CoA
dehydrogenase
activity
2100
3430544
3430546
3473994
3473995
13233
13235
YES
Null
—
2101
3436512
3436513
3479961
3479963
13233
13235
YES
Null
—
2102
3441287
3441288
3484737
3487503
13233
13235
YES
O05793, O08362
—
2103
3455437
3456765
3501662
3501663
13233
13235
YES
P95191
receptor activity
2104
3484092
3484093
3528980
3528984
13233
13235
YES
O53309
—
2105
3484287
3486424
3529178
3529179
13233
13235
YES
Null
—
2106
3488662
3488663
3531407
3531409
13233
13235
YES
O53312
—
2107
3501951
3501952
3544697
3544699
13233
13235
YES
O53326
—
2108
3508479
3508480
3551226
3552575
13233
13235
YES
Null
—
2109
3508604
3508605
3552709
3554058
13233
13235
YES
Null
—
2110
3513313
3513315
3558776
3558777
13233
13235
YES
Null
—
2111
3521477
3521488
3566939
3566940
13233
13235
YES
Null
—
2112
3535183
3535184
3580635
3580637
13233
13235
YES
O05863
enzyme activity
2113
3537673
3537674
3583126
3583130
13233
13235
YES
O05860
enzyme activity
2114
3545179
3545181
3590635
3590636
13233
13235
YES
Null
—
2115
3545228
3545230
3590683
3590684
13233
13235
YES
Null
—
2116
3549001
3549042
3594455
3594456
13233
13235
YES
Null
—
2117
3552793
3552795
3598191
3598192
13233
13235
YES
Null
—
2118
3564990
3564992
3610387
3610388
13233
13235
YES
O05879
molecular_function
unknown
2119
3600628
3600629
3646024
3646037
13233
13235
YES
P96870
transferase activity
2120
3618520
3618521
3663928
3663982
13233
13235
YES
P96886
—
2121
3662150
3662151
3707621
3707625
13233
13235
YES
Null
—
2122
3681154
3681156
3723901
3723902
13233
13235
YES
O53388
—
2123
3692113
3692114
3738414
3738416
13233
13235
YES
O53394, O53395
—
2124
3692228
3692247
3738530
3738531
13233
13235
YES
O53395
—
2125
3692363
3692364
3738647
3738758
13233
13235
YES
O53395
—
2126
3694087
3694165
3740704
3740705
13233
13235
YES
O53395
—
2127
3694390
3694391
3740920
3740930
13233
13235
YES
O53395
—
2128
3694743
3694812
3741282
3741283
13233
13235
YES
O53395
—
2129
3695504
3695505
3741965
3741967
13233
13235
YES
O53395
—
2130
3700589
3700590
3747051
3747053
13233
13235
YES
O50378
—
2131
3706947
3706948
3753410
3753680
13233
13235
YES
Null
—
2132
3708737
3708738
3755201
3755207
13233
13235
YES
Null
—
2133
3713227
3713228
3759696
3759698
13233
13235
YES
O50379
—
2134
3733169
3733265
3779639
3779640
13233
13235
YES
O50396
—
2135
3733306
3733316
3779671
3779672
13233
13235
YES
O50396
—
2136
3744771
3744772
3791127
3791132
13233
13235
YES
O50406
enzyme activity
2137
3748507
3748510
3794864
3794865
13233
13235
YES
Null
—
2138
3748698
3748699
3795053
3796402
13233
13235
YES
Null
—
2139
3754439
3754440
3802152
3802218
13233
13235
YES
O50415
—
2140
3754539
3754580
3802327
3802328
13233
13235
YES
O50415
—
2141
3754972
3754973
3802700
3802710
13233
13235
YES
O50415
—
2142
3756095
3756164
3803832
3803833
13233
13235
YES
O50415
—
2143
3772838
3773120
3820497
3820498
13233
13235
YES
Null
—
2144
3795208
3795209
3842576
3847493
13233
13235
YES
Q50703, O06246
—
2145
3810175
3810176
3862469
3862471
13233
13235
YES
Null
—
2146
3822425
3822426
3874720
3874722
13233
13235
YES
O06320
—
2147
3826298
3826299
3878594
3878598
13233
13235
YES
Null
—
2148
3826332
3826333
3878631
3878633
13233
13235
YES
Null
—
2149
3843412
3843413
3897070
3897774
13233
13235
YES
O06342
enzyme activity
2150
3845388
3845389
3899759
3899762
13233
13235
YES
O06343
molecular_function
unknown
2151
3873325
3873326
3927698
3927779
13233
13235
YES
O53552
—
2152
3873813
3873814
3928276
3928317
13233
13235
YES
O53552
—
2153
3874278
3874297
3928795
3928796
13233
13235
YES
O53552
—
2154
3874602
3874665
3929101
3929102
13233
13235
YES
O53552
—
2155
3874830
3874831
3929257
3929276
13233
13235
YES
O53552
—
2156
3877295
3877305
3931731
3931732
13233
13235
YES
O53553
—
2157
3877742
3877743
3932169
3932328
13233
13235
YES
O53553
—
2158
3878312
3878340
3932781
3932782
13233
13235
YES
O53553
—
2159
3879828
3879829
3934873
3934922
13233
13235
YES
O53553
—
2160
3888742
3888752
3944049
3944050
13233
13235
YES
O53557
hydroxymethylglutaryl-
CoA reductase
(NADPH) activity
2161
3889054
3889064
3944352
3944353
13233
13235
YES
O53557
hydroxymethylglutaryl-
CoA reductase
(NADPH) activity
2162
3892768
3892769
3947748
3948330
13233
13235
YES
O53559
—
2163
3898149
3898150
3954929
3954931
13233
13235
YES
O53563
monooxygenase
activity
2164
3951089
3951090
4007870
4007872
13233
13235
YES
P96848
arylamine N-
acetyltransferase
activity
2165
3964661
3964663
4021443
4021444
13233
13235
YES
P96861
RNA binding
activity
2166
3968799
3968800
4025580
4025582
13233
13235
YES
Null
—
2167
3980409
3980437
4037191
4037192
13233
13235
YES
O06287
—
2168
3980524
3980525
4037279
4037281
13233
13235
YES
O06287
—
2169
3996679
3996680
4053435
4053537
13233
13235
YES
O06272, O06271
—
2170
3999617
3999619
4056484
4056485
13233
13235
YES
Null
—
2171
4031594
4031711
4094354
4094355
13233
13235
YES
O69621
—
2172
4031993
4031994
4094627
4094644
13233
13235
YES
Null
—
2173
4032348
4032349
4094998
4095000
13233
13235
YES
O69623
—
2174
4036755
4036757
4099406
4099407
13233
13235
YES
Null
—
2175
4076537
4076539
4139187
4139188
13233
13235
YES
O69664
glycerol kinase
activity
2176
4092930
4093092
4155579
4155580
13233
13235
YES
P96420
enzyme activity
2177
4094427
4094428
4156905
4156946
13233
13235
YES
Null
—
2178
4107128
4107129
4169665
4169667
13233
13235
YES
O69691
—
2179
4108423
4108425
4170961
4170962
13233
13235
YES
O69692
—
2180
4133434
4133436
4197137
4197138
13233
13235
YES
Null
—
2181
4134910
4134911
4198612
4198614
13233
13235
YES
Null
—
2182
4154969
4154971
4218672
4218673
13233
13235
YES
P72040
—
2183
4247018
4247020
4310742
4310743
13233
13235
YES
P96242
proteolysis and
peptidolysis
2184
4254698
4254699
4318421
4318691
13233
13235
YES
Null
—
2185
4274868
4274869
4338592
4338594
13233
13235
YES
Null
—
2186
4277269
4277306
4340994
4340995
13233
13235
YES
P96213
—
2187
4277709
4277722
4341398
4341399
13233
13235
YES
P96213
—
2188
4295484
4295503
4359161
4359162
13233
13235
YES
O69743
—
2189
4295520
4295548
4359179
4359180
13233
13235
YES
O69743
—
2190
4297431
4297432
4361063
4361065
13233
13235
YES
Q933K8
—
2191
4297455
4297457
4361088
4361089
13233
13235
YES
Q933K8
—
2192
4307387
4307388
4371019
4373416
13233
13235
YES
O05457, O05455
—
2193
4307808
4307809
4373846
4373848
13233
13235
YES
O05454
—
2194
4308332
4308333
4374371
4374373
13233
13235
YES
Null
—
2195
4312098
4312100
4378138
4378139
13233
13235
YES
O05450
—
2196
4316061
4316062
4382100
4382102
13233
13235
YES
O05448
—
2197
4317102
4317108
4383142
4383143
13233
13235
YES
O07036
—
2198
4318998
4318999
4385033
4385035
13233
13235
YES
O05446
—
2199
4334624
4334625
4400660
4400662
13233
13235
YES
O53590
DNA binding
activity
2200
3076218
3076219
3122987
3123052
13233
13235
YES
Null
—
2201
71576
71614
71584
71585
147805
147807
NO
NULL
NULL
2202
131213
131215
131174
131175
578886
578887
NO
NULL
NULL
2203
147853
147854
147812
147814
582109
582110
NO
NULL
NULL
2204
230770
230772
230575
230576
596768
596769
NO
NULL
NULL
2205
291957
291959
293631
293632
612279
612281
NO
NULL
NULL
2206
578459
578500
577494
577495
664896
664897
NO
NULL
NULL
2207
612063
612064
610910
610912
704228
704229
NO
NULL
NULL
2208
743870
744394
742632
742633
730004
730005
NO
NULL
NULL
2209
804268
804309
802498
802499
737681
737682
NO
NULL
NULL
2210
856450
856451
854258
854260
804527
804680
NO
NULL
NULL
2211
953566
953567
952809
952811
815060
815062
NO
NULL
NULL
2212
961024
961025
960268
960309
960120
960270
NO
NULL
NULL
2213
1064550
1064551
1064081
1064110
1090204
1090205
NO
NULL
NULL
2214
1090629
1090631
1090189
1090190
1172885
1172887
NO
NULL
NULL
2215
1165969
1165971
1165520
1165521
1277359
1277361
NO
NULL
NULL
2216
1173288
1173289
1172837
1172839
1305018
1305133
NO
NULL
NULL
2217
1306903
1306904
1305528
1305643
1312879
1312880
NO
NULL
NULL
2218
1314587
1314589
1313336
1313337
1365329
1365330
NO
NULL
NULL
2219
1475063
1475064
1477025
1477027
1408866
1408867
NO
NULL
NULL
2220
1539986
1539987
1541949
1543298
1476568
1476570
NO
NULL
NULL
2221
1837548
1837549
1852180
1852182
1489302
1489303
NO
NULL
NULL
2222
1892915
1892916
1907517
1907558
1606135
1606137
NO
NULL
NULL
2223
1914068
1914069
1928724
1928726
1630252
1630253
NO
NULL
NULL
2224
1941012
1941053
1955670
1955671
1644464
1644505
NO
NULL
NULL
2225
2064977
2064978
2074511
2074614
1843089
1843091
NO
NULL
NULL
2226
2087040
2087041
2096828
2096830
1886393
1886394
NO
NULL
NULL
2227
2093386
2093387
2103175
2103177
1898321
1898362
NO
NULL
NULL
2228
2099733
2099735
2109523
2109524
1919528
1919530
NO
NULL
NULL
2229
2199225
2199227
2207589
2207590
2094050
2094052
NO
NULL
NULL
2230
2254439
2254440
2270521
2270531
2100397
2100399
NO
NULL
NULL
2231
2347255
2347256
2365412
2366761
2132111
2132112
NO
NULL
NULL
2232
2349048
2349049
2368563
2368565
2484768
2484769
NO
NULL
NULL
2233
2382325
2382432
2401925
2401926
2484875
2484876
NO
NULL
NULL
2234
2410508
2410509
2430114
2431463
2529221
2529262
NO
NULL
NULL
2235
2502267
2502271
2523205
2523206
2562613
2562614
NO
NULL
NULL
2236
2511025
2511026
2531961
2532058
2701263
2701264
NO
NULL
NULL
2237
2544362
2544364
2566766
2566767
2721050
2721071
NO
NULL
NULL
2238
2592156
2592158
2614558
2614559
2790757
2790759
NO
NULL
NULL
2239
2673694
2673779
2705602
2705603
2846431
2846432
NO
NULL
NULL
2240
2692384
2692385
2724199
2724220
2953712
2953714
NO
NULL
NULL
2241
2752776
2752777
2784614
2785963
2977206
2977208
NO
NULL
NULL
2242
2762072
2762073
2795268
2795270
3088594
3088595
NO
NULL
NULL
2243
2938901
2938902
2982418
2982420
3113937
3114520
NO
NULL
NULL
2244
2947177
2947218
2990695
2990696
3114673
3114674
NO
NULL
NULL
2245
3075770
3075771
3119217
3119800
3116761
3116762
NO
NULL
NULL
2246
3075914
3076356
3119953
3119954
3117201
3117264
NO
NULL
NULL
2247
3076439
3076501
3120027
3120028
3150246
3150287
NO
NULL
NULL
2248
3078601
3078745
3122118
3122119
3220467
3220468
NO
NULL
NULL
2249
3078967
3078968
3122331
3122394
3233882
3233923
NO
NULL
NULL
2250
3112605
3112606
3156032
3156073
3285765
3285766
NO
NULL
NULL
2251
3196190
3196191
3239559
3239600
3330159
3330160
NO
NULL
NULL
2252
3248018
3248123
3291442
3291443
3345553
3345554
NO
NULL
NULL
2253
3293332
3293333
3336642
3336751
3370822
3370824
NO
NULL
NULL
2254
3307774
3307815
3351211
3351212
3475760
3475762
NO
NULL
NULL
2255
3313357
3313358
3356738
3356740
3561846
3561847
NO
NULL
NULL
2256
3371757
3371758
3415194
3415209
3585541
3585542
NO
NULL
NULL
2257
3430544
3430546
3473994
3473995
3589158
3589159
NO
NULL
NULL
2258
3436512
3436513
3479961
3479963
3589214
3589215
NO
NULL
NULL
2259
3484287
3486424
3529178
3529179
3589361
3589363
NO
NULL
NULL
2260
3508479
3508480
3551226
3552575
3590883
3590885
NO
NULL
NULL
2261
3508604
3508605
3552709
3554058
3590911
3590912
NO
NULL
NULL
2262
3513313
3513315
3558776
3558777
3685808
3685849
NO
NULL
NULL
2263
3521477
3521488
3566939
3566940
3702512
3702516
NO
NULL
NULL
2264
3545179
3545181
3590635
3590636
3717525
3717526
NO
NULL
NULL
2265
3545228
3545230
3590683
3590684
3747436
3747442
NO
NULL
NULL
2266
3549001
3549042
3594455
3594456
3787100
3787101
NO
NULL
NULL
2267
3662150
3662151
3707621
3707625
3811352
3811353
NO
NULL
NULL
2268
3706947
3706948
3753410
3753680
3835096
3835097
NO
NULL
NULL
2269
3708737
3708738
3755201
3755207
3864545
3864549
NO
NULL
NULL
2270
3748507
3748510
3794864
3794865
3864582
3864584
NO
NULL
NULL
2271
3748698
3748699
3795053
3796402
3903645
3903646
NO
NULL
NULL
2272
3772838
3773120
3820497
3820498
4017722
4017724
NO
NULL
NULL
2273
3810175
3810176
3862469
3862471
4086889
4086906
NO
NULL
NULL
2274
3826298
3826299
3878594
3878598
4091666
4091667
NO
NULL
NULL
2275
3826332
3826333
3878631
3878633
4109424
4109425
NO
NULL
NULL
2276
3968799
3968800
4025580
4025582
4160762
4160763
NO
NULL
NULL
2277
3999617
3999619
4056484
4056485
4348926
4348927
NO
NULL
NULL
2278
4031993
4031994
4094627
4094644
4366675
4366677
NO
NULL
NULL
2279
4036755
4036757
4099406
4099407
NO
NULL
NULL
2280
4094427
4094428
4156905
4156946
NO
NULL
NULL
2281
4133434
4133436
4197137
4197138
NO
NULL
NULL
2282
4134910
4134911
4198612
4198614
NO
NULL
NULL
2283
4254698
4254699
4318421
4318691
NO
NULL
NULL
2284
4274868
4274869
4338592
4338594
NO
NULL
NULL
2285
4308332
4308333
4374371
4374373
NO
NULL
NULL
2286
3076218
3076219
3122987
3123052
NO
NULL
NULL
Table II: List of insertion/deletions (indels) in Mycobacaterium tuberculosis / M. bovis BCG
Polymorphism ID: The ID by which the polymorphism can be identified
BCG Start: The position in the genome of M. bovis BCG at which insertion/deletion starts
BCG End: The position in the genome of M. bovis BCG at which insertion/deletion ends
H37Rv Start: The position in the genome of M. tuberculosis H37Rv at which insertion/deletion starts
H37Rv End: The position in the genome of M. tuberculosis H37Rv at which insertion/deletion ends
CDC1551 Start: The position in the genome of M. tuberculosis CDC1551 at which insertion/deletion starts
CDC1551 End: The position in the genome of M. tuberculosis CDC1551 at which insertion/deletion ends
ORF: Indicates whether the polymorphism occurs in an open reading frame (yes) or not (no)
GO ID: The ID for the sequence in the gene ontology database
Putative function: The putative function of the gene in which the SNP occurs.
[0245]
TABLE 3
List of long polymorphisms in Mycobacterium tuberculosis / M. bovis BCG.
Polymorphism
BCG
H37Rv
H37Rv
ID
Start
BCG End
start
end
CDC start
CDC end
ORF
GO ID
Putative Function
2287
55529
55544
55543
55552
103765
105054
Yes
P71707
enzyme activity
2288
103810
105100
103773
105062
103765
105054
Yes
Q50655,
—
Q10891
2289
337700
337733
336678
336711
103765
105054
Yes
O53684
—
2290
339670
339722
338666
338718
103765
105054
Yes
O53684
—
2291
468517
468610
467498
467589
103765
105054
Yes
O53722
—
2292
840823
840895
838955
838967
103765
105054
Yes
O53810
—
2293
891209
892235
889018
891403
103765
105054
Yes
O07182
DNA binding activity
2294
928362
928365
927446
927461
103765
105054
Yes
O53844
—
2295
1094366
1094867
1093925
1094414
103765
105054
Yes
O53891
—
2296
1413023
1413095
1414785
1414947
103765
105054
Yes
Q11053
protein kinase activity
2297
1466961
1466963
1468912
1468925
103765
105054
Yes
Q10621
DNA binding activity
2298
1530977
1531052
1532940
1533015
103765
105054
Yes
Q11031
—
2299
1531093
1531199
1533056
1533162
103765
105054
Yes
Q11031
—
2300
1619416
1619437
1623086
1623088
103765
105054
Yes
Null
—
2301
1629885
1631221
1633536
1634635
103765
105054
Yes
O06810
—
2302
1633501
1634095
1636765
1637347
103765
105054
Yes
O06808
—
2303
1634927
1634959
1638179
1638211
103765
105054
Yes
O06808
—
2304
1773935
1775045
1788567
1789677
103765
105054
Yes
O06603,
—
O06602
2305
1986939
1988741
1996098
1998299
103765
105054
Yes
O06798
nucleic acid binding
activity
2306
2156908
2157537
2165848
2165901
103765
105054
Yes
O07716
enzyme activity
2307
2241088
2241814
2262170
2262896
103765
105054
Yes
O53461
nucleic acid binding
activity
2308
2278758
2278826
2294843
2294911
103765
105054
Yes
O53490
enzyme activity
2309
2278938
2278961
2295023
2295046
103765
105054
Yes
O53490
enzyme activity
2310
2279216
2280345
2295301
2296430
103765
105054
Yes
O53490
enzyme activity
2311
2285306
2286046
2301391
2302131
103765
105054
Yes
O53490
enzyme activity
2312
2501326
2501345
2522176
2522283
103765
105054
Yes
Null
—
2313
2604210
2605004
2635574
2636928
103765
105054
Yes
P95248
—
2314
2912021
2912672
2944553
2945204
103765
105054
Yes
O06199
—
2315
3079181
3079369
3122617
3123099
103765
105054
Yes
Null
—
2316
3079550
3079876
3123280
3123311
103765
105054
Yes
Null
—
2317
3189218
3189388
3232699
3232757
103765
105054
Yes
Null
—
2318
3204423
3204457
3247847
3247881
103765
105054
Yes
Q10977
enzyme activity
2319
3334709
3334850
3378091
3378288
103765
105054
Yes
P31500
—
2320
3336266
3336348
3379704
3379786
103765
105054
Yes
O53268
—
2321
3689443
3689509
3732189
3735810
103765
105054
Yes
O53393
carboxypeptidase A
activity
2322
3689905
3689925
3736206
3736226
103765
105054
Yes
O53393
carboxypeptidase A
activity
2323
3692719
3692740
3739123
3739357
103765
105054
Yes
O53395
—
2324
3703709
3703744
3750172
3750207
103765
105054
Yes
O50378
—
2325
3838472
3838474
3890772
3892132
103765
105054
Yes
Null
—
2326
3876017
3876037
3930462
3930473
103765
105054
Yes
O53552
—
2327
3878151
3878280
3932746
3932749
103765
105054
Yes
O53553
—
2328
3879035
3879494
3933477
3934539
103765
105054
Yes
O53553
—
2329
3879583
3879686
3934628
3934731
103765
105054
Yes
O53553
—
2330
3879863
3880576
3934956
3936335
103765
105054
Yes
O53553
—
2331
3885770
3886315
3941529
3941721
103765
105054
Yes
O53556,
—
O53557
2332
3887733
3887868
3943139
3943175
103765
105054
Yes
O53557
hydroxymethylglutaryl-
CoA reductase (NADPH)
activity
2333
3890973
3891602
3946262
3946876
103765
105054
Yes
O53559
—
2334
3891837
3892400
3947111
3947380
103765
105054
Yes
O53559
—
2335
3892771
3892967
3948342
3949747
103765
105054
Yes
O53559
—
2336
4127053
4127055
4189590
4190758
103765
105054
Yes
O69705
—
2337
4189866
4189868
4253568
4253581
103765
105054
Yes
Q10621
DNA binding activity
2338
4190616
4190621
4254329
4254345
103765
105054
Yes
Null
—
2339
1973115
1973588
2628042
2630136
103765
105054
Yes
P95245,
—
P95246
—
2340
3079605
3079661
3119272
3119329
103765
105054
Yes
Null
Null
2341
1619416
1619437
1623086
1623088
1622970
1622972
No
Null
Null
2342
2501326
2501345
2522176
2522283
2354339
2354347
No
Null
Null
2343
3079181
3079369
3122617
3123099
2519450
2519556
No
Null
Null
2344
3079550
3079876
3123280
3123311
2520462
2520465
No
Null
Null
2345
3189218
3189388
3232699
3232757
2985403
2985518
No
Null
Null
2346
3838472
3838474
3890772
3892132
3018402
3018431
No
Null
Null
2347
4190616
4190621
4254329
4254345
3226853
3226952
No
Null
Null
2348
3079605
3079661
3119272
3119329
3589269
3589323
No
Null
Null
2349
4245189
4245204
No
Null
Null
2350
4246654
4246670
No
Null
Null
2351
3113992
3114049
No
Null
Null
Table III: List of long polymorphisms in Mycobacaterium tuberculosis / M. bovis BCG
Polymorphism ID: The ID by which the polymorphism can be identified
BCG Start: The position in the genome of M. bovis BCG at which multiple polymorhisms start occurring
BCG End: The position in the genome of M. bovis BCG at which multiple polymorhisms end
H37Rv Start: The position in the genome of M. tuberculosis H37Rv at which multiple polymorhisms start
H37Rv End: The position in the genome of M. tuberculosis H37Rv at multiple polymorhisms end
C1551 Start: The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms start
CDC1551 End: The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms ends
ORF: Indicates whether the polymorphism occurs in an open reading frame (yes) or not (no)
GO ID: The ID for the sequence in the gene ontology database
Putative function: The putative function of the gene in which the SNP occurs.
[0246]
TABLE 4
a:
List of Polymorphisms (Single Nucleotide Polymorphisms) in genes involved in cell wall synthesis
Polymorphism
BCG
Query
Query
Query
Query
Type of
Putative
ID
BCG Position
base
BCG AA
name
Position
base
aa
ORF
SNP
GO ID
Function
48
53663
T
L
H37Rv
53677
C
P
Yes
NS, NC
P71707
Cell wall
synthesis
48
53663
T
L
CDC1551
53623
C
P
Yes
NS, NC
Q8VKS5
Cell wall
synthesis
1014
2393645
G
P
H37Rv
2413129
A
L
Yes
NS, NC
O06224
Cell wall
synthesis
1014
2393645
G
P
CDC1551
2411822
A
L
Yes
NS, NC
O06224
Cell wall
synthesis
1015
2393760
A
L
H37Rv
2413244
C
V
Yes
NS, C
O06224
Cell wall
synthesis
1015
2393760
A
L
CDC1551
2411937
C
V
Yes
NS, C
O06224
Cell wall
synthesis
1240
2987804
G
H
H37Rv
3031165
A
Y
Yes
NS, C
O07218
Cell wall
synthesis
1240
2987804
G
H
CDC1551
3026104
A
Y
Yes
NS, C
O07218
Cell wall
synthesis
1746
4176966
T
I
H37Rv
4240668
C
T
Yes
NS, NC
P72059
Cell wall
synthesis
1746
4176966
T
I
CDC1551
4232983
C
T
Yes
NS, NC
P72059
Cell wall
synthesis
1749
4182846
G
S
H37Rv
4246548
A
N
Yes
NS, C
P72030
Cell wall
synthesis
1749
4182846
G
S
CDC1551
4238863
A
N
Yes
NS, C
P72030
Cell wall
synthesis
1751
4183941
C
A
H37Rv
4247643
A
E
Yes
NS, NC
P72030
Cell wall
synthesis
1751
4183941
C
A
CDC1551
4239958
A
E
Yes
NS, NC
P72030
Cell wall
synthesis
Polymorphism
ID
BCG start
BCG end
Query name
Query start
Query end
ORF
GO ID
Putative Function
b:
List of Polymorphisms (Insertions/deletions) in genes involved in cell wall synthesis
1906
936197
936204
H37Rv
935446
935447
Yes
O53850
Cell wall synthesis
1947
1439690
1439691
H37Rv
1441542
1441686
Yes
Q10614
Cell wall synthesis
2094
3294465
3294466
H37Rv
3337893
3337903
Yes
P95114
Cell wall synthesis
1906
936197
936204
CDC1551
935348
935349
Yes
O53850
Cell wall synthesis
1947
1439690
1439691
CDC1551
1441030
1441174
Yes
Q10614
Cell wall synthesis
2094
3294465
3294466
CDC1551
3332273
3332283
Yes
P95114
Cell wall synthesis
c:
List of Polymorphisms (long polymorphisms) in genes involved in cell wall synthesis
2287
55529
55544
H37Rv
55543
55552
Yes
P71707
Cell wall Synthesis
Table IV: List of long polymorphisms in genes involved in cell wall synthesis
Polymorphism ID: The ID by which the polymorphism can be identified
BCG Start: The position in the genome of M. bovis BCG at which multiple polymorhisms start occurring
BCG End: The position in the genome of M. bovis BCG at which multiple polymorhisms end
H37Rv Start: The position in the genome of M. tuberculosis H37Rv at which multiple polymorhisms start
H37Rv End: The position in the genome of M. tuberculosis H37Rv at multiple polymorhisms end
C1551 Start: The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms start
CDC1551 End: The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms ends
ORF: Indicates whether the polymorphism occurs in an open reading frame (yes) or not (no)
GO ID: The ID for the sequence in the gene ontology database
Putative function: The putative function of the gene in which the SNP occurs.
[0247]
TABLE 5
a: List of Polymorphisms (Single Nucleotide Polymorphisms) in transcription factors.
Polymorphism
BCG
BCG
BCG
Query
Query
Query
Query
Type of
ID
Position
base
AA
name
Position
base
aa
ORF
SNP
GO ID
Putative Function
63
86899
G
V
H37Rv
86862
A
I
Yes
NS, C
O53623
Transcription factor
63
86899
G
V
CDC1551
86854
A
I
Yes
NS, C
O53623
Transcription factor
188
366022
T
V
H37Rv
364973
C
A
Yes
NS, C
O07229
Transcription factor
188
366022
T
V
CDC1551
365037
C
A
Yes
NS, C
O07229
Transcription factor
228
456342
G
R
H37Rv
455323
C
P
Yes
NS, NC
O53712
Transcription factor
228
456342
G
R
CDC1551
455414
C
P
Yes
NS, NC
O53712
Transcription factor
231
467402
C
A
H37Rv
466383
A
D
Yes
NS, NC
O53720
Transcription factor
231
467402
C
A
CDC1551
466474
A
D
Yes
NS, NC
O53720
Transcription factor
299
634973
C
V
CDC1551
635181
T
I
Yes
NS, C
Q8VKJ4
Transcription factor
313
671788
A
H
H37Rv
670543
G
R
Yes
NS, NC
O53773
Transcription factor
313
671788
A
H
CDC1551
671996
G
R
Yes
NS, NC
O53773
Transcription factor
326
700963
T
I
H37Rv
699716
C
V
Yes
NS, C
O07776
Transcription factor
326
700963
T
I
CDC1551
701166
C
V
Yes
NS, C
O07776
Transcription factor
405
912091
C
P
H37Rv
911259
T
L
Yes
NS, NC
O53830
Transcription factor
405
912091
C
P
CDC1551
911170
T
L
Yes
NS, NC
O53830
Transcription factor
433
941645
G
P
H37Rv
940888
C
A
Yes
NS, NC
O53856
Transcription factor
433
941645
G
P
CDC1551
940790
C
A
Yes
NS, NC
O53856
Transcription factor
483
1097474
A
S
H37Rv
1097021
G
G
Yes
NS, NC
O53894
Transcription factor
483
1097474
A
S
CDC1551
1097062
G
G
Yes
NS, NC
O53894
Transcription factor
598
1375153
G
P
H37Rv
1373907
A
S
Yes
NS, NC
O86313
Transcription factor
598
1375153
G
P
CDC1551
1373397
A
S
Yes
NS, NC
O86313
Transcription factor
611
1401640
G
V
H37Rv
1400394
A
M
Yes
NS, NC
Q11039
Transcription factor
611
1401640
G
V
CDC1551
1399883
A
M
Yes
NS, NC
Q11039
Transcription factor
639
1476918
T
*
H37Rv
1478881
C
W
Yes
NS, TP
Q10630
Transcription factor
639
1476918
T
*
CDC1551
1478424
C
W
Yes
NS, TP
Q10630
Transcription factor
640
1477120
C
V
H37Rv
1479083
T
I
Yes
NS, C
Q10630
Transcription factor
640
1477120
C
V
CDC1551
1478626
T
I
Yes
NS, C
Q10630
Transcription factor
659
1524738
T
V
H37Rv
1526701
G
G
Yes
NS, C
Q11028
Transcription factor
659
1524738
T
V
CDC1551
1527918
G
G
Yes
NS, C
Q8VK33
Transcription factor
660
1525971
C
A
H37Rv
1527934
A
D
Yes
NS, NC
Q11028
Transcription factor
660
1525971
C
A
CDC1551
1529151
A
D
Yes
NS, NC
Q8VK33
Transcription factor
677
1534974
T
T
H37Rv
1536937
C
A
Yes
NS, NC
Q11034
Transcription factor
677
1534974
T
T
CDC1551
1538155
C
A
Yes
NS, NC
Q11034
Transcription factor
700
1580686
C
L
H37Rv
1584377
A
I
Yes
NS, C
P71675
Transcription factor
700
1580686
C
L
CDC1551
1584233
A
I
Yes
NS, C
P71675
Transcription factor
722
1643728
T
V
H37Rv
1646980
C
A
Yes
NS, C
O53151
Transcription factor
722
1643728
T
V
CDC1551
1647138
C
A
Yes
NS, C
O53151
Transcription factor
801
1886196
G
A
H37Rv
1900798
A
V
Yes
NS, C
O53922
Transcription factor
801
1886196
G
A
CDC1551
1891602
A
V
Yes
NS, C
O53922
Transcription factor
1061
2504215
G
A
H37Rv
2525150
T
D
Yes
NS, NC
Q10528
Transcription factor
1061
2504215
G
A
CDC1551
2522412
T
D
Yes
NS, NC
Q10528
Transcription factor
1099
2609911
G
R
H37Rv
2641838
A
H
Yes
NS, NC
O05839
Transcription factor
1099
2609911
G
R
CDC1551
2639170
A
H
Yes
NS, NC
O05839
Transcription factor
1174
2825466
T
D
H37Rv
2858667
G
A
Yes
NS, NC
P95020
Transcription factor
1174
2825466
T
D
CDC1551
2854156
G
A
Yes
NS, NC
P95020
Transcription factor
1241
2988773
C
A
H37Rv
3032134
T
V
Yes
NS, C
Q50765
Transcription factor
1241
2988773
C
A
CDC1551
3027073
T
V
Yes
NS, C
Q50765
Transcription factor
1261
3043278
T
I
H37Rv
3086725
C
M
Yes
NS, NC
O33321
Transcription factor
1261
3043278
T
I
CDC1551
3081450
C
M
Yes
NS, NC
O33321
Transcription factor
1264
3053917
C
A
H37Rv
3097365
A
D
Yes
NS, NC
O33330
Transcription factor
1264
3053917
C
A
CDC1551
3092089
A
D
Yes
NS, NC
O33330
Transcription factor
1405
3404010
A
C
H37Rv
3447460
G
R
Yes
NS, NC
Q06861
Transcription factor
1405
3404010
A
C
CDC1551
3443253
G
R
Yes
NS, NC
Q06861
Transcription factor
1503
3626758
A
V
H37Rv
3672229
G
A
Yes
NS, C
P96896
Transcription factor
1503
3626758
A
V
CDC1551
3667068
G
A
Yes
NS, C
P96896
Transcription factor
b: List of Polymorphisms (Insertions/Deletions) in transcription factors.
Polymorphism
Functional
Putative
ID
BCG start
BCG end
Query name
Query start
Query end
ORF
Annotation
Function
1849
194495
194498
H37Rv
194303
194304
Yes
O07410
Transcription
Factor
2074
3042938
3042939
H37Rv
3086361
3086386
Yes
O33321
Transcription
Factor
2199
4334624
4334625
H37Rv
4400660
4400662
Yes
O53590
Transcription
Factor
1902
890037
890038
CDC1551
889115
889117
Yes
Q8VKD9
Transcription
Factor
1945
1404177
1404178
CDC1551
1402420
1405418
Yes
Q11063
Transcription
Factor
2074
3042938
3042939
CDC1551
3081086
3081111
Yes
O33321
Transcription
Factor
Table V: List of long polymorphisms in Transcription factors
Polymorphism ID The ID by which the polymorphism can be identified
BCG Start The position in the genome of M. bovis BCG at which multiple polymorhisms start occurring
BCG End The position in the genome of M. bovis BCG at which multiple polymorhisms end
H37Rv Start The position in the genome of M. tuberculosis H37Rv at which multiple polymorhisms start
H37Rv End The position in the genome of M. tuberculosis H37Rv at multiple polymorhisms end
C1551 Start The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms start
CDC1551 End The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms ends
ORF Indicates whether the polymorphism occurs in an open reading frame (yes) or not (no)
GO ID The ID for the sequence in the gene ontology database
Putative function The putative function of the gene in which the SNP occurs.
[0248]
TABLE 6
a: List of Polymorphisms(Single Nucleotide Polymorphisms) in genes involved in lipid metabolism
Polymorphism
BCG
BCG
BCG
Query
Query
Query
Query
Type of
Putative
ID
Position
base
AA
name
Position
base
aa
ORF
SNP
GO ID
Function
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
29
26034
G
P
CDC1551
26035
C
A
Yes
NS, NC
P71591
Transport
69
96136
A
I
H37Rv
96099
G
V
Yes
NS, C
Q10884
Transport
72
100624
G
A
H37Rv
100587
A
T
Yes
NS, NC
Q10876
Transport
72
100624
G
A
CDC1551
100579
A
T
Yes
NS, NC
Q10876
Transport
79
126600
A
S
H37Rv
126561
C
A
Yes
NS, NC
Q10900
Transport
79
126600
A
S
CDC1551
126554
C
A
Yes
NS, NC
Q10900
Transport
80
126840
G
P
H37Rv
126801
A
S
Yes
NS, NC
Q10900
Transport
80
126840
G
P
CDC1551
126794
A
S
Yes
NS, NC
Q10900
Transport
82
130172
A
V
H37Rv
130133
G
A
Yes
NS, C
Q10900
Transport
82
130172
A
V
CDC1551
130126
G
A
Yes
NS, C
Q10900
Transport
99
170273
G
L
H37Rv
170081
A
F
Yes
NS, NC
P96820
Transport
99
170273
G
L
CDC1551
170254
A
F
Yes
NS, NC
P96820
Transport
123
227215
G
V
H37Rv
227020
A
I
Yes
NS, C
O53645
Transport
123
227215
G
V
CDC1551
227134
A
I
Yes
NS, C
Q8VKP9
Transport
124
227738
T
M
H37Rv
227543
C
T
Yes
NS, NC
O53645
Transport
124
227738
T
M
CDC1551
227657
C
T
Yes
NS, NC
Q8VKP9
Transport
125
228053
T
L
H37Rv
227858
C
P
Yes
NS, NC
O53645
Transport
125
228053
T
L
CDC1551
227972
C
P
Yes
NS, NC
Q8VKP9
Transport
141
262385
A
N
H37Rv
262158
G
D
Yes
NS, NC
P96400
Transport
141
262385
A
N
CDC1551
262274
G
D
Yes
NS, NC
P96400
Transport
156
292523
G
A
H37Rv
294196
T
E
Yes
NS, NC
O53666
Transport
156
292523
G
A
CDC1551
294313
T
E
Yes
NS, NC
O53666
Transport
157
292778
C
R
H37Rv
294451
T
K
Yes
NS, C
O53666
Transport
157
292778
C
R
CDC1551
294568
T
K
Yes
NS, C
O53666
Transport
201
394778
A
Y
H37Rv
393746
G
H
Yes
NS, C
O08447
Transport
201
394778
A
Y
CDC1551
393808
G
H
Yes
NS, C
O08447
Transport
218
441762
C
A
H37Rv
440743
T
V
Yes
NS, C
O06312
Transport
218
441762
C
A
CDC1551
440833
T
V
Yes
NS, C
O06312
Transport
221
446432
T
S
H37Rv
445413
C
G
Yes
NS, NC
O53703
Transport
221
446432
T
S
CDC1551
445503
C
G
Yes
NS, NC
O53703
Transport
222
446797
T
H
H37Rv
445778
C
R
Yes
NS, NC
O53703
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
222
446797
T
H
CDC1551
445868
C
R
Yes
NS, NC
O53703
Transport
226
452456
G
S
H37Rv
451437
A
F
Yes
NS, NC
O53708
Transport
226
452456
G
S
CDC1551
451527
A
F
Yes
NS, NC
O53708
Transport
234
472937
G
A
H37Rv
471916
A
V
Yes
NS, C
P95200
Transport
234
472937
G
A
CDC1551
472009
A
V
Yes
NS, C
P95200
Transport
247
502639
T
V
H37Rv
501618
C
A
Yes
NS, C
P96261
Transport
247
502639
T
V
CDC1551
503069
C
A
Yes
NS, C
P96261
Transport
250
515676
G
A
H37Rv
514655
T
E
Yes
NS, NC
P96271
Transport
250
515676
G
A
CDC1551
516106
T
E
Yes
NS, NC
P96271
Transport
280
582972
A
F
H37Rv
581819
G
L
Yes
NS, NC
Q11157
Transport
280
582972
A
F
CDC1551
583188
G
L
Yes
NS, NC
Q11157
Transport
383
846049
C
V
H37Rv
843857
T
I
Yes
NS, C
O53815
Transport
383
846049
C
V
CDC1551
846000
T
I
Yes
NS, C
O53815
Transport
384
846399
G
A
H37Rv
844207
A
V
Yes
NS, C
O53815
Transport
384
846399
G
A
CDC1551
846350
A
V
Yes
NS, C
O53815
Transport
406
913660
G
L
H37Rv
912828
C
F
Yes
NS, NC
O53832
Transport
406
913660
G
L
CDC1551
912739
C
F
Yes
NS, NC
O53832
Transport
468
1041172
C
A
H37Rv
1040704
A
S
Yes
NS, NC
O05870
Transport
468
1041172
C
A
CDC1551
1040719
A
S
Yes
NS, NC
O05870
Transport
469
1043636
C
A
H37Rv
1043167
T
V
Yes
NS, C
P15712
Transport
469
1043636
C
A
CDC1551
1043182
T
V
Yes
NS, C
P15712
Transport
477
1080631
A
N
H37Rv
1080190
G
D
Yes
NS, NC
P77894
Transport
477
1080631
A
N
CDC1551
1080205
G
D
Yes
NS, NC
P77894
Transport
478
1083482
A
H
H37Rv
1083041
C
Q
Yes
NS, NC
P71539
Transport
478
1083482
A
H
CDC1551
1083056
C
Q
Yes
NS, NC
P71539
Transport
483
1097474
A
S
H37Rv
1097021
G
G
Yes
NS, NC
O53894
Transport
483
1097474
A
S
CDC1551
1097062
G
G
Yes
NS, NC
O53894
Transport
485
1102935
T
L
H37Rv
1102482
G
V
Yes
NS, C
O53899
Transport
485
1102935
T
L
CDC1551
1102523
G
V
Yes
NS, C
O53899
Transport
561
1290071
C
L
H37Rv
1288697
G
V
Yes
NS, C
O06559
Transport
561
1290071
C
L
CDC1551
1288187
G
V
Yes
NS, C
O06559
Transport
562
1291161
G
G
H37Rv
1289787
A
D
Yes
NS, NC
O06559
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
562
1291161
G
G
CDC1551
1289277
A
D
Yes
NS, NC
O06559
Transport
563
1295376
T
V
H37Rv
1294002
C
A
Yes
NS, C
O06562
Transport
563
1295376
T
V
CDC1551
1293492
C
A
Yes
NS, C
O06562
Transport
567
1307530
C
S
H37Rv
1306279
A
I
Yes
NS, NC
O50431
Transport
567
1307530
C
S
CDC1551
1305769
A
I
Yes
NS, NC
O50431
Transport
568
1309207
T
N
H37Rv
1307956
G
T
Yes
NS, C
O50431
Transport
568
1309207
T
N
CDC1551
1307446
G
T
Yes
NS, C
O50431
Transport
595
1368728
G
G
H37Rv
1367482
T
W
Yes
NS, NC
O33220
Transport
595
1368728
G
G
CDC1551
1366972
T
W
Yes
NS, NC
O33220
Transport
602
1383703
C
R
H37Rv
1382457
T
H
Yes
NS, NC
O50455
Transport
602
1383703
C
R
CDC1551
1381947
T
H
Yes
NS, NC
O50455
Transport
609
1396254
G
G
H37Rv
1395008
A
R
Yes
NS, NC
O50465
Transport
609
1396254
G
G
CDC1551
1394497
A
R
Yes
NS, NC
O50465
Transport
780
1825125
C
R
H37Rv
1839757
G
G
Yes
NS, NC
O06151
Transport
780
1825125
C
R
CDC1551
1830666
G
G
Yes
NS, NC
O06151
Transport
805
1897364
A
F
H37Rv
1912022
C
V
Yes
NS, NC
O33188
Transport
805
1897364
A
F
CDC1551
1902826
C
V
Yes
NS, NC
O33188
Transport
815
1921036
G
A
H37Rv
1935693
T
S
Yes
NS, NC
O33206
Transport
815
1921036
G
A
CDC1551
1926497
T
S
Yes
NS, NC
O33206
Transport
816
1921535
A
Q
H37Rv
1936192
G
R
Yes
NS, NC
O33206
Transport
816
1921535
A
Q
CDC1551
1926996
G
R
Yes
NS, NC
O33206
Transport
822
1937372
C
P
H37Rv
1952030
G
A
Yes
NS, NC
P71984
Transport
822
1937372
C
P
CDC1551
1942833
G
A
Yes
NS, NC
P71984
Transport
823
1938167
T
Y
H37Rv
1952825
C
H
Yes
NS, C
P71984
Transport
823
1938167
T
Y
CDC1551
1943628
C
H
Yes
NS, C
P71984
Transport
828
1949354
C
G
H37Rv
1963955
T
D
Yes
NS, NC
P71994
Transport
828
1949354
C
G
CDC1551
1954815
T
D
Yes
NS, NC
P71994
Transport
829
1949427
G
H
H37Rv
1964028
C
D
Yes
NS, NC
P71994
Transport
829
1949427
G
H
CDC1551
1954888
C
D
Yes
NS, NC
P71994
Transport
840
1965950
C
T
H37Rv
1980550
T
M
Yes
NS, NC
O65936
Transport
840
1965950
C
T
CDC1551
1971410
T
M
Yes
NS, NC
O65936
Transport
849
2002085
G
Q
H37Rv
2011625
C
H
Yes
NS, NC
O33180
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
849
2002085
G
Q
CDC1551
2009047
C
H
Yes
NS, NC
O33180
Transport
879
2042298
T
*
H37Rv
2051841
C
Q
Yes
NS, TP
O53958
Transport
879
2042298
T
*
CDC1551
2049263
C
Q
Yes
NS, TP
Q8VJW0
Transport
880
2043142
C
S
H37Rv
2052685
G
*
Yes
NS, TP
O53958
Transport
880
2043142
C
S
CDC1551
2050107
G
*
Yes
NS, TP
Q8VJW0
Transport
885
2053386
C
V
H37Rv
2062920
T
I
Yes
NS, C
Q50614
Transport
885
2053386
C
V
CDC1551
2060259
T
I
Yes
NS, C
Q50614
Transport
886
2054840
G
A
H37Rv
2064374
A
V
Yes
NS, C
Q50614
Transport
886
2054840
G
A
CDC1551
2061713
A
V
Yes
NS, C
Q50614
Transport
904
2092402
A
W
H37Rv
2102191
G
R
Yes
NS, NC
P95160
Transport
904
2092402
A
W
CDC1551
2099413
G
R
Yes
NS, NC
P95160
Transport
907
2097719
T
M
H37Rv
2107509
C
T
Yes
NS, NC
P95155
Transport
907
2097719
T
M
CDC1551
2104731
C
T
Yes
NS, NC
P95155
Transport
914
2112834
G
A
H37Rv
2122623
A
V
Yes
NS, C
P95143
Transport
914
2112834
G
A
CDC1551
2119846
A
V
Yes
NS, C
P95143
Transport
915
2113185
G
A
H37Rv
2122974
C
G
Yes
NS, C
P95143
Transport
915
2113185
G
A
CDC1551
2120197
C
G
Yes
NS, C
P95143
Transport
929
2141958
T
T
H37Rv
2151676
G
P
Yes
NS, NC
O07727
Transport
929
2141958
T
T
CDC1551
2148969
G
P
Yes
NS, NC
O07727
Transport
930
2145004
A
L
H37Rv
2154722
C
R
Yes
NS, NC
Q08129
Transport
930
2145004
A
L
CDC1551
2152015
C
R
Yes
NS, NC
Q08129
Transport
953
2201224
C
G
H37Rv
2222306
T
D
Yes
NS, NC
Q10875
Transport
953
2201224
C
G
CDC1551
2219640
T
D
Yes
NS, NC
Q10875
Transport
980
2271395
A
V
H37Rv
2287480
G
A
Yes
NS, C
O53485
Transport
980
2271395
A
V
CDC1551
2289814
G
A
Yes
NS, C
O53485
Transport
1008
2369039
A
D
H37Rv
2388639
G
G
Yes
NS, NC
O33261
Transport
1009
2369143
A
S
H37Rv
2388743
G
G
Yes
NS, NC
O33261
Transport
1009
2369143
A
S
CDC1551
2387320
G
G
Yes
NS, NC
O33261
Transport
1036
2438267
C
I
H37Rv
2459232
G
M
Yes
NS, NC
Q10387
Transport
1036
2438267
C
I
CDC1551
2456567
G
M
Yes
NS, NC
Q10387
Transport
1062
2507835
A
V
H37Rv
2528771
G
A
Yes
NS, C
O53528
Transport
1062
2507835
A
V
CDC1551
2526031
G
A
Yes
NS, C
O53528
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
1077
2541551
C
A
H37Rv
2563956
A
E
Yes
NS, NC
Q59570
Transport
1077
2541551
C
A
CDC1551
2559803
A
E
Yes
NS, NC
Q59570
Transport
1086
2569172
G
V
H37Rv
2591575
C
L
Yes
NS, C
P71894
Transport
1086
2569172
G
V
CDC1551
2587422
C
L
Yes
NS, C
Q8VJL6
Transport
1110
2660947
A
N
H37Rv
2692873
G
S
Yes
NS, C
P71748
Transport
1110
2660947
A
N
CDC1551
2690205
G
S
Yes
NS, C
P71748
Transport
1112
2661841
G
S
H37Rv
2693770
A
N
Yes
NS, C
P71748
Transport
1112
2661841
G
S
CDC1551
2691102
A
N
Yes
NS, C
P71748
Transport
1113
2663078
T
H
H37Rv
2695007
C
R
Yes
NS, NC
P71746
Transport
1113
2663078
T
H
CDC1551
2692339
C
R
Yes
NS, NC
P71746
Transport
1138
2729181
A
I
H37Rv
2761016
G
M
Yes
NS, NC
O53186
Transport
1138
2729181
A
I
CDC1551
2757863
G
M
Yes
NS, NC
O53186
Transport
1139
2733102
A
L
H37Rv
2764937
G
P
Yes
NS, NC
O53189
Transport
1139
2733102
A
L
CDC1551
2761784
G
P
Yes
NS, NC
O53189
Transport
1192
2880160
G
P
H37Rv
2912710
T
T
Yes
NS, NC
Q50635
Transport
1192
2880160
G
P
CDC1551
2908855
T
T
Yes
NS, NC
Q50635
Transport
1193
2880535
T
T
H37Rv
2913085
C
A
Yes
NS, NC
Q50635
Transport
1193
2880535
T
T
CDC1551
2909230
C
A
Yes
NS, NC
Q50635
Transport
1194
2881707
C
S
H37Rv
2914257
T
N
Yes
NS, C
Q50634
Transport
1194
2881707
C
S
CDC1551
2910402
T
N
Yes
NS, C
Q50634
Transport
1216
2935735
C
A
H37Rv
2968270
T
V
Yes
NS, C
P71942
Transport
1216
2935735
C
A
CDC1551
2964416
T
V
Yes
NS, C
P71942
Transport
1227
2959751
G
G
H37Rv
3003112
C
A
Yes
NS, C
O07187
Transport
1227
2959751
G
G
CDC1551
2998058
C
A
Yes
NS, C
O07187
Transport
1228
2959795
T
C
H37Rv
3003156
G
G
Yes
NS, NC
O07187
Transport
1228
2959795
T
C
CDC1551
2998102
G
G
Yes
NS, NC
O07187
Transport
1230
2963874
G
R
H37Rv
3007235
A
*
Yes
NS, TP
O07192
Transport
1230
2963874
G
R
CDC1551
3002180
A
*
Yes
NS, TP
O07192
Transport
1231
2967056
G
V
H37Rv
3010417
A
I
Yes
NS, C
O07194
Transport
1231
2967056
G
V
CDC1551
3005362
A
I
Yes
NS, C
O07194
Transport
1242
2993548
G
T
H37Rv
3036909
A
I
Yes
NS, NC
O33229
Transport
1242
2993548
G
T
CDC1551
3031848
A
I
Yes
NS, NC
O33229
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
1243
2993831
C
A
H37Rv
3037192
G
P
Yes
NS, NC
O33229
Transport
1243
2993831
C
A
CDC1551
3032131
G
P
Yes
NS, NC
O33229
Transport
1292
3096227
G
P
H37Rv
3139653
C
A
Yes
NS, NC
P71619
Transport
1292
3096227
G
P
CDC1551
3133869
C
A
Yes
NS, NC
Q8VJC1
Transport
1293
3096535
A
L
H37Rv
3139961
G
P
Yes
NS, NC
P71619
Transport
1294
3096724
A
I
H37Rv
3140150
C
S
Yes
NS, NC
P71619
Transport
1296
3099150
A
L
H37Rv
3142577
G
P
Yes
NS, NC
P71616
Transport
1296
3099150
A
L
CDC1551
3136791
G
P
Yes
NS, NC
P71616
Transport
1332
3192343
C
G
H37Rv
3235712
G
R
Yes
NS, NC
Q10970
Transport
1332
3192343
C
G
CDC1551
3230035
G
R
Yes
NS, NC
Q10970
Transport
1333
3193344
C
R
H37Rv
3236713
A
L
Yes
NS, NC
Q10970
Transport
1333
3193344
C
R
CDC1551
3231036
A
L
Yes
NS, NC
Q10970
Transport
1345
3229711
G
D
H37Rv
3273135
C
H
Yes
NS, NC
P96205
Transport
1345
3229711
G
D
CDC1551
3267458
C
H
Yes
NS, NC
P96205
Transport
1387
3343657
A
V
H37Rv
3387094
G
A
Yes
NS, C
O53275
Transport
1387
3343657
A
V
CDC1551
3382833
G
A
Yes
NS, C
O53275
Transport
1396
3377371
G
G
H37Rv
3420822
A
D
Yes
NS, NC
P95099
Transport
1396
3377371
G
G
CDC1551
3416547
A
D
Yes
NS, NC
P95099
Transport
1416
3430975
A
I
H37Rv
3474424
G
V
Yes
NS, C
O05783
Transport
1416
3430975
A
I
CDC1551
3470223
G
V
Yes
NS, C
O05783
Transport
1417
3431707
G
D
H37Rv
3475156
A
N
Yes
NS, NC
O05783
Transport
1417
3431707
G
D
CDC1551
3470955
A
N
Yes
NS, NC
O05783
Transport
1447
3476153
G
A
H37Rv
3521041
A
T
Yes
NS, NC
P95173
Transport
1447
3476153
G
A
CDC1551
3516528
A
T
Yes
NS, NC
P95173
Transport
1453
3488207
G
L
H37Rv
3530952
C
V
Yes
NS, C
O53311
Transport
1453
3488207
G
L
CDC1551
3528588
C
V
Yes
NS, C
O53311
Transport
1454
3489142
T
E
H37Rv
3531888
G
D
Yes
NS, C
O53313
Transport
1454
3489142
T
E
CDC1551
3529524
G
D
Yes
NS, C
O53313
Transport
1466
3528181
C
D
H37Rv
3573633
T
N
Yes
NS, NC
O53346
Transport
1466
3528181
C
D
CDC1551
3568540
T
N
Yes
NS, NC
O53346
Transport
1479
3562541
A
C
H37Rv
3607938
G
R
Yes
NS, NC
O05875
Transport
1479
3562541
A
C
CDC1551
3602842
G
R
Yes
NS, NC
O05875
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
1482
3569604
T
H
H37Rv
3615000
C
R
Yes
NS, NC
O05884
Transport
1482
3569604
T
H
CDC1551
3609903
C
R
Yes
NS, NC
Q8VJ44
Transport
1499
3619961
A
D
H37Rv
3665432
G
G
Yes
NS, NC
P96888
Transport
1499
3619961
A
D
CDC1551
3660271
G
G
Yes
NS, NC
P96888
Transport
1511
3644541
G
S
H37Rv
3690012
A
L
Yes
NS, NC
O53355
Transport
1511
3644541
G
S
CDC1551
3684851
A
L
Yes
NS, NC
Q8VJ36
Transport
1512
3645379
C
A
H37Rv
3690850
T
T
Yes
NS, NC
O53355
Transport
1512
3645379
C
A
CDC1551
3685689
T
T
Yes
NS, NC
Q8VJ36
Transport
1520
3661401
G
E
H37Rv
3706872
C
D
Yes
NS, C
O53371
Transport
1520
3661401
G
E
CDC1551
3701763
C
D
Yes
NS, C
O53371
Transport
1587
3816846
A
D
H37Rv
3869141
C
A
Yes
NS, NC
O33354
Transport
1587
3816846
A
D
CDC1551
3855093
C
A
Yes
NS, NC
O33354
Transport
1608
3839628
A
V
H37Rv
3893286
G
A
Yes
NS, C
O06339
Transport
1608
3839628
A
V
CDC1551
3887122
G
A
Yes
NS, C
O06339
Transport
1609
3839818
A
F
H37Rv
3893476
G
L
Yes
NS, NC
O06339
Transport
1609
3839818
A
F
CDC1551
3887312
G
L
Yes
NS, NC
O06339
Transport
1621
3869973
T
V
H37Rv
3924346
C
A
Yes
NS, C
O53550
Transport
1621
3869973
T
V
CDC1551
3918182
C
A
Yes
NS, C
O53550
Transport
1638
3947819
G
R
H37Rv
4004600
A
Q
Yes
NS, NC
P96845
Transport
1638
3947819
G
R
CDC1551
3996744
A
Q
Yes
NS, NC
P96845
Transport
1639
3948329
C
S
H37Rv
4005110
G
W
Yes
NS, NC
P96845
Transport
1639
3948329
C
S
CDC1551
3997254
G
W
Yes
NS, NC
P96845
Transport
1640
3951962
G
T
H37Rv
4008744
A
I
Yes
NS, NC
P96849
Transport
1640
3951962
G
T
CDC1551
4000886
A
I
Yes
NS, NC
P96849
Transport
1644
3964308
T
S
H37Rv
4021090
G
A
Yes
NS, NC
P96860
Transport
1644
3964308
T
S
CDC1551
4013232
G
A
Yes
NS, NC
P96860
Transport
1682
4043080
C
G
H37Rv
4105730
T
E
Yes
NS, NC
O69634
Transport
1682
4043080
C
G
CDC1551
4097990
T
E
Yes
NS, NC
O69634
Transport
1683
4043104
T
Q
H37Rv
4105754
C
R
Yes
NS, NC
O69634
Transport
1683
4043104
T
Q
CDC1551
4098014
C
R
Yes
NS, NC
O69634
Transport
1684
4044421
C
R
H37Rv
4107071
T
Q
Yes
NS, NC
O69634
Transport
1684
4044421
C
R
CDC1551
4099331
T
Q
Yes
NS, NC
O69634
Transport
29
26034
G
P
H37Rv
26053
C
A
Yes
NS, NC
P71591
Transport
1692
4065667
G
Q
H37Rv
4128317
C
E
Yes
NS, NC
O69653
Transport
1692
4065667
G
Q
CDC1551
4120575
C
E
Yes
NS, NC
O69653
Transport
1716
4113722
A
R
H37Rv
4176259
G
G
Yes
NS, NC
O69695
Transport
1716
4113722
A
R
CDC1551
4168574
G
G
Yes
NS, NC
O69695
Transport
1790
4266511
T
H
H37Rv
4330235
C
R
Yes
NS, NC
P96219
Transport
1790
4266511
T
H
CDC1551
4322561
C
R
Yes
NS, NC
P96219
Transport
1824
4335857
G
G
H37Rv
4401894
A
D
Yes
NS, NC
P52214
Transport
1824
4335857
G
G
CDC1551
4394201
A
D
Yes
NS, NC
P52214
Transport
b: List of Polymorphisms(Insertions/Deletions) in genes involved in lipid metabolism
Polymorphism
BCG
BCG
Query
Query
Query
Putative
ID
start
end
name
start
end
ORF
GO ID
Function
1837
82490
82491
H37Rv
82452
82454
Yes
O53618
Transport
1838
125870
125872
H37Rv
125832
125833
Yes
Q10900
Transport
1854
257984
258014
H37Rv
257786
257787
Yes
P96397
Transport
1883
669950
669952
H37Rv
668706
668707
Yes
O53772
Transport
1902
890037
890038
H37Rv
887845
887847
Yes
O07268
Transport
1917
1041920
1041922
H37Rv
1041452
1041453
Yes
P95302
Transport
1919
1087886
1087887
H37Rv
1087445
1087447
Yes
O86319
Transport
1946
1407255
1407256
H37Rv
1409016
1409018
Yes
Q11058
Transport
1964
1744186
1744191
H37Rv
1760169
1760170
Yes
Q10761
Transport
1971
1879687
1879698
H37Rv
1894299
1894300
Yes
O53916
Transport
1994
2116913
2116915
H37Rv
2126702
2126703
Yes
O07753
Transport
2006
2184230
2184231
H37Rv
2192593
2192595
Yes
P95275
Transport
2032
2504789
2504790
H37Rv
2525724
2525726
Yes
O53525
Transport
2037
2540853
2540854
H37Rv
2563256
2563259
Yes
Q59570
Transport
2040
2584392
2584410
H37Rv
2606795
2606796
Yes
P71879
Transport
2044
2661152
2661153
H37Rv
2693078
2693088
Yes
P71748
Transport
2075
3043634
3043635
H37Rv
3087081
3087083
Yes
P30234
Transport
2084
3098539
3098540
H37Rv
3141965
3141967
Yes
P71617
Transport
2099
3381643
3381645
H37Rv
3425094
3425095
Yes
P95097
Transport
2103
3455437
3456765
H37Rv
3501662
3501663
Yes
P95191
Transport
2163
3898149
3898150
H37Rv
3954929
3954931
Yes
O53563
Transport
1837
82490
82491
CDC1551
82444
82446
Yes
O53618
Transport
1854
257984
258014
CDC1551
257902
257903
Yes
P96397
Transport
1883
669950
669952
CDC1551
670159
670160
Yes
O53772
Transport
1902
890037
890038
CDC1551
889115
889117
Yes
Q8VKD9
Transport
1917
1041920
1041922
CDC1551
1041467
1041468
Yes
P95302
Transport
1919
1087886
1087887
CDC1551
1087460
1087462
Yes
O86319
Transport
1946
1407255
1407256
CDC1551
1408505
1408507
Yes
Q11058
Transport
1964
1744186
1744191
CDC1551
1760325
1760326
Yes
Q10761
Transport
1994
2116913
2116915
CDC1551
2123925
2123926
Yes
O07753
Transport
2006
2184230
2184231
CDC1551
2189926
2189928
Yes
P95275
Transport
2037
2540853
2540854
CDC1551
2559103
2559106
Yes
Q59570
Transport
2040
2584392
2584410
CDC1551
2602641
2602642
Yes
P71879
Transport
2044
2661152
2661153
CDC1551
2690410
2690420
Yes
P71748
Transport
2075
3043634
3043635
CDC1551
3081806
3081808
Yes
P30234
Transport
2084
3098539
3098540
CDC1551
3136179
3136181
Yes
P71617
Transport
2099
3381643
3381645
CDC1551
3420887
3420888
Yes
P95097
Transport
2102
3441287
3441288
CDC1551
3480536
3483302
Yes
O05793
Transport
2163
3898149
3898150
CDC1551
3947715
3947717
Yes
O53563
Transport
[0249]
TABLE 7
List of Polymorphisms in genes encoding membrane transport proteins
BCG
BCG
BCG
Query
Query
Query
Query
Type of
Putative
Polymorphism ID
Position
base
AA
name
Position
base
aa
ORF
SNP
GO ID
Function
632
1457413
G
G
H37Rv
1459362
T
V
Yes
NS, C
Q10606
Lipid
Metabolism
632
1457413
G
G
CDC1551
1458905
T
V
Yes
NS, C
Q10606
Lipid
Metabolism
Table VII: List of long polymorphisms in genes encoding membrane transport proteins
Polymorphism ID The ID by which the polymorphism can be identified
BCG Start The position in the genome of M. bovis BCG at which multiple polymorhisms start occurring
BCG End The position in the genome of M. bovis BCG at which multiple polymorhisms end
H37Rv Start The position in the genome of M. tuberculosis H37Rv at which multiple polymorhisms start
H37Rv End The position in the genome of M. tuberculosis H37Rv at multiple polymorhisms end
C1551 Start The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms start
CDC1551 End The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms ends
ORF Indicates whether the polymorphism occurs in an open reading frame (Yes) or not (no)
GO ID The ID for the sequence in the gene ontology database
Putative function The putative function of the gene in which the SNP occurs.
[0250]
TABLE 8
List of Polymorphisms in genes implicated in virulence
Polymorphism
Gene
BCG
BCG
BCG
Query
Query
Query
Query
is
Is non-
Putative
ID
name
Position
base
AA
Name
position
base
AA
ORF
nsSNP
cons
GO ID
Function
285
proC
591914
C
D
H37Rv
590761
G
E
Yes
NS
C
Q11141
oxidoreductase
activity
285
proC
591914
C
D
CDC1551
592131
G
E
Yes
NS
C
Q11141
oxidoreductase
activity
1348
fadD28
3239912
T
I
H37Rv
3283336
G
S
Yes
NS
NC
P96290
calcium ion
binding activity
1348
fadD28
3239912
T
I
CDC1551
3277659
G
S
Yes
NS
NC
P96290
calcium ion
binding activity
1349
fadD28
3240065
G
R
H37Rv
3283489
A
Q
Yes
NS
NC
P96290
calcium ion
binding activity
1349
fadD28
3240065
G
R
CDC1551
3277812
A
Q
Yes
NS
NC
P96290
calcium ion
binding activity
1350
fadD28
3240165
C
G
H37Rv
3283589
G
G
Yes
S
Null
Null
Null
1350
fadD28
3240165
C
G
CDC1551
3277912
G
G
Yes
S
Null
Null
Null
1351
mmpL7
3242680
A
V
H37Rv
3286104
C
V
Yes
S
Null
Null
Null
1351
mmpL7
3242680
A
V
CDC1551
3280427
C
V
Yes
S
Null
Null
Null
1352
mmpL7
3243139
T
A
H37Rv
3286563
C
A
Yes
S
Null
Null
Null
1352
mmpL7
3243139
T
A
CDC1551
3280886
C
A
Yes
S
Null
Null
Null
274
pcaA
561876
G
L
H37Rv
560855
C
L
Yes
S
Null
Null
Null
274
pcaA
561876
G
L
CDC1551
562305
C
L
Yes
S
Null
Null
Null
275
pcaA
562317
T
A
H37Rv
561296
C
A
Yes
S
Null
Null
Null
275
pcaA
562317
T
A
CDC1551
562746
C
A
Yes
S
Null
Null
Null
1561
dnaE2
3736194
A
S
H37Rv
3782550
G
S
Yes
S
Null
Null
Null
1561
dnaE2
3736194
A
S
CDC1551
3774786
G
S
Yes
S
Null
Null
Null
1562
dnaE2
3736445
T
R
H37Rv
3782801
G
R
Yes
S
Null
Null
Null
1562
dnaE2
3736445
T
R
CDC1551
3775037
G
R
Yes
S
Null
Null
Null
Table VIII: List of long polymorphisms in genes implicated in virulence
Polymorphism ID The ID by which the polymorphism can be identified
BCG Start The position in the genome of M. bovis BCG at which multiple polymorhisms start occurring
BCG End The position in the genome of M. bovis BCG at which multiple polymorhisms end
H37Rv Start The position in the genome of M. tuberculosis H37Rv at which multiple polymorhisms start
H37Rv End The position in the genome of M. tuberculosis H37Rv at multiple polymorhisms end
C1551 Start The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms start
CDC1551 End The position in the genome of M. tuberculosis CDC1551 at which multiple polymorhisms ends
ORF Indicates whether the polymorphism occurs in an open reading frame (Yes) or not (no)
GO ID The ID for the sequence in the gene ontology database
Putative function The putative function of the gene in which the SNP occurs.
[0251] | The present invention is directed to novel nucleotide sequences to be used for diagnosis, identification of the strain, typing of the strain and giving orientation to its potential degree of virulence, infectivity and/or latency for all infectious diseases more particularly tuberculosis. The present invention also includes method for the identification and selection of polymorphisms associated with the virulence' and/or infectivity in infectious diseases more particularly in tuberculosis by a comparative genomic analysis of the sequences of different clinical isolates/strains of infectious organisms. The regions of polymorphisms, can also act as potential drug targets and vaccine targets. More particularly, the invention also relates to identifying virulence factors of M. tuberculosis strains and other infectious organisms to be included in a diagnostic DNA chip allowing identification of the strain, typing of the strain and finally giving orientation to its potential degree of virulence. Although the present invention has been illustrated with specific reference to the polymorphic region in the Mycobacterium tuberculosis, the said invention is not to be understood and construed as being limited to Tuberculosis but is applicable to all infectious diseases. | 2 |
TECHNICAL FIELD
The present invention relates to a method for preparing an MOF solid of a crystallized and porous aluminum aromatic azocarboxylate, in a nonaqueous organic medium.
It also relates to solids made up of metal-organic frameworks (MOF) of aluminum aromatic azocarboxylates that may be obtained by the method of the invention as well as to their uses for the storage of liquid or gaseous molecules, for selective gas separation and catalysis.
In the description below, the references between brackets [ ] refer to the list of references presented at the end of the text.
RELATED ART
Metal-organic Frameworks (MOF) constitute a new class of microporous solids (or even mesoporous for part of them). It relies on the concept of a three-dimensional assembly of rigid organic ligands (comprising a benzene ring, for example) with metal centers. The latter can be arranged to form isolated clusters, infinite chains or inorganic layers which connect to each other through the organic ligands via carboxylate or amine type connections. Several groups Yaghi [1], Kitagawa [2] and Férey [3], have exposed this kind of strategy for forming crystallized solids providing three-dimensional frames with exceptional porosity properties (BET surface area>3000 m 2 ·g −1 ).
Usually, this kind of materials is characterized by the specific surface area thereof (giving a precise idea of their accessible porosity for incorporating molecules). These specific surface area values (expressed in m 2 per gram of material) are measured by the Brunauer-Emmett-Teller (or BET) methods which makes it possible to examine the surface of the pores by chemisorption of nitrogen at 77 K (multilayer model) or Langmuir which uses the same process with a single layer model. These new materials prove to be very good adsorbents for gases such as hydrogen [4-6], methane [7, 8] or carbon dioxide [8]. Thus, they can replace activated carbons or zeolites. Moreover, this kind of solids (some of which being biocompatible) may have applications for encapsulating and controlled salting out of medicated molecules [9].
From an industrial valorization standpoint, several research groups have particularly focused their researches on this new emergent class of porous materials. Indeed, the German company BASF (Ludwigshafen, Germany) and the Yaghi Group (UCLA, the USA) have developed the synthesis processes and the forming of new solids essentially based on divalent (1st series of alkaline-earth transition metals) or trivalent (rare earths) elements combining organic ligands (mainly aromatic carboxylates) [10, 11].
Methods for preparing solids incorporating metals such as for example aluminum and zinc and organic ligands such as for example terephtalic acid, trimesic acid, naphthalene-2,6-dicarboxylic acid have also been described [12, 13].
For more than ten years, the team of Gérard Férey (Versailles) focused on the synthesis and the characterization of Metal-Organic Framework (MOF) type porous solids by developing several research directions [3], in particular the synthesis of MOF solids incorporating aluminum. In particular, the synthesis of crystallized porous aluminum carboxylates such as for example aluminum terephthalate MIL-53 [14], aluminum naphthalate MIL-69 [15] and aluminum trimesates MIL-96 [16] and MIL-110 [17] have been described. Mil-n means Materials of the Lavoisier Institute (Materiaux de l'Institut Lavoisier in French). Some of these solids have very interesting adsorption capacities [5, 8] for gases (H 2 , CO 2 , CH 4 ).
It should be noted that two other materials of the series, zinc terephthalate MOF-5 [18] and copper trimestate HKUST-1 [19] have also been described.
Other materials were obtained with terephtalic acid under other synthesis conditions or other ligands (for example trimesic acid, naphthalene-1,4-dicarboxylic acid, benzene-1,2,4,5 tetracarboxylic acid) [20]. The synthesis of aluminum carboxylates with trimesic acid in the presence of DMF solvent (N,N′-dimethylformamide) [21], with fumaric acid [22] or with mixed carboxylates of aluminum and another metal (for example Ti, Mg, La, Mo) [23]. Finally, a Norwegian patent of the university of Oslo [24] also sets forth the preparation of MIL-53 type solids from terephthalic acid functionalized with amino groups (—NH 2 ).
Among the various families of studied compounds, that incorporating aluminum is more particularly sought by industries owing to the low production cost of this kind of materials. Moreover, as a light element, the aluminum based materials may have high storage capacities for molecules such as H 2 , CH 4 , CO 2 , etc
To date, among the known processes for preparing MOFs, in particular aluminum based MOFs, no process describes the preparation of MOF materials containing aluminum azocarboxylate ligands. Neither have the structure of these materials and the topology of the constituting elements been studied in the prior art.
However, surprisingly, crystallized aluminum azocarboxylate based MOFs proved to be particularly interesting in terms of porosity and purity.
Generally, it is difficult to control the structural organization and the porosity of MOF materials. This can for example be related to the risks of interpenetration and interleaving of the frameworks during the formation of these materials which can lead to a dense material with reduced pores. Thus, the obtained material can exhibit a heterogeneous structure with inappropriate porosity.
Therefore, it would be interesting to be able to prepare aluminum azocarboxylate based MOFs for which the structures can be controlled in order to obtain specific properties in particular a crystallized structure, a customized pore diameter, adapted to the molecules to be adsorbed, an improved specific surface area and/or adsorption capacity, etc.
In addition, aluminum based MOF solids obtained by the majority of known processes may not be adapted to the desired application as they may include several phases, be in amorphous form or contain undesirable secondary substances obtained and not eliminated during the preparation of the MOF solids. Moreover, said solids do not always exhibit a sufficient porosity, and thus a sufficient adsorption capacity. To date, no methods exist for preparing aluminum azocarboxylate MOFs which can provide MOF type aluminum azocarboxylates having the required purity, porosity and crystallinity properties, with a good yield.
Thus, there exists a real need for a method for preparing aluminum azocarboxylates of metal-organic framework, MOF, type, which may be reproduced, and is industrially applicable.
Moreover, there exists a real need for a method for preparing MOF type aluminum azocarboxylates which, without resorting to additional steps in particular purification and/or crystallization steps, can lead to a crystallized MOF solid, made up of a single phase, highly pure (free from any secondary product) and exhibiting a sufficient porosity adapted to the use for which the MOF is intended.
DESCRIPTION OF THE INVENTION
The purpose of the present invention is precisely to meet this requirement by providing a method for preparing a MOF solid of a crystallized and porous aluminum aromatic azocarboxylate, including at least the following steps of:
(i) mixing in a non-aqueous organic solvent:
at least a metal inorganic precursor in the form of a metal Al, a metal salt Al3 + or a coordination complex including metal ion Al3 + ; and at least an organic precursor of the ligand L, L being an aromatic azodi-, azotri-, azotetra-carboxylate ligand of formula R 0 R 1 N 2 (COO − ) q where R 0 and R 1 independently from each other, represent,
a mono- or poly-cyclic, fused or non fused, aryl radical, including 6 to 50 carbon atoms, for example 6 to 27 carbon atoms, a mono- or poly-cyclic, fused or non fused, heteroaryl radical including 4 to 50 carbon atoms, for example 4 to 20 carbon atoms,
the R 0 radical being optionally substituted by one or more groups independently selected from the group including C 1-10 alkyl, C 2-10 alkene, C 2-10 alkyne, C 3-10 cycloalkyl, C 1-10 heteroalkyl, C 1-10 haloalkyl, C 6-10 aryl, C 3-20 heterocyclic, C 6-10 aryl C 1-10 alkyl, C 5-10 heteroaryl C 1-10 alkyl, F, Cl, Br, I, —NO 2 , —CN, —CF 3 , —CH 2 CF 3 , —OH, —CH 2 OH, —CH 2 CH 2 OH, —NH 2 , —CH 2 NH 2 , —NHCHO, —COOH, —CONH 2 , —SO 3 H, —PO 3 H 2 ,
q=2 to 4;
(II) heating the mixture obtained in (i) at a temperature of at least 50° C. so as to obtain said solid.
In the frame of the present invention the terms “crystallized solid” and “crystalline solid” may be indifferently used to indicate a solid in which the atoms, the ions or the molecules form long distance ordered arrangements in the three space dimensions, leading to a single signature composed of a specific succession of diffraction peaks (X-rays for example) for each solid.
An “amorphous solid” is a solid where the atoms, ions or molecules, although locally ordered, disorderly stack up at long distance. This leads to a signature of one or more very wide diffraction peaks (X-rays for example) preventing a precise identification of the material (as several solids can coexist and lead to the same diffraction signature).
In many solids, the atoms, ions or molecules can adopt several arrangements according to their formation conditions. These different arrangements constitute the various existing “phases” of the solid in a given chemical system. The physical properties like the melting point and the density of the various phases are distinguished, permitting the differentiation of the solids.
within the meaning of the present invention, what is meant by “alkyl” is a saturated, optionally substituted, linear or branched carbon radical including 1 to 12 carbon atoms, for example 1 to 10 carbon atoms, for example 1 to 8 carbon atoms, for example 1 to 6 carbon atoms.
For example, an alkyl radical may be a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl radical or like radicals.
Within the meaning of the present invention, what is meant by “alkene” is a linear or branched, cyclic or acyclic, unsaturated hydrocarbon radical including at least a double carbon-carbon bond. The alkenyl radical may comprise 2 to 20 carbon atoms, for example 2 to 10 carbon atoms, more particularly 2 to 8 carbon atoms, even more particularly 2 to 6 carbon atoms. For example, an alkenyl radical may be an allyl, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl radical or like radicals.
The term “alkyne” designates a linear or branched, cyclic or acyclic unsaturated hydrocarbon radical, including at least a triple carbon-carbon bond. The alkynyl radical may comprise 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more particularly 1 to 8 carbon atoms, even more particularly 2 to 6 carbon atoms. For example, an alkynyl radical may be an ethynyl, 2-propynyl (propargyl), 1-propynyl radical or like radicals.
Within the meaning of the present invention, what is meant by “aryl” is an aromatic system including at least a ring satisfying Hückel's aromaticity rule. Said aryl is optionally substituted and may comprise from 6 to 50 carbon atoms, for example 6 to 27 carbon atoms, in particular 6 to 14 carbon atoms, more particularly 6 to 12 carbon atoms. For example, an aryl radical may be a phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl group or like radicals.
within the meaning of the present invention, what is meant by “heteroaryl”, is a system including at least an aromatic ring of 4 to 50 carbon atoms, for example 4 to 20 carbon atoms, and at least a heteroatom selected from the group including in particular sulfur, oxygen, nitrogen. Said heteroaryl may be substituted. For example, a heteroaryl radical may be a pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl radical and like radicals.
Within the meaning of the present invention, what is meant by “cycloalkyl” is a cyclic, saturated or unsaturated, optionally substituted carbon radical, which may comprise 3 to 10 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclobutyl, 2,3-dimethylcyclobutyl, 4-methylcyclobutyl, 3-cyclopentylpropyl may be mentioned.
Within the meaning of the present invention, what is meant by “haloalkyl” is an alkyl radical such as previously defined, said alkyl system including at least a halogen selected from the group including fluorine, chlorine, bromine, iodine.
Within the meaning of the present invention, what is meant by “heteroalkyl”, is an alkyl radical such as previously defined, said alkyl system including at least a heteroatom, particularly, a heteroatom selected from the group including sulfur, oxygen, nitrogen, phosphorus.
Within the meaning of the present invention, what is meant by “heterocycle” is a saturated or unsaturated, optionally substituted, cyclic carbon radical including at least a heteroatom and which may comprise 3 to 20 carbon atoms, preferably 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms. The heteroatom may be for example selected from the group including sulfur, oxygen, nitrogen, phosphorus. For example, a heterocyclic radical may be a pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, or tetrahydrofuryl group.
Within the meaning of the present invention, what is meant by “alkoxy”, “aryloxy”, “heteroalkoxy” and “heteroaryloxy”, respectively, is an alkyl, aryl, heteroalkyl and heteroaryl radical bonded to an oxygen atom. For example, an alkoxy radical may be a methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, n-hexoxy radical or like radicals.
The term “substituted” designates for example the replacement of a hydrogen atom in a structure given by a group such as previously defined. When more than one position can be substituted, the substituents may be same or different at each position.
In the context of the invention, the organic solvent can be made up of only one solvent or a mixture of organic solvents.
The term “nonaqueous solvent” advantageously refers to a solvent or a mixture of solvents containing up to 5 wt %, preferably 1 wt %, more preferably 0.1 wt % and even more preferably up to 0.01 wt % of water with respect to the total weight of all solvents.
The nonaqueous organic solvent can be selected from the group including N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), dioxane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, cyclohexanol, pyridine, toluene, ethyl acetate, dimethyl sulfoxide (DMSO).
The nonaqueous organic solvent is more particularly selected from the group including DMF, DEF, dioxane, methanol, ethanol, DMSO.
The metal inorganic precursor in step (i) may be a metal Al, metal salt Al 3+ or a coordination complex including metal ion Al 3+ . When it is metal salt, the counter-ion may be an inorganic ion selected from the group including sulfate, nitrate, nitrite, sulphite bisulfite, phosphate, phosphite, fluoride, chloride, bromide, iodide, perchlorate, carbonate, bicarbonate. The counter-ion may also be an organic ion selected from the group including acetates, formates, oxalates, citrates, ethoxy, isoproxy. Preferably, the metal inorganic precursor is a metal salt Al 3+ .
The crystalline spatial organization of the solids of this invention forms the basis of the particular characteristics and features of these materials. In particular, it governs the size of the pores, which affects the specific surface area of the materials and the adsorption characteristics. It also governs the density of the materials which is relatively weak, the proportion of metal in these materials, the stability of the materials, the rigidity and the flexibility of the structures, etc
Moreover, the pore size may be adjusted by the choice of appropriate Ligands L. In the method of the invention, the Ligand L is more particularly an aromatic azodi- or azotetra-carboxylic ligand, selected from the group including:
C 12 H 8 N 2 (CO 2 − ) 2 (azobenzene-4,4′-dicarboxylate),
C 12 H 6 Cl 2 N 2 (CO 2 − ) 2 (dichloro-azobenzene-4,4′-dicarboxylate),
C 12 H 6 N 2 (CO 2 − ) 4 (azobenzene-3,3′,5,5′-tetracarboxylate),
C 12 H 6 N 2 (OH) 2 (CO 2 − ) 2 (dihydroxy-azobenzene-4,4′-dicarboxylate).
In step (i) the metal inorganic precursor and the organic precursor of the Ligand L can be mixed in a molar ratio comprised between 1 and 5.
As already indicated, MOF solids according to the invention have a crystallized structure which provides these materials with specific properties. In the method according to the invention, crystallization is carried out in a precise temperature range. Thus, in step (ii), the mixture is heated at a temperature ranging from 50° C. to 150° C. The mixture may be heated for 1 to 10 days. One day corresponds to 24 hours. The mixture may be heated in a closed cell.
Step (ii) may be carried out with an autogenous pressure higher than 10 5 Pa. An “autogenous” pressure corresponds to the pressure generated by the reagents at a given temperature in a closed reaction cell.
The solid obtained at the end of step (ii) may be further subjected to an activation step (iii) in which said solid is heated at a temperature of 100° C. to 300° C., preferably of 100° C. to 200° C. In this step, the solid may be heated for 1 to 48 hours.
The activation step (iii) may be optionally carried out in a mixture of solvent(s) selected from the group including DMF, DEF, methanol, ethanol, DMSO or water.
With this activation step (iii) it is particularly possible to empty the pores of the MOF solid of the invention and make them available for the intended use of said solid. Emptying can be done, for example, by the departure of the water, solvent molecules and/or if necessary, of the molecules of Ligands L present in the reaction medium. Resulting MOF solids will then have a stronger adsorption and storage capacity.
The object of the present invention is also an MOF solid of a crystallized and porous aluminum aromatic azocarboxylate that may be obtained by the method according to the invention, including a three-dimensional succession of patterns of formula (I):
Al m O k X l L p (I)
in which:
Al represents the metal ion Al 3+ ; m is 1 to 15, for example 1 to 8; k is 0 to 15, for example 1 to 8; l is 0 to 10, for example 1 to 8; p is 1 to 10, for example 1 to 5;
m, k, l and p are selected so as to respect the neutrality of the charges of said pattern;
X is an anion selected from the group including OH − , Cl − , F − , I − , Br − , SO 4 2− , NO 3 —, ClO 4 − , PF 6 − , BF 3 − , R 2 —(COO − ) n , R 2 —(SO 3 − ) n , R 2 —(PO 3 − ) n , where R 2 is hydrogen, linear or branched, optionally substituted C 1-12 alkyl, n=1 to 4; L is a ligand such as previously defined.
Aluminum aromatic azocarboxylate MOF solids prepared by the method of the invention exhibit some advantages of which:
they are crystallized solids, they are highly pure (no secondary product such as for example aluminum hydroxyl is detected), and the exhibit a significant porosity (Langmuir surface up to 3500 m 2 /g) allowing to particularly control the adsorption characteristics of certain molecules.
Preferably, X is selected from the group including OH − , Cl − , F − , ClO 4 − .
MOF Solids according to the invention preferably comprise Al from 5 to 50% in wt %.
MOF Solids that may be obtained by the method of the invention have pores, and more particularly micro- and/or meso-pores. The micropores can be defined as pores having a diameter lower than or equal to 2 nm (diameter≦2 nm) and the mesopores as pores having a diameter higher than 2 nm and that up to 50 nm (2 nm<diameter<50 nm). Preferably, the diameter of the pores of the MOF solid of the invention ranges from 0.2 to 6 nm. The presence of micro- and meso-pores may be followed by sorption measurements so as to determine the capacity of the MOF solid to absorb nitrogen at 77K according to DIN 66131.
The specific surface area of the solids made up of porous and crystallized aluminum aromatic azocarboxylate MOFs, that may be obtained by the method of the invention, may be measured by the BET method and determined and calculated by the Langmuir model. Said solids may have a BET surface area from 50 to 4200 m 2 /g, more particularly from 100 to 3000 m 2 /g. They may also have a Langmuir surface area from 50 to 6000 m 2 /g, more particularly from 150 to 3500 m 2 /g.
MOF solids according to the invention advantageously have a porous volume of 0.3 to 4 cm 3 /g. Within the framework of the invention, porous volume means the volume accessible for gas or liquid molecules.
Within the framework of this invention, MOF solids may have a gas load capacity from 0.5 to 50 mmol of gas per gram of dry solid. The load capacity means the gas storage capacity or the quantity of gas adsorbed by the solid. These values and this definition also apply to the load capacity of liquids.
MOF solids of this invention may particularly exhibit the advantage of a thermal stability up to a temperature of 500° C. More particularly, these solids may have a thermal stability between 250° C. and 450° C.
MOF solids of the invention are crystallized and may preferably be in the form of crystallites with a length which varies from 0.05 to 100 μm, more particularly from 0.05 to 20 μm. They are preferably in the form of small crystals having a particular morphology (needles, plates, octahedral, etc.) also permitting their precise identification by examination through a scanning electron microscope (SEM).
As already indicated, MOF solids according to the invention have a crystallized structure and are highly pure providing these materials with specific properties.
Contrary to the known solids, aluminum azocarboxylate MOF solids according to the invention are composed of a single phase. That means that the other phases that may exist in the considered chemical system are not present mixed with the solid.
Moreover, aluminum azocarboxylate MOF solids that may be obtained by a preparation process as previously described, exhibit a degree of purity of at least 95%, in particular at least 98 mass %. The purity of MOF solids of the invention may be in particular determined by elementary chemical analysis, X-rays diffraction, scanning electron microscopy. Thus, the obtained MOF solids, do not comprise, or very little, secondary products such as for example aluminum hydroxide of formula Al(OH) 3 or AlO(OH) or the other phases of the considered chemical system appearing under other synthesis conditions.
The particular structural characteristics of the solids of the present invention make them high load capacity, highly selective, and highly pure adsorbents. Thus, they make the selective adsorption, and thus, the selective separation of gas molecules such as for example of NO, N 2 , H 2 S, H 2 , CH 4 , O 2 , CO, CO 2 . . . ) molecules, possible.
The object of the present invention is also the use of a solid composed of crystallized and porous aluminum azocarboxylates MOF for the storage of liquid or gas molecules, for selective gas separation [25] or for catalysis [26].
Other advantages will become more apparent to the skilled person upon reading the examples below, illustrated by the accompanying figures, given by way of illustration.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 represents the X-ray diffraction diagram of the phase MIL-130 (Al) (CuK D ). The X-coordinate represents the angular variation in 2D) (°). The ordinate represents the relative diffraction peak intensity.
FIG. 2 represents the phase MIL-130 adsorption isotherm N 2 at 77K of. The ratio p/p 0 which corresponds to the relative pressure is given in X-coordinate. The volume of adsorbed gas per gram of product (cm 3 ·g −1 ) is represented on the ordinate.
FIG. 3 represents the thermogravimetric analysis curve of MIL-130 (Al) (under O 2 stream, 3° C.·min −1 ). The percentage of the mass loss is represented on the ordinate. The heating temperature is represented on the X-coordinate.
FIG. 4 represents the photography (scanning electron microscopy) of a sample of MIL-130 (Al) showing hexagonal rod shaped crystallites.
FIG. 5 represents the photography (scanning electron microscopy) of a sample of MIL-130 (Al) showing ovoid crystallite aggregates shaped crystallites.
FIG. 6 represents the photography (scanning electron microscopy) of a sample of MIL-130 (Al) showing ovoid plates shaped crystallites.
EXAMPLES
The following examples describe the synthesis of solids made up of MOFs of microporous aluminum aromatic azocarboxylate (noted Mil-n) obtained with azobenzene carboxylate type ligands and more particularly with the azodibenzene-4,4′-dicarboxylate. The synthesized compounds (noted Mil-n) were then characterized by X-ray powder diffraction, by thermogravimetric analysis, scanning electron microscopy (SEM) and their specific surface areas were measured by the BET method.
The diffraction diagrams were recorded using a diffractometer (Siemens D5000) in Bragg-Brentano reflection geometry on an angular 2theta field of 2 to 40° with a pitch and a count time of 0.02° and 1 second, respectively (CuK D1,2 radiation). The thermogravimetric analysis (TA Instrument 2050) was carried out from a sample of 5 or 20 mg heated on a balance at 20 to 600° C. under oxygen stream with a heating rate of 3° C.·min −1 . With regard to the examination with the scanning electron microscope (LEO 1530), the samples were metallized with carbon then placed in a vacuum room under the electron beam. The specific surface areas were measured on a Micromeritics ASAP2010 apparatus from 100 mg samples which were heated beforehand under vacuum at 200° C. for 12 hours.
Example 1
Preparation of MIL-130 (Al)
Compound MIL-130 (Al) is obtained from a mixture of 3.6 g of aluminum nitrate (AI(NO 3 ) 3 .9H 2 O), 1.2 g of azodibenzene-4,4′-dicarboxylic acid and 70 ml of DMF (N,N′-dimethylformamide) placed in a 125 ml Teflon cell then inserted in a Parr steel autoclave (registered trademark). The reaction takes place at 100° C. for 7 days in an oven. 2 g of MIL-130 (Al) are obtained. The product is activated by heating at 200° C. over night.
A second preparation may be prepared from a mixture of 0.36 g aluminum perchlorate (AI(CIO 4 ) 3 .9H 2 O), 0.1 g of azodibenzene-4,4′-dicarboxylic acid, 5 ml of DMF (N,N′-dimethylformamide) placed in a 23 ml Teflon cell then a Parr type steel autoclave (trade name). The reaction takes place at 100° C. for 7 days in an oven. 0.11 g of MIL-130 (Al) are obtained.
A third preparation may be prepared from a mixture of 0.19 g of aluminum chloride hexahydrate (AI(Cl) 3 .6H 2 O), 0.1 g of azodibenzene-4,4′-dicarboxylic acid, 5 ml of DMF (N,N′-dimethylformamide) placed in a 23 ml Teflon cell then a steel autoclave of trade name Parr (registered trademark). The reaction takes place at 100° C. for 7 days in an oven. 0.07 g of MIL-130 (Al) are obtained.
A fourth preparation may be prepared from a mixture of 0.1 g of anhydrous aluminum chloride (AI(Cl) 3 ), 0.1 g of azodibenzene-4,4′-dicarboxylic acid, 5 ml of DMF (N,N′-dimethylformamide) placed in a 23 ml Teflon cell then a steel autoclave of brand name Parr (registered trademark). The reaction takes place at 100° C. for 7 days in an oven. 0.07 g of MIL-130 (Al) are obtained.
A fifth preparation may be prepared from a mixture of 0.1 g of anhydrous aluminum chloride (AI(Cl) 3 ), 0.1 g of azodibenzene-4,4′-dicarboxylic acid, 5 ml of DMF (N,N′-dimethylformamide) placed in a 23 ml Teflon cell then a steel autoclave of brand name Parr (registered trademark). The reaction takes place at 100° C. for 4 hours in an oven. 0.07 g of MIL-130 (Al) are obtained.
The examination of these solids (for example, the fourth preparation) with the electron microscope shows the presence of small hexagonal rod-shaped crystals with a mean size of 0.2 to 0.8 microns ( FIG. 4 ), of ovoid crystallite aggregates ( FIG. 5 ) from the second preparation or of ovoid plates ( FIG. 6 ) from the first preparation.
The Bragg peaks of the powder diagram may correspond to a hexagonal mesh with parameters a=b=33.264 (1) Â and C=4.681 (1) Â, V=4417.5 (1) Â 3 . The X-ray Diffractogram is shown on FIG. 1 .
The BET surface area is of 1770 m 2 /g and the Langmuir surface is of 3190 m 2 /g. The adsorption isotherm exhibits a step for p/p 0 =0.15, which is characteristic of mesoporous cavities or tunnels ( FIG. 2 ). The thermogravimetric analysis indicates that the material MIL-100 (Al) is stable up to 420° C. ( FIG. 3 ).
The combination of these various characterization analyses (XRD, SEM) shows that it is a very well identified material with a high crystalline purity. Following the XRD observation, a compound, for which phase MIL-130 (AI) represents the major part at least up to 95% (in mass) may be defined.
LIST OF REFERENCES
[1] Reticular Synthesis and the Design of New Materials, O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi and J. Kim, Nature, 423, 705-14 (2003).
[2] Functional Porous Coordination Polymers, S. Kitagawa, R. Kitaura and S.-l. Noro, Angew. Chem. Int. Ed., 43, 2334-75 (2004).
[3] Hybrid Porous Solids: Past, Present, Future, G. Férey, Chem. Soc. Rev., 37, 191-214 (2008).
[4] Hydrogen Storage in Microporous Metal-Organic Frameworks, N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O'Keeffe and O. M. Yaghi, Science, 300, 1127-9 (2003).
[5] Hydrogen Adsorption in the Nanoporous Metal-benzenedicarboxylate M(OH) (O 2 C—C 6 H4-CO 2 ) (M=Al 3+ , Cr 3+ ), MIL-53, G. Férey, M. Latroche, C. Serre, F. Millange, T. Loiseau and A. Percheron-Guéegan, Chem. Commun., 2976-7 (2003).
[6] Hydrogen Storage in the Giant-Pore Metal-Organic Frameworks MIL-100 and MIL-101, M. Latroche, S. Surblé, C. Serre, C. Mellot-Draznieks, P. L. Llewellyn, J.-H. Lee, J.-S. Chang, S. H. Jhung and G. Férey, Angew. Chem. Int. Ed., 45, 8227 (2006).
[7] Systematic Design of Pore Size and Functionality in Isoreticular MOFs and their Application in Methane Storage, M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wächter, M. O'Keeffe and O. M. Yaghi, Nature, 295, 469-72 (2002).
[8] Different Adsorption Behaviors of Methane and Carbon Dioxide in the Isotypic Nanoporous Metal Terephthalates MIL-53 and MIL-47, S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau and G. Férey, J. Am. Chem. Soc, 127, 13519-21 (2005).
[9] Metal-Organic Frameworks as Efficient Materials for Drug Delivery, P. Horcajada, C. Serre, M. Vallet-Regi, M. Sebban, F. Taulelle and G. Férey, Angew. Chem. Int. Ed., 45, 5974 (2006).
[10] High Gas Adsorption in a Microporous Metal-Organic Framework with Open-Framework, O. M. Yaghi, WO 2006/110740 (2006).
[11] Isoreticular Metal-Organic Framework Process for Forming the Same and Systematic Design of Pore size and Functionality therein, with Application for Gas Storage, WO 02/088148 (2002).
[12] Metal-Organic Frameworks—Prospective Industrial Applications, U. Müller, M. Schubert, F. Teich, H. Pütter, K. Schierle-Arndt and J. Pastre, J. Mater. Chem., 16, 626-36 (2006).
[13] Shaped Bodies Containing Metal-Organic Frameworks, M. Hesse, U. Müller, O. M. Yaghi, WO 2006/050898 (2006).
[14] A Rationale for the Large Breathing of the Porous Aluminum Terephthalate (MIL-53) Upon Hydration, T. Loiseau, C. Serre, C. Huguenard, G. Fink, F. Taulelle, M. Henry, T. Bataille and G. Férey, Chem. Eur. J., 10, 1373-82 (2004).
[15] Hydrothermal Synthesis and Crystal Structure of a New Three-Dimensional Aluminum-Organic Framework MIL-69 with 2,6-Naphthalenedicarboxylate (ndc), AI(OH)(ndc)QH 2 O, T. Loiseau, C. Mellot-Draznieks, H. Muguerra, G. Férey, M. Haouas and F. Taulelle, C. R. Chimie, Special Issue on Crystalline and Organized Porous Solids, 8, 765-72 (2005).
[16] MIL-96, a Porous Aluminum Trimesate 3D Structure Constructed from a Hexagonal Network of 18-Membered Rings and μ 3 -0×0-Centered Trinuclear Units, T. Loiseau, L. Lecroq, C. Volkringer, J. Marrot, G. Férey, M. Haouas, F. Taulelle, S. Bourrelly, P. L. Llewellyn and M. Latroche, J. Am. Chem. Soc, 128, 10223-30 (2006).
[17] A Microdiffraction Set-up for Nanoporous Metal-Organ ic-Framework-Type Solids, C. Volkringer, D. Popov, T. Loiseau, N. Guillou, G. Férey, M. Haouas, F. Taulelle, C. Mellot-Draznieks, M. Burghammer and C. Riekel, Nature Matehals, 6, 760-4 (2007).
[18] Design and Synthesis of an Exceptionally Stable and Highly Porous Metal-Organic Framework. H. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi, Nature, 402, 276-9 (1999).
[19] A Chemically Functionalizable Nanoporous Material [Cu 3 (TMA) 2 (H 2 O) 3 ] n , S. S.-Y. Chui, S. M.-F. Lo, J. P. H. Charmant, A. Guy Orpen and I. D. Williams, Science, 283, 1148 (1999).
[20] Method for Producing Organometallic Framework Materials Containing Main Group Metal Ions, M. Schubert, U. Müller, M. Tonigold, R. Ruetz, WO 2007/023134 (2007).
[21] Mesoporous Metal-Organic Framework, M. Schubert, U. Müller, H. Mattenheimer, M. Tonigold, WO 2007/023119 (2007).
[22] Organometallic Aluminum Fumarate Backbone Material, C. Kiener, U. Müller, M. Schubert, WO 2007/118841 (2007).
[23] Dotierte Metallorganische Gerüstmaterialien, M. Schubert, U. Müller, R. Ruetz, S. Hatscher, DE 10 2005 053 430 (2005).
[24] MOF-Compounds as Gas Adsorbers, K. O. Kongshaug, R. H. Heyn, H. Fjellvag, R. Blom, WO 2007/128994 (2007).
[25] <<How hydration drastically improves adsorption selectivity for CO2 over CH 4 in the flexible Chromium terephthalate MIL-53>>, P. L. Llewellyn, S. Bourrelly, C. Serre, Y. Filinchuk and G. Férey, Angew. Chem. Int. Ed. 45 7751-4 (2006).
[26] <<Synthesis and catalysis properties of MIL-100(Fe), an iron(111) carboxylate with large pores>> P. Horcajada, S. Surble, C. Serre, D.-Y. Hong, Y.-K. Seo, J.-S Chang, J.-M. Greneche, I. Margiolaki and G. Férey, Chem. Commun. 2820-2 (2007); <<Catalytic properties of MIL-101>> A. Henschel, K. Gedrich, R. Kraehnert and S. Kaskel, Chem. Commun. 4192-4 (2008); <<Amine grafting on coordinatively unsaturated metal centers of MOFs: consequences for catalytis and metal encapsulation>> Y. K. Hwang, D.-Y. Hong, J.-S. Chang, S. H. Jhung, Y.-K. Seo, J. Kim, A. Vimont, M. Daturi, C. Serre and G. Férey, Angew. Chem. Int. Ed. 47 4144-8 (2008). | The present invention relates to a method for preparing an MOF solid of a crystallised and porous aluminium aromatic azocarboxylate, in a non-aqueous organic medium. The invention also relates to solids made up of metal-organic frameworks (MOF) of aluminium aromatic azocarboxylates capable of being obtained by the method of the invention, as well as to the uses thereof for the storage of liquid or gaseous molecules, for selective separation of gas and for catalysis. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a light manipulating device, and more particularly to a sunlight manipulating device.
[0003] 2. Description of the Prior Art
[0004] Solar energy belong to clean energy and inexhaustible, and therefore how to effectively utilizesolar energy is the main development direction of industry. At present, the major application of solar energy includes generating electric power, heating or illuminating. In order to effectively utilize solar energy, conventional solar cells are mostly set in space in direct sunlight, i.e. setting in outdoors. The life of solar cells setting in outdoors may be shortened due to climatic factors.
[0005] In addition, if the power consumption for illumination is greater than the amount of power generation by solar energy, the introduction of sunlight for illumination is obviously better for energy utilization. However, most of the conventional solar cell is set in facing the sun and large area manner to facilitate absorbing solar energy. In other words, the solar cell shadows the most sunlight which results the shadowed sunlight cannot be used as illumination purpose. To move the solar cell with large area requires not only more space and it is not easy.
[0006] Accordingly, it is highly desirable to manipulate the sunlight to efficiently use solar energy.
SUMMARY OF THE INVENTION
[0007] The present invention is directed to a sunlight manipulating device which uses a light focusing module and a light deflection module to guide sunlight to a target area, so that an installation of a solar cell, a heating device or a light guide element can be more flexible, such as in a sheltered environment or erected installation.
[0008] In one embodiment, the proposed sunlight manipulating device includes a light focusing module and a light deflection module. The light focusing module is configured for converging incident sunlight on a focal region. The light deflection module is arranged on the focal region or adjacent to the focal region to deflect the converged sunlight to a target area, wherein the target area is diverged from an optical axis of the light focusing module.
[0009] The objective, technologies, features and advantages of the present invention will become apparent from the following description in conjunction with the accompanying drawings wherein certain embodiments of the present invention are set forth by way of illustration and example.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The foregoing conceptions and their accompanying advantages of this invention will become more readily appreciated after being better understood by referring to the following detailed description, in conjunction with the accompanying drawings, wherein:
[0011] FIG. 1 is a diagram schematically illustrating a sunlight manipulating device according to the first embodiment of the present invention;
[0012] FIG. 2 is a diagram schematically illustrating a sunlight manipulating device according to the second embodiment of the present invention;
[0013] FIG. 3 is a diagram schematically illustrating a sunlight manipulating device according to the third embodiment of the present invention;
[0014] FIG. 4 is a diagram schematically illustrating a sunlight manipulating device according to the fourth embodiment of the present invention;
[0015] FIG. 5 is a diagram schematically illustrating a sunlight manipulating device according to the fifth embodiment of the present invention;
[0016] FIG. 6 is a diagram schematically illustrating a sunlight manipulating device according to the sixth embodiment of the present invention;
[0017] FIG. 7 a and FIG. 7 b are diagrams schematically illustrating a sunlight manipulating device according to the seventh embodiment of the present invention;
[0018] FIG. 8 is a diagram schematically illustrating a sunlight manipulating device according to the eighth embodiment of the present invention; and
[0019] FIG. 9 is a diagram schematically illustrating a sunlight manipulating device according to the ninth embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] Various embodiments of the present invention will be described in detail below and illustrated in conjunction with the accompanying drawings. In addition to these detailed descriptions, the present invention can be widely implemented in other embodiments, and apparent alternations, modifications and equivalent changes of any mentioned embodiments are all included within the scope of the present invention and based on the scope of the Claims. In the descriptions of the specification, in order to make readers have a more complete understanding about the present invention, many specific details are provided; however, the present invention may be implemented without parts of or all the specific details. In addition, the well-known steps or elements are not described in detail, in order to avoid unnecessary limitations to the present invention. Same or similar elements in Figures will be indicated by same or similar reference numbers. It is noted that the Figures are schematic and may not represent the actual size or number of the elements. For clearness of the Figures, some details may not be fully depicted.
[0021] Referring to FIG. 1 , a sunlight manipulating device according to the first embodiment of the present invention comprises a light focusing module 11 and a light deflection module 12 . The light focusing module 11 can converge incident sunlight SL 1 on a focal region. For example, the light focusing module 11 may be a Fresnel lens, but is not limited thereto. Other lenses or mirrors having the function of converging light can implement the present invention. In one embodiment, the focal region may be a focal point or focal line. The light deflection module 12 is arranged on the focal region or adjacent to the focal region converging the sunlight SL 1 , so that the light deflection module 12 deflects the converged sunlight SL 2 to a target area 20 . The target area 20 is diverged from an optical axis A of the light focusing module 11 . In one embodiment, the light deflection module 12 may be a reflective element or a refractive element. In the embodiment shown in FIG. 1 , the light deflection module 12 is a reflective element. It can be understood that the light deflection module 12 may be a single optical element which includes a plurality of reflecting surfaces or refractive surfaces. For example, the light deflection module 12 may be a prism. Furthermore, the position of the sun changes over time and the focal region also moves depending on the movement of the sun. Therefore, in one embodiment, the size or moveable path of the light deflection module 12 covers a movement trajectory of the focal region caused by movement of the sun.
[0022] In one embodiment, a light entrance surface of a solar cell, a heating device or a light guide element can be installed at the target area 20 to utilize the deflected sunlight SL 2 from the light deflection module 12 . According to the embodiment shown in FIG. 1 , the installation of a solar cell, a heating device or a light guide element can be more flexible by using the sunlight manipulating device of the present invention to adjust the light path of the incident sunlight SL 1 . For example, the solar cell can be installed at a sheltered environment so that the damage of solar cell caused by wind, rain or other climatic factors can be avoided and the operating life of solar cell can be extended. In addition, the solar cell may be installed in erected manner to reduce the space required for the installation of solar cell. It can be understood that the sunlight SL 2 irradiating to the target area 20 may not be used for any purpose.
[0023] Referring to FIG. 2 to illustrate the sunlight manipulating device according to the second embodiment of the present invention. Compared to the first embodiment shown in FIG. 1 , the difference between the two is that the light focusing module 11 of the second embodiment is a variable focal length element, and the remaining components are the same as the first embodiment. In one embodiment, the trench of Fresnel lens can be filled with a material which has the same or similar refractive index with that of the Fresnel lens, so that the focusing effect of the light focusing module 11 will be significantly reduced. At this time, the incident sunlight SL 1 passing through the light focusing module 11 is almost no convergence and most of the incident sunlight SL 1 will not be deflected to the target area 20 by the light deflection module 12 , and therefore, most of the incident sunlight SL 1 can be used as the illumination purpose. On the contrary, the filled material can be drawn out from the Fresnel lens to restore the convergence function of the Fresnel lens, and therefore, the converged sunlight SL 2 can be deflected to the target area 20 as the other of the applications. Briefly, it can be controlled whether the incident sunlight SL 1 irradiates to the target area 20 or not by adjusting the focal length of the light focusing module 11 . It can be understood that the target area 20 is diverged from a projection area along the optical axis A of the light focusing module 11 so as to avoid shadow the incident sunlight SL 1 by the solar cell, the heating device or the light guide element installed at the target area 20 .
[0024] Referring to FIG. 3 and FIG. 4 to illustrate the sunlight manipulating device according to the third embodiment and fourth embodiment of the present invention. Compared to the first embodiment shown in FIG. 1 , the difference between the two is that the third embodiment and fourth embodiment further comprise a driving element 13 connected with the light deflection module 12 , and the remaining components are the same as the first embodiment. The driving element 13 is able to drive the light deflection module 12 in a manner of rotation (as shown in FIG. 3 ), linear movement (as shown in FIG. 4 ) or the combination thereof so as to make the light deflection module 12 diverge from the focal region. At this time, the converged sunlight SL 2 from the light focusing module 11 will not be deflected to the target area 20 by the light deflection module 12 , and the converged sunlight SL 2 passing through the focal region will diffuse to form a wider range of irradiation region, for example, as an illumination purposes. It can be understood that part of the light deflection module 12 diverges from the focal region so that part of the converged sunlight SL 2 is deflected to the target area 20 and another part of the converged sunlight SL 2 is used for illumination purposes.
[0025] Referring to FIG. 5 to illustrate the sunlight manipulating device according to the fifth embodiment of the present invention. Compared to the first embodiment shown in FIG. 1 , the difference between the two is that the light deflection module 12 of the fifth embodiment comprises a plurality of optical elements 121 , 122 , and the remaining components are the same as the first embodiment. As shown in FIG. 5 , the optical element 122 includes a curved surface, so that the optical element 122 can further converge the sunlight SL 2 converged by the light focusing module 11 to irradiate a smaller target area 20 . It can be understood that the light deflection module 12 including a single optical element with curved surface is also able to implement the function of further converging the sunlight SL 2 .
[0026] Referring to FIG. 6 to illustrate the sunlight manipulating device according to the sixth embodiment of the present invention. Compared to the fifth embodiment shown in FIG. 5 , the difference between the two is that the sixth embodiment further comprises a driving element 13 connected with the optical element 121 of the light deflection module 12 , and the remaining components are the same as the fifth embodiment. As the third embodiment and the fourth embodiment shown in FIG. 3 and FIG. 4 , the driving element 13 is able to drive the optical element in rotation or linear movement manner to make the optical element 121 diverge from the focal region of the light focusing module 11 , so that the converged sunlight SL 2 passing through the focal region will diffuse for the illumination purpose. It can be understood that the same purpose can be achieved by driving the light deflection module 12 including the optical elements 121 , 122 to diverge from the focal region of the light focusing module 11 by the driving element 13 . In one embodiment, the driving element 13 may drive the optical element 121 in rotation manner to make the sunlight SL 2 converged by the light focusing module 11 deflect to other direction for irradiating a wider range of the target area 20 , instead of deflecting to the optical element 122 .
[0027] Referring to FIG. 7 a and FIG. 7 b to illustrate the sunlight manipulating device according to the seventh embodiment of the present invention. Compared to the first embodiment shown in FIG. 1 , the difference between the two is that the seventh embodiment further comprises at least one of a filter element 14 and a scattering element 15 , and the remaining components are the same as the first embodiment. The filter element 14 and the scattering element 15 may be driven by the driving element (not shown in FIG. 7 a and FIG. 7 b ) to selectively move to the focal region or adjacent to the focal region in linear movement or rotation manner. According to the foregoing structure, for example as the illumination purpose, the filter element 14 or the scattering element 15 can be moved to the focal region to filter or scatter the converged sunlight SL 2 to achieve better illumination effects.
[0028] Referring to FIG. 8 to illustrate the sunlight manipulating device according to the eighth embodiment of the present invention. Compared to the first embodiment shown in FIG. 1 , the difference between the two is that the light focusing module and the light deflection module of the eighth embodiment are a plurality, wherein the light focusing module 11 a is corresponding with the light deflection module 12 a and the light focusing module 11 b is corresponding with the light deflection module 12 b, and the remaining components are the same as the first embodiment. As shown in FIG. 8 , the groups of the light focusing module and the light deflection module deflect the converged sunlight SL 2 to the same target area 20 . According to this structure, more sunlight can be obtained per unit area of the target area 20 .
[0029] Referring to FIG. 9 to illustrate the sunlight manipulating device according to the ninth embodiment of the present invention. Compared to the first embodiment shown in FIG. 1 , the difference between the two is that the light focusing module 11 is an asymmetric focusing optical element. Briefly, the focal region of the light focusing module 11 is diverged from a physical center axis C of the light focusing module 11 . Therefore, the setting position of the light deflection module 12 is diverged from the physical center axis C of the light focusing module 11 , which improve the installation of the light focusing module 12 be more flexible.
[0030] Referring to FIG. 9 again, in one embodiment, the light deflection module 12 may be a reflective filter. In other words, a first light WL 1 of a first wavelength range among the converged sunlight can be deflected to the target area 20 by the light deflection module 12 , and a second light WL 2 of a second wavelength range among the converged sunlight transmits through the light deflection module 12 . According to this structure, the second light WL 2 can be used for illumination or irradiating plants to promote plants growth, and the first light WL 1 can be for generating electric power or heating. It can be understood that the first light WL 1 irradiating to the target area 20 may not be used for any purpose.
[0031] To summarize the foregoing descriptions, the sunlight manipulating device of the present invention uses the light focusing module and the light deflection module to adjust the light path of the incident sunlight and guide the sunlight to the target area, so that the installation of the solar cell, the heating device or the light guide element can be more flexible, such as in a sheltered environment or erected installation. In addition, the light path of the incident sunlight can be changed by controlling the light focusing module or the light deflection module so as to selectively adjust the application of the sunlight.
[0032] While the invention is susceptible to various modifications and alternative forms, a specific example thereof has been shown in the drawings and is herein described in detail. It should be understood, however, that the invention is not to be limited to the particular form disclosed, but to the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the scope of the appended claims. | A sunlight manipulating device includes a light focusing module and a light deflection module. The light focusing module is configured for converging incident sunlight on a focal region. The light deflection module is arranged on the focal region or adjacent to the focal region and configured for deflecting the converged sunlight to a target area, wherein the target area is diverged from an optical axis of the light focusing module. The above-mentioned sunlight manipulating device allows more diverse configurations for solar cells, heating devices and light guide elements or the like means. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of and claims the benefit of U.S. patent application Ser. No. 14/013,889, filed Aug. 29, 2013, which is a continuation-in-part of and claims the benefit of U.S. patent application Ser. No. 13/018,077, filed Jan. 31, 2011, now U.S. Pat. No. 8,534,982, all of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to a loading system for a vehicle, and particularly to a rotating lift system for loading and unloading equipment, such as combine heads and other agricultural implements, on trailers.
[0004] 2. Description of the Related Art
[0005] Implements and equipment for tillage, cultivation and other agricultural operations have been developed with the objectives of increasing efficiency and lowering operating costs. For example, wider equipment tends to be more efficient because greater field areas can be covered with fewer passes in less time. Tractors have tended to become larger in order to accommodate such wider implements and their greater towing power requirements.
[0006] Modern agricultural operations commonly require equipment adapted for transporting over public roads. For example, many farmers and farming operations work multiple, noncontiguous fields with the same equipment, which must be configured to comply with traffic regulations, including maximum width requirements. Various implement transport mechanisms have been developed for this purpose. For example, implements are commonly designed to fold and unfold between field use and transport configurations.
[0007] Transporting oversize implements commonly involves placing them on transport vehicles, such as trailers, with their long dimensions generally aligned with the direction of travel. For example, the Mefferd et al. U.S. Pat. No. 4,060,259 shows an implement supported on auxiliary wheels and drawn by a vehicle attached to an end of the implement. Alternatively, an implement can be reoriented by a device that rotates it. For example, the Van Selus U.S. Pat. No. 3,727,698 discloses a trailer apparatus incorporating a turntable supported on a trailer body wherein a lift and support assembly is mounted on the turntable for lifting an implement and supporting it in an elevated position with the elongated dimension of the implement extending parallel to the direction of travel.
[0008] A further example is shown in the Shannon U.S. Pat. No. 4,286,918, which discloses an implement transporter including a trailer having a lifting and rotating mechanism for engaging, lifting and rotating an implement. The weight of the implement is supported by a roller, and the lifting mechanism is guided through an arcuate path-of-movement by an arm pivoted adjacent to one side of the trailer whereby the supported implement may be rotated 90 degrees relative to the trailer.
[0009] Yet another example is shown in the Pingry et al. U.S. Pat. No. 6,238,170, which describes an implement transporter including a trailer having a lifting and rotating mechanism for engaging, lifting and rotating the implement. The trailer includes a turntable supporting a cantilevered arm and the cantilevered arm includes a lift and support assembly.
[0010] Existing pieces of equipment for hauling large implements or other objects may be oversized for some situations or for some users' needs. The prior art references above, for example, would be more equipment than necessary for many smaller applications.
[0011] Heretofore there has not been available a lift mechanism with the advantages and features of the present invention.
SUMMARY OF THE INVENTION
[0012] In the practice of an aspect of the present invention a rotator arm, a rotator arm guide, an arcuate rotation track and a load lift assembly are provided for engaging, lifting and rotating an implement, thereby moving the implement between perpendicularly opposed field use and transport positions. The rotator arm is connected to a pivot member for rotation about a vertical axis. The rotator arm guide is connected to the opposite end of the rotator arm. The rotator arm guide is adapted for engaging and moving along the rotation track. The load lift assembly is mounted on the rotator arm and is adapted for engaging an implement's three point hitch or header attachment and lifting the implement or header.
[0013] An alternative embodiment lifting system is connected to a standard hitch trailer along a pair of carriage rails. The lifting system is pushed forwards and backwards on the trailer by a hydraulic piston-and-cylinder, from a transport position to a loading position. A second hydraulic piston-and-cylinder raises and lowers a linkage assembly for connecting with a three-point hitch of an implement or load. The load is then raised and pulled back onto the trailer such that it is placed over the axle and wheels of the trailer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The drawings constitute a part of this specification and include exemplary embodiments of the present invention illustrating various objects and features thereof.
[0015] FIG. 1 is an isometric view of a rotating lift system embodying an aspect of the present invention.
[0016] FIG. 2 is an isometric view of the rotating lift system with the load lift assembly in a lowered, loading position.
[0017] FIG. 3 is an isometric view of the rotating lift system with the load lift assembly in a raised, loading position.
[0018] FIG. 4 is an enlarged, isometric view taken generally within the circle shown in FIG. 1 of the rotating lift system of the present invention with the load lift assembly in a raised, rotated, transport position.
[0019] FIG. 5 is an exploded, isometric view of the rotating lift system.
[0020] FIG. 6 is an enlarged, isometric view of the rotating lift system, shown without the load lift assembly.
[0021] FIG. 7A and FIG. 7B are isometric views of the load lift assembly in lowered and raised positions, respectively.
[0022] FIG. 8 is an enlarged, isometric view of the header adapter from FIG. 6 , shown with three point hitch connectors of the load lift assembly attached thereto.
[0023] FIG. 9 is an isometric view of the header adapter showing the header adapter brackets and the three-point hitch connection pins.
[0024] FIG. 10 is a top plan view showing the movement of a rotator arm and a rotator arm guide along a rotation track as a rotation cylinder is retracted.
[0025] FIG. 11 is a sectional view taken generally along line 11 - 11 in FIG. 10 showing the movement of a stow lock from a support position to a storage position as a stow lock cylinder is extended.
[0026] FIG. 12 is an isometric view of the load lift assembly, shown with a three point hitch implement connected thereto.
[0027] FIG. 13A is an enlarged, isometric view of a stabilizer.
[0028] FIG. 13B is an enlarged, isometric view, particularly showing the stow lock, the stow lock cylinder and a stow lock rotation shaft.
[0029] FIG. 14 is an enlarged, isometric view, particularly showing the header adapter and a header adapter storage bracket.
[0030] FIG. 15 is an enlarged, isometric view, particularly showing a modified trailer frame with a gooseneck attachment.
[0031] FIG. 16 is an enlarged, isometric view, particularly showing modified header adapter brackets.
[0032] FIG. 17 is a schematic diagram of the hydraulic system.
[0033] FIG. 18 is an isometric view of an alternative embodiment load lift assembly with an extended, telescoping light bar.
[0034] FIG. 19 is an isometric view thereof, showing the light bar being retracted into the structure of the load lift assembly.
[0035] FIG. 20 is an isometric view thereof, showing the light bar being fully retracted into the structure of the load lift assembly.
[0036] FIG. 21 is a side elevational view thereof, demonstrating the functionality of the telescoping light bar.
[0037] FIG. 22 is an isometric view of an alternative embodiment load lift assembly.
[0038] FIG. 23 is an isometric view of yet another alternative embodiment load lift assembly including its typical environment of a trailer, the alternative embodiment load lift assembly being in a first, transport position.
[0039] FIG. 24 is an isometric view thereof, the alternative embodiment load lift assembly being in a second, loading position.
[0040] FIG. 25 is an isometric view thereof, the alternative embodiment load lift assembly being in a third, lifting position.
[0041] FIG. 26 is a side elevational view of the embodiment shown in FIG. 23 .
[0042] FIG. 27 is a side elevational view of the embodiment shown in FIG. 25 .
[0043] FIG. 28 is a side elevational view of the embodiment shown in FIG. 24 .
[0044] FIG. 29 is a top plan view of the embodiment shown in FIG. 24 .
[0045] FIG. 30 is a rear elevational view thereof.
[0046] FIG. 31 is an isometric view of the embodiment of FIGS. 23-30 without its typical environment.
[0047] FIG. 32 is a partially exploded isometric view thereof.
[0048] FIG. 33 is a three-dimensional isometric view of the embodiment shown in FIG. 25 , having a pair of outriggers mounted to the rear of the trailer frame.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
I. Introduction and Environment
[0049] As required, detailed aspects of the present invention are disclosed herein, however, it is to be understood that the disclosed aspects are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art how to variously employ the present invention in virtually any appropriately detailed structure.
[0050] Certain terminology will be used in the following description for convenience in reference only and will not be limiting. For example, up, down, front, back, right and left refer to the invention as orientated in the view being referred to. The words, “inwardly” and “outwardly” refer to directions toward and away from, respectively, the geometric center of the aspect being described and designated parts thereof. Forwardly and rearwardly are generally in reference to the direction of travel, if appropriate. Said terminology will include the words specifically mentioned, derivatives thereof and words of similar meaning
II. Preferred Embodiment or Aspect of the Self Loading Trailer
[0051] Referring to the drawings in more detail; the reference numeral 1 generally designates a rotating lift system embodying the present invention, as shown in FIGS. 1-17 . Without limitation on the range of useful applications of the rotating lift system 1 , an exemplary application is disclosed comprising: a trailer frame 14 including a rear set of wheels 28 mounted on a rear axle 46 and a forward set of wheels 29 mounted on a forward axle 45 , the axles 45 and 46 being mounted on the trailer frame 14 ; a pair of stabilizers 8 mounted on the rear of the trailer frame 14 ; and a jack 7 mounted on the front of the trailer frame 14 . The trailer frame 14 supports a rotator arm 18 , a rotator arm guide 37 , a pin assembly 17 , an engine 13 , an engine enclosure 12 and a rotation track 3 .
[0052] The pin assembly 17 is mounted on a side of the trailer frame 14 and includes a pin assembly housing 16 , a rotator arm pin 24 and a rotation cylinder pin 25 . The rotator arm 18 , having a first end 35 and a second end 36 , is rotatably connected on its first end 35 to the pin assembly 17 at the rotator arm pin 24 and is rotatable about a vertical axis between a first, load position shown in FIGS. 2 and 3 and a second, transport position shown in FIG. 4 . The second end 36 of the rotator arm 18 is attached to rotator arm guide 37 . The rotator arm guide 37 engages the rotation track 3 with guide wheels 38 . The rotation track 3 is mounted on the trailer frame 14 and is arcuately shaped and concentric with the vertical axis of rotation of the rotator arm 18 .
[0053] A rotation cylinder 22 connects to the pin assembly 17 at a rotation cylinder pin 25 and connects to the rotator arm 18 at a cylinder arm connection pin 23 . The rotation cylinder 22 actuates the movement of the rotator arm 18 between its first and second positions. A load lift assembly 2 is mounted on the rotator arm 18 with a pair of lift arm attachment brackets 30 and a top link attachment bracket 31 . The load lift assembly 2 comprises a pair of lower linkage subassemblies 50 , a lift arm crossbar 58 and an upper linkage subassembly 70 .
[0054] Referring to FIGS. 7A and 7B , the lower linkage subassemblies 50 are each attached to the rotator arm 18 by a pair of lift arm attachment brackets 30 . Each lower linkage subassembly 50 comprises the pair of lift arm attachment brackets 30 , a pair of forward lower link members 54 , a lower linkage pin 53 , a lift cylinder pin 57 , a pair of rearward lower link members 55 , a lower lift arm linkage pin 59 , a pair of lower lift arm linkage members 56 , a lift arm pin 52 , a lift arm 51 , a lower connector 60 and a lift cylinder 20 . For each lower linkage subassembly 50 , the forward lower link members 54 are each movably connected on one end to the lift arm attachment brackets 30 by the lower linkage pin 53 and are attached on their respective opposite ends to the rearward lower link members 55 by the lift cylinder pin 57 , the rearward lower link members 55 each being attached on their respective opposite ends to the lower lift arm link members 56 by the lower lift arm linkage pin 59 . For each lower linkage subassembly 50 , the lower lift arm link members 56 are each attached on one end to the lift arm attachment brackets 30 by the lift arm pin 52 . For each lower linkage subassembly 50 , the lower lift arm 51 is attached to the lower lift arm link members 56 and the lower connector 60 is attached to the end of the lower lift arm 51 . The lower connectors 60 are adapted for connecting to a three-point hitch. The lower linkage subassemblies 50 are connected by the lift arm crossbar 58 , which is attached on either end to the lower lift arms 51 . For each lower linkage subassembly 50 , the lift cylinder 20 is attached on one end to the lift arm pin 52 and on the opposite end to the lift cylinder pin 57 . The lift cylinders 20 actuate the lifting movement of the load lift assembly 2 between its first, lowered position ( FIG. 7A ) and its second, raised position ( FIG. 7B ).
[0055] The upper linkage subassembly 70 is attached to the rotator arm 18 by a pair of top link attachment brackets 31 . The upper linkage subassembly 70 comprises the pair of top link attachment brackets 31 , a pair of forward upper link members 72 , an upper linkage pin 71 , a top link pin 73 , an upper lift arm 74 , a cross bar pin 75 , a pair of upper third arm link members 76 , an upper link slide arm tube 77 , an upper link slide arm 78 , an upper connector 79 and a top link cylinder 26 . The forward upper link members 72 are each attached on one end to the top link attachment brackets 31 and are each attached on their respective opposite ends to the end of the upper lift arm 74 by the top link pin 73 . The upper lift arm 74 is attached on its opposite end to the lift arm crossbar 58 by the crossbar pin 75 . The upper third arm link members 76 are each attached on one end to the ends of the forward upper link members 72 and the end of the upper lift arm 74 by the top link pin 73 . The pair of upper third arm link members 76 opposite ends are each attached to the top link slide arm tube 77 . The top link slide arm 78 , having a first end and a second end, is slidably seated inside the top link slide arm tube 77 . The top link cylinder 26 is attached on one end to the top link pin 73 and is attached on its opposite end to the first end of the top link slide arm 78 . The upper connector 79 is attached to the second end of the top link slide arm 78 and is adapted for connecting to a three point hitch. The top link cylinder 26 actuates the movement of the top link slide arm between its first, extended position and its second, retracted position.
[0056] Referring to FIGS. 8 and 9 , a header adapter 4 comprising a head lift adapter 92 is attached at both of its ends to a pair of vertical header members 93 ; a horizontal header member 97 is attached on either of its ends to the opposite ends of the pair of vertical header members 93 ; a pair of head adapter brackets 94 are each attached to the vertical header members 93 ; multiple header adapter bracket pins 95 are adapted for connecting the header adapter brackets 94 to the vertical header members 93 ; a pair of lower header pins 91 and an upper header pin 90 are adapted for connecting the header adapter 4 to the load lift assembly 2 by the three point hitch connectors 60 and 79 ; and a pair of header elbows 98 are each attached to the horizontal header member 97 and to a respective vertical header member 93 . The header adapter brackets 94 form hooks 100 receiving a header 19 . The lower header pins 91 connect to the header adapter 4 and extend through the vertical header members 93 and the header elbows 98 . A load, such as a combine header, can be placed on and transported by the rotating lift system 1 by mounting the header adapter 4 on the load lift assembly 2 , as described above. Chains 99 are attached to each header adapter bracket 94 and are adapted for wrapping around part of a combine header and thereby securing it to the header adapter 4 .
[0057] Referring to FIGS. 11 and 13B , a stow lock 10 , having first and second ends, is attached at its first end to a stow lock pivot member 34 . The stow lock pivot member 34 is rotatably attached at each end to the trailer frame 14 and is rotatable between a first, lowered position adapted to allow clearance for the rotator arm 18 to pass over the stow lock 10 and a second, raised position adapted for the second end of the stow lock 10 to engage and support the lift arm crossbar 58 . A stow lock cylinder 11 having first and second ends is attached at its first end to the trailer frame 14 and is attached at its second end to the stow lock pivot member 34 by a stow lock pin 33 . The stow lock cylinder 11 actuates the movement of the stow lock 10 between its raised and lowered positions.
[0058] Referring to FIG. 10 , the rotator arm guide 37 is attached to the rotator arm second end 36 in the preferred embodiment and has two guide wheels 38 . The weight of the load lift assembly 2 along with the weight of the load attached to it, such as the header adapter 4 and/or an implement 19 , is supported on the trailer frame 14 by the two guide wheels 38 engaging the rotation track 3 , and the pin assembly 17 . In addition to carrying the weight as described above, the two guide wheels 38 provide stabilization to the load lift assembly 2 by distributing the weight forward of and behind the rotator arm 18 . Further, the use of a rotator arm guide 37 provides a wider base along which to space the guide wheels 38 , thus providing even greater stabilization of the load lift assembly 2 .
[0059] Referring to FIGS. 1 , 10 and 11 , the pin assembly housing 16 supports a hydraulic reservoir 6 and a hydraulic valve assembly 44 . The hydraulic valve assembly 44 is used to control the hydraulic system 41 , and thus the lifting and rotating of the rotating lift system 1 . A unique feature of the rotating lift system 1 is the location of the hydraulic valve assembly 44 , which location enables an operator to control the lifting and rotating mechanisms of the rotating lift system 1 from a single location.
[0060] Referring to FIGS. 2 , 3 , 4 , 7 A and 7 B, a method of lifting an implement 19 or 21 comprises a three step process where first the load lift assembly 2 attaches to the implement 19 or 21 , second the load lift assembly 2 lifts the implement 19 or 21 to a raised position (as shown in FIG. 3 ), and third the rotator arm 18 rotates the load lift assembly 2 and the attached implement 19 or 21 to a transport position (as shown in FIG. 4 ). The implement 21 includes a three point hitch connection and is attached to the rotating lift system 1 by attaching the three-point hitch connectors, the lower connectors 60 and the upper connector 79 to the implement 21 .
[0061] The implement 19 includes a header connection and is attached to the rotating lift system 1 by positioning the header adapter 4 at a point where the implement 19 rests on the header adapter brackets 94 and against the header lift adapter 92 . The implement 19 or 21 is raised by the lower lift arms 51 being raised by the extension of the lift cylinders 20 . The implement 19 or 21 is rotated to a transport position as the rotator arm 18 rotates about the rotator arm pin 24 . To further stabilize and secure the loaded implement 19 for transport, the stow lock 10 is rotated into its raised position and engages the lift arm cross bar 58 .
[0062] Referring to FIG. 14 , header adapter storage brackets 96 a, 96 b are attached to the trailer frame 14 . When not in use, the header adapter 4 can be stored in the header adapter storage brackets 96 a, 96 b by securing it with the lower header pins 91 and the upper header pin 90 . Referring to FIG. 17 , a hydraulic system 41 is attached to various points as defined above and is connected by hoses ( FIG. 17 ) and is operated in a conventional manner. The hydraulic system 41 includes a pump 40 driven by the engine 13 , which hydraulically connects to the other hydraulic system components via a filter 42 .
[0063] Referring to FIGS. 1 and 13A , each stabilizer 8 attached to the rear of the trailer frame 14 comprises a pair of stabilizer trailer brackets 80 , a stabilizer cylinder 81 , a stabilizer cylinder trailer pin 82 , a stabilizer link 83 , a stabilizer link trailer pin 84 , a pair of stabilizer brackets 85 , a stabilizer cylinder pin 86 , a stabilizer link pin 87 , and a stabilizer pad 88 . The stabilizer trailer brackets 80 are attached to the trailer frame 14 . Each stabilizer cylinder 81 is attached at its first end to a stabilizer trailer bracket 80 by a stabilizer cylinder trailer pin 82 . Each stabilizer cylinder 81 second end is attached to a respective stabilizer bracket 85 by a stabilizer cylinder pin 86 . Each stabilizer link 83 has a first end attached to the stabilizer trailer brackets 80 by a stabilizer link trailer pin 84 and a second end attached to a stabilizer bracket 85 by a stabilizer link pin 87 . Each stabilizer pad 88 is attached to a respective stabilizer link 83 by a respective stabilizer link pin 87 .
[0064] When loading an implement 19 , the combined weight of the rotating lift system 1 and the implement 19 is transferred to the stabilizers 8 from the wheels 28 and 29 by lowering the stabilizer 8 . The stabilizers 8 are lowered by the stabilizer cylinders 81 extending causing the stabilizer pads 88 and stabilizer links 83 to rotate counterclockwise in an arcuate path until the stabilizer pad 88 engages the ground and lifts the rotating lift system 1 enough to effectuate the weight transfer.
[0065] Referring to FIG. 1 , the rotating lift system 1 is shown with a bumper pull trailer hitch 15 . Referring to FIG. 15 , an alternative embodiment rotating lift system 101 is shown with a gooseneck trailer hitch 115 . FIG. 16 shows sloped header adapter brackets 194 , which are an alternative to the header adapter brackets 94 for accommodating combine headers and other loads with structural configurations corresponding to the alternative header adapter brackets 194 . It will be appreciated that other adapters can be utilized with the rotating lift system 1 for loading and transporting a variety of loads with various configurations in multiple sizes.
III. Alternative Embodiment or Aspect of the Self Loading Trailer
[0066] FIGS. 18-21 show an alternative embodiment self-loading trailer 201 , including a modified trailer body 214 having receiver slots 216 for receiving the telescoping rails 206 of a telescoping light bar assembly 204 . A light bar 210 is affixed to the ends of the telescoping rails 206 via quick release connecting pins 215 or similar semi-permanent connections. The light bar 210 includes safety lights 212 which extend the reach of the safety lights of the original trailer 214 beyond the overhang distance 220 of the end of the transported implement 19 . For example, the light bar 210 may include brake lights and turning signals which receive the appropriate signals from the trailer 214 or the truck towing the trailer.
[0067] A number of pin receiver holes 208 are located in the sides of the rails 206 . These pin holes allow the telescoping rails to be locked at varying distances from the trailer 214 via a corresponding pin hole 218 located in the trailer. Similarly, the light bar 210 is connected to the opposite end of the rails 206 .
IV. Alternative Embodiment or Aspect Load Lift Assembly
[0068] FIG. 22 shows an alternative embodiment of a load lift assembly 252 which generally includes the same components mentioned above. However, the alternative embodiment includes a pair of gas struts 256 used to assist with the lifting and lowering action of the load lift assembly 252 during connecting and disconnecting of three point implements. The struts are affixed to the upper linkage assembly 270 .
V. Alternative Embodiment Implement Lift System 302
[0069] FIGS. 23-32 show an alternative embodiment Implement Lift System 302 , which is typically composed of a lifting assembly 304 mounted onto a trailer frame 314 as shown in FIGS. 23-30 . FIGS. 31-32 show the lifting assembly 304 by itself. The lifting assembly 304 may be mounted to another vehicle type other than a trailer; however, the preferred embodiment would be deployed within a trailer.
[0070] The trailer includes a frame 314 , a hitch 315 for towing the trailer, an optional chain 316 for added security and stability, a jack 307 for stabilizing the trailer when hooking or unhooking from a towing vehicle (not shown), and a pair of tires 328 mounted about an axle assembly 346 . The tires could be mounted on an actual axle; however, as shown in the FIGS. 23-30 , the axle assembly mounts the wheels to the frame 314 of the trailer and provides a structural support between the wheels. When an implement 305 is loaded onto the trailer, ideally it will be centrally held over the axle assembly 346 for superior support while transporting the implement.
[0071] As shown in the progression of FIGS. 23-25 , the lifting assembly 304 is transferred from a first, transport position as shown in FIG. 23 , to a second, loading position as shown in FIG. 24 , to a third, lifted position as shown in FIG. 25 . Once the implement 305 or other object is lifted, the lifting assembly 304 is transferred back to the transport position as shown in FIG. 23 , now with a loaded implement or other object. FIG. 26 demonstrates how an implement 305 would be positioned over the axle assembly 346 and wheels 328 of the trailer when the implement lift system 302 is in the transport position, thereby providing the most stability for the transported implement 305 .
[0072] The lifting assembly 304 is designed to attach to a three-point hitch of an implement or some other object to be lifted. A pair of lower lift arms 351 pinned to arms of a lift arm weldment 318 with mounting pins 352 , the lower lift arms 351 connect to two points of the three-point hitch. The lift arm weldment 318 is mounted to lift arm weldment mounting end brackets 319 and lift arm weldment center brackets 354 affixed to the main frame of the lifting assembly 304 . The lift arm weldment 318 and lift arms 351 form the lower linkage assembly 350 . A top link assembly 379 connects to the third point of the three-point hitch. The top link assembly 379 is pivotally pinned to a pair of top link mounting brackets 378 which are affixed to the main frame of the lifting assembly 304 . The main frame of the lifting assembly is bounded by a pair of carriage weldments 336 which have carriage rollers 338 designed to allow the assembly 304 to slide easily along carriage guides 324 which are part of the trailer frame 314 .
[0073] The lifting assembly 304 is moved along the carriage guides 324 of the trailer frame 314 by a piston-and-cylinder arm 310 which is powered by a hydraulic reservoir assembly 340 and motor 313 . A second piston-and-cylinder arm 312 causes the lower linkage assembly to pivot about the lift arm weldment mounting brackets 319 , thereby raising and lowering the arms 351 and any implement attached thereto. A set of controls 342 are connected to the hydraulic system 340 and operate the hydraulics which power hydraulic arms 310 , 312 . A lift lock weldment 356 stabilizer arm helps to secure the lower linkage assembly 350 in position by being received by a lift lock weldment receiver 358 mounted to the frame of the lifting assembly 304 . The lift lock weldment 356 physically prevents the lift arms 351 and lift arm weldment 318 from dropping an attached implement. A lift link 331 also pivotally joins the lift arms 351 and lift arm weldment 318 to a pair of rear lift arm brackets 320 which are pivotally mounted to a pair of rear mounting brackets 322 . The end of the lift lock weldment 356 and the piston-and-cylinder arm 312 are also pivotally mounted to the rear lift arm brackets 320 . This entire assembly allows all of these elements to freely pivot, allowing the lower linkage assembly 350 to be lifted or lowered.
[0074] In operation, the lifting assembly 304 is pushed to the rear of the trailer frame 314 via the hydraulic piston-and-cylinder arm 310 . The lower linkage assembly 350 and top link assembly 379 are hydraulically lowered using the other piston-and-cylinder arm 312 . The implement 305 is connected to the lower linkage assembly 350 liftarms 351 and the top link assembly 379 via a three-point hitch. The piston-and-cylinder arm 312 then hydraulically raises the lower linkage assembly 350 and top link assembly 379 , and the lift lock weldment 356 locks into the lift lock weldment receiver 358 , physically restraining the implement from dropping without an operator operating the controls 342 instructing it to be dropped. The entire lifting assembly 304 is then drawn back towards the front of the trailer frame 314 , and the implement is stored above the wheels 328 and axle assembly 346 of the trailer for transport. The implement 305 can be unloaded using these same steps.
[0075] As indicated in FIGS. 26 , 31 , and 32 , implement connections 368 connect the hydraulic systems of the implement 305 hooked up to the lift assembly 304 . The implement 305 may then be controlled using the controls 342 and the hydraulic reservoir assembly 340 of the lift assembly 304 . This allows the operator to hydraulically rotate the implement 305 using the implement's own controllable elements in the event that the implement would not fit within standard transportation dimensions for roads and hi-ways. An example may be a bladed implement for earth grading which can be pivoted about a center point once the implement is pulled onto the trailer of the lifting system 302 .
[0076] FIG. 33 includes a pair of outriggers 308 mounted to the rear of the trailer frame 314 . These outriggers 308 stabilize the trailer and the loading system 302 while the implement is being loaded onto the trailer. If, for example, the loading system 302 is deployed in an area with soft ground underneath, the outriggers help to prevent the trailer from tipping while the load is added to the trailer. Here, the outriggers 308 are shown with a hand crank and a wide splayed footing. The hand crank could be replaced with any other mechanical means for raising and lowering the outrigger. When not in use, the outriggers may be rotated for storage or removed entirely from the trailer frame.
[0077] It is to be understood that the invention can be embodied in various forms, and is not to be limited to the examples discussed above. The range of components and configurations which can be utilized in the practice of the present invention is virtually unlimited. | A lift system and method for transporting agricultural implements. The lift system includes a pair of lower linkage arms, an upper link, and at least four carriage wheels for transporting the lift system along carriage guide rails of a trailer frame. A load lift assembly is mounted on the trailer and is movable between lowered, loading position, a raised position, and a transport position. It is capable of connecting to a load having a three-point hitch. A gas strut may optionally be equipped to aid in the lifting process. A telescoping light bar may be included to increase safety while in transport. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation application of U.S. application Ser. No. 11/654,083 filed on Jan. 17, 2007, which claims priority to earlier filed U.S. provisional application Ser. No. 60/759,606 filed on Jan. 17, 2006, the entire contents of each of which are incorporated herein by their reference. The electrical energy harvesting power sources disclosed herein are described in detail in U.S. patent application Ser. Nos. 10/235,997 (now U.S. Pat. No. 7,231,874) and 11/116,093 (now U.S. Pat. No. 7,312,557), each of which are incorporated herein by their reference.
GOVERNMENTAL RIGHTS
This invention was made with Government support under Contract No. DAAE30-03-C1077, awarded by the U.S. Army. The Government may have certain rights in this invention.
BACKGROUND
1. Field
The present invention relates generally to power supplies, and more particularly, to power supplies for projectiles, which generate power due to an acceleration of the projectile.
2. Prior Art
Fuzing of munitions is necessary to initiate a firing of the munition. Currently, there is no reliable and simple mechanism for differentiating an accidental drop of a munition from a firing acceleration, to prevent an accidental drop from initiating a fuzing of the munition. Similarly, there is a need to reliably validate firing and start of the flight of a munition. For rounds with booster rockets, this capability can provide the means to validate firing, firing duration and termination. Munitions further require the capability to detect target impact, to differentiate between hard and soft targets and to provide a time-out signal for unexploded rounds. Lastly, in order to recover unexploded rounds (munitions) it would be desirable for the munition to have the capability to notify a recovery crew.
SUMMARY
The power sources/generators/supplies disclosed in U.S. patent application Ser. Nos. 10/235,997 and 11/116,093 are based on the use of piezoelectric elements. Such power sources are designed to harvest electrical energy from the firing acceleration as well as from the aerodynamics induced motions and vibration of the projectile during the entire flight. The energy harvesting power sources can withstand firing accelerations of over 100,000 Gs and can be designed to address the power requirements of various fuzes, communications gear, sensory devices and the like in munitions.
The electrical energy harvesting power sources are based on a novel approach, which stores mechanical energy from the short pulse firing accelerations, and generates power over significantly longer periods of time by vibrating elements, thereby increasing the amount of harvested energy by orders of magnitude over conventional methods of directly harvesting energy from the firing shock. With such power sources, electrical power is also generated during the entire flight utilizing the commonly present vibration disturbances of various kinds of sources, including the aerodynamics disturbances or spinning. Such power sources may also be used in a hybrid mode with other types of power sources such as chemical reserve batteries to satisfy any level of power requirements in munitions.
While the piezoelectric power generators are generally suitable for many applications, they are particularly well suited for low to medium power requirements, particularly when safety and very long shelf life are critical factors.
The electrical energy harvesting power sources for munitions are based on a novel use of stacked piezoelectric elements. Piezoelectric elements have long been used in accelerometers to measure acceleration and in force gages for measuring dynamic forces, particularly when they are impulsive (impact) type. In their stacked configuration, the piezoelectric elements have also been widely used as micro-actuators for high-speed and ultra-accuracy positioning applications with low voltage input requirement and for high-frequency vibration suppression. The piezoelectric elements have also been used as ultrasound sources and for the generation and suppression of acoustic signals and noise.
In the present application, the electrical energy harvesting power sources are used for powering fuzing electronics as acceleration and motion sensors, acoustic sensors, micro-actuation devices, etc., that could be used to enhance fusing safety and performance. As such, the developed electrical energy harvesting power sources, in addition to being capable of replacing or at least supplementing chemical batteries, have significant added benefits in rendering fuzing safer and enhancing its operational performance. Fir example, the piezoelectric-based electrical energy harvesting power sources can provide the following safety and performance enhancing capabilities:
1. Capability to detect accidental drops and differentiate them from the firing acceleration. 2. Capability to validate firing and start of the flight. For rounds with booster rockets, this capability will provide the means to validate firing, firing duration and termination. 3. Capability to detect target impact. 4. Capability to differentiate between hard and soft targets. 5. Capability to provide time-out signal for unexploded rounds. 6. In an unexploded round, the capability to detect acoustic and vibration wake-up signals generated by a recovery crew and respond to the same via an RF or acoustic signal or the like.
Accordingly, a system is provided for recovering an unexploded munition. The system comprising: a power supply having a piezoelectric material for generating power from an induced vibration; and a processor operatively connected to the power supply for monitoring an output from the power supply after the power supply has stopped generating power from a firing of the munition and generating a beacon signal upon the detection of the output.
The beacon signal can be a radio-frequency signal.
The beacon signal can be coded with additional information. The additional information can location data from a GPS receiver.
Also provided is a method for recovering an unexploded munition. The method comprising: providing the munition with a power supply having a piezoelectric material for generating power from an induced vibration; inducing a vibration; monitoring an output from the power supply after the power supply has stopped generating power from a firing of the munition; and generating a beacon signal upon the detection of the output.
The method can further comprise coding the beacon signal with additional information.
Still yet provided is a method for detonating an unexploded munition. The method comprising: providing the munition with a power supply having a piezoelectric material for generating power from an induced vibration; inducing a vibration; monitoring an output from the power supply after the power supply has stopped generating power from a firing of the munition; and generating a detonation signal upon the detection of the output to detonate the munition.
The method can further comprise transmitting a second detonation signal for detonation of at least one other unexploded munition.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects, and advantages of the apparatus and methods of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where:
FIG. 1 illustrates a schematic cross section of an exemplary power generator for fuzing of a munition.
FIG. 2 illustrates a schematic view of a system of harvesting electric charges generated by the power generator of FIG. 1 .
FIG. 3 illustrates a longitudinal acceleration (firing force, which is equal to the longitudinal acceleration times the mass of the round) versus time plot for a fired munition.
DETAILED DESCRIPTION
In the methods and apparatus disclosed herein, the spring end of a mass-spring unit is attached to a housing (support) unit via one or more piezoelectric elements, which are positioned between the spring end of the mass-spring and the housing unit. A housing is intended to mean a support structure, which partially or fully encloses the mass-spring and piezoelectric elements. On the other hand, a support unit may be positioned interior to the mass-spring and/or the piezoelectric elements or be a frame structure that is positioned interior and/or exterior to the mass-spring and/or piezoelectric elements. The assembly is provided with the means to preload the piezoelectric element in compression such that during the operation of the power generation unit, tensile stressing of the piezoelectric element is substantially avoided. The entire assembly is in turn attached to the base structure (e.g., gun-fired munitions). When used in applications that subject the power generation unit to relatively high acceleration/deceleration levels, the spring of the mass-spring unit is allowed to elongate and/or compress only within a specified limit. Once the applied acceleration/deceleration has substantially ended, the mass-spring unit begins to vibrate, thereby applying a cyclic force to the piezoelectric element, which in turn is used to generate electrical energy. The housing structure or the base structure or both may be used to provide the limitation in the maximum elongation and/or compression of the spring of the mass-spring unit (i.e., the amplitude of vibration). Each housing unit may be used to house more than one mass-spring unit, each via at least one piezoelectric element.
In the following schematic the firing acceleration is considered to be upwards as indicated by arrow 113 .
In FIG. 1 , power generation unit 100 includes a spring 105 , a mass 110 , an outer shell 108 , a piezoelectric (stacked and washer type) generator 101 , one socket head cap screw 104 and a stack of Belleville washers 103 (each of the washers 103 in the stack is shown schematically as a single line). Piezoelectric materials are well known in the art. Furthermore, any configuration of one or more of such materials can be used in the power generator 100 . Other fasteners, which may be fixed or removable, may be used and other means for applying a compressive or tensile load on the piezoelectric generator 101 may be used, such as a compression spring. The piezoelectric generator 101 is sandwiched between the outer shell 108 and an end 102 of the spring, and is held in compression by the Belleville washer stack 103 (i.e., preloaded in compression) and the socket head cap screw 104 . The mass 109 is attached (e.g., screwed, bonded using adhesives, press fitted, etc.) to another end 106 of the spring 105 . The piezoelectric element 101 is preferably supported by a relatively flat and rigid surface to achieve a relatively uniform distribution of force over the surface of the element. This might be aided by providing a very thin layer of hard epoxy or other similar type of adhesives on both contacting surfaces of the piezoelectric element. The housing 108 may be attached to the base 107 by the provided flange 111 using well known methods, or any other alternative method commonly used in the art such as screws or by threading the outer housing and screwing it to a tapped base hole, etc. The mass 109 is provided with an access hole 110 for tightening the screw 104 during assembly. Between the free end 106 of the spring and the base 107 (or if the mass 109 projects outside the end 106 of the spring, then between the mass 109 and the base 107 ) a gap 112 is provided to limit the maximum expansion of the spring 105 . Alternatively, the gap 112 may be provided by the housing 108 itself. The gap 112 also limits the maximum amplitude of vibration of the mass-spring unit.
During firing of a projectile (the base structure 107 ) containing such power generation unit 100 , the firing acceleration is considered to be in the direction 113 . The firing acceleration acts on the mass 109 (and the mass of the spring 105 ), generating a force in a direction opposite to the direction of the acceleration that tends to elongate the spring 105 until the end 106 of the spring (or the mass 109 if it is protruding from the end 106 of the spring) closes the gap 112 . For a given power generator 100 , the amount of gap 112 defines the maximum spring extension, thereby the maximum (tensile) force applied to the piezoelectric element 101 . As a result, the piezoelectric element is protected from being damaged by tensile loading. The gap 112 also defines the maximum level of firing acceleration that is going to be utilized by the power generation unit 100 .
When the firing acceleration has ended, i.e., after the projectile has exited the gun barrel, the mechanical (potential) energy stored in the elongated spring is available for conversion into electrical energy. This can be accomplished by harvesting the varying voltage generated by the piezoelectric element 101 as the mass-spring element vibrates. The spring rate and the maximum allowed deflection determine the amount of mechanical energy that is stored in the spring 105 . The effective mass and spring rate of the mass-spring unit determine the frequency (natural frequency) with which the mass-spring element vibrates. By increasing (decreasing) the mass or by decreasing (increasing) the spring rate of the mass-spring unit, the frequency of vibration is decreased (increased). In general, by increasing the frequency of vibration, the mechanical energy stored in the spring 105 can be harvested at a faster rate. Thus, by selecting appropriate spring 105 , mass 109 and gap 112 , the amount of electrical energy that can be generated and the rate of electrical energy generation can be matched with the requirements of a projectile.
In FIG. 1 , the spring 105 is shown to be a helical spring. The preferred helical spring, however, has three or more equally spaced helical strands to minimize the sideways bending and twisting of the spring during vibration. In general, any other type of spring may be used as long as they provide for vibration in the direction of providing cyclic tensile-compressive loading of the piezoelectric element.
The power generation unit 100 of FIG. 1 is described herein by way of example only and not to limit the scope or spirit of the present invention. Other embodiments described in U.S. patent application Ser. Nos. 10/235,997 and 11/116,093 can also be used in the applications described below as well as any other type of power generation unit which harvests electrical energy from a vibrating mass due to the acceleration of a projectile/munition as well as from the aerodynamics induced motions and vibration of the projectile during the entire flight.
The schematic of FIG. 2 shows a typical system of harvesting electric charges generated by the piezoelectric element of the energy harvesting power generation unit 100 as the mass-spring element of the power source begins to vibrate upon exiting the gun barrel. Electronic conditioning circuitry 202 , well known in the art, would, for example, convert the oscillatory (AC) voltages generated by the piezoelectric element to a DC voltage and then regulate it and provide it for direct use or for storage in a storage device 204 such as a capacitor or a rechargeable battery as shown in the schematic of FIG. 2 . The piezoelectric output is connected by wires 203 to the electronic converter/regulator/charger 202 , the output of which is connected to the storage device (a capacitor or rechargeable battery) 204 by wires 205 , or is used to directly run a load 206 via wires 207 . A processor 208 is also provided for processing information from the output of the power generation unit 100 . Although the processor 208 is shown connected by way of wiring 209 to the electronic conditioning circuitry 202 , it can be connected to or integral with any of the shown components such that it is operative to process the output or output information from the power generation unit 100 .
Accidental Drop Detection and Differentiation from Firing
During the firing, the force exerted by the spring element of the power generation unit 100 generates a charge and thereby a voltage across the piezoelectric element that is proportional to the acceleration level being experienced. The generated voltage is proportional to the applied acceleration since the applied acceleration works on the mass of the spring-mass element of the energy harvesting power source (in fact the mass of the piezoelectric element itself as well), thereby generating a force proportional to the applied acceleration level.
In certain situations and particularly in the presence of noise and at relatively low acceleration levels, the mass-spring system of the power generation unit 100 begins to vibrate and generates an oscillatory (AC) voltage with a DC bias, which is still proportional to the level of acceleration that is applied to the munitions. Hereinafter, when vibratory motion is present, the piezoelectric voltage output is intended to indicate the level of the aforementioned DC bias.
The level of voltage produced by the piezoelectric element is therefore proportional to the level of acceleration that is experienced by the munitions in the longitudinal (firing) direction. This information is obviously available as a function of time. A typical such longitudinal acceleration (firing force, which is equal to the longitudinal acceleration times the mass of the round) versus time plot may look as shown in FIG. 3 . From this plot, the processor 208 may calculate information such as the peak acceleration (impulsive force) level and the acceleration (firing force) duration, Δt, can be measured. The processor 208 can be dedicated for such calculations or used for controlling other functions of the munition. The plot information can also be used to calculate the average acceleration (firing force) level and the total applied impulse (the area under the force versus time curve of FIG. 3 or the product of the average firing force times the time duration). The amount of impulse that the round is subjected to in its longitudinal (firing) direction is thereby known. In practice, the processor may be used onboard the munitions (or the generally present fuzing processor could be used) to make the above time and voltage (acceleration or firing force) measurements and perform the indicated calculations and provide the safety and fuzing decision making capabilities that are indicated in the remainder of this disclosure.
However, a round is subjected to such input impulses in its longitudinal direction during its firing as well as during accidental dropping. The level of input impulse due to accidental dropping of the round is, however, orders of magnitude smaller than that of firing.
For example, consider a situation in which a round is dropped on a very rigid concrete slab, generating around 15,000 G of acceleration in the longitudinal direction (here, it is assumed that the round is dropped perfectly on its base, resulting in the highest possible longitudinal impact acceleration). Assuming that the elastic deformation that occurs during the impact is in the order of 0.1 mm, a conservative estimate of the impact duration with a constant acceleration of 15,000 Gs becomes about 0.04 msec. Now, even if we assume a similar acceleration profile in the gun barrel, but spread it over a time duration of 8 msec (close to what is experienced in many large caliber guns), then the impulse experienced during the firing is (8/0.04) or 200 times larger than that experienced during a drop over a hard surface. This is obviously a conservative estimate and the actual ratio can be expected to be much higher since in most situations, the round is not expected to land perfectly on its base and on a very hard surface and that the firing acceleration is expected to be significantly larger than those experienced in an accidental drop.
The above example clearly shows that by measuring the impact impulse, accidental drops can be readily differentiated from the firing acceleration by the processor 208 . This characteristic of the present piezoelectric based power generation units 100 can be readily used to construct a safety feature to prevent arming of the fuzing during accidental drops and/or to take some other preventive measures. This safety feature can be readily implemented in the electrical energy collection and regulation electronics of the power source or in the fuzing electronics (e.g., the processor 208 can have an input into the electrical energy collection and regulation electronics 202 of the power source or in the fuzing electronics to prevent fuzing when the calculated impact pulse is below a predetermined threshold value indicative of a firing).
Firing Validation and Booster Firing and Duration Time and Total Impulse
As was described in the previous section on accidental drop detection and differentiation from firing, the firing impulse as well as its acceleration profile and time duration can be readily measured and/or calculated from the output of the piezoelectric elements of the power generation units 100 by the processor 208 . Similarly, the completion of the firing acceleration cycle and the start of the free flight are readily indicated by the piezoelectric element. In the presence of firing boosters, their time of activation; the duration of booster operation, and the total exerted impulse on the round can also be determined by the processor 208 from the output of the power generation unit 100 .
As a result, the piezoelectric based power generation units provide the means to validate firing; determine the beginning of the free flight; and when applicable, validate booster firing and its duration.
Target Impact Detection
During the flight, the munition/projectile is decelerated by aerodynamic drag. Projectiles are commonly designed to produce minimal drag. As a result, the deceleration in the axial direction is fairly low. In addition, there may also be components of vibratory motions present in the axial direction. Axially oriented piezoelectric based power generation units 100 can also be very insensitive to lateral accelerations, which are also usually fairly small except for high spinning rate projectiles.
When impact occurs (assuming that the impact force is at least partially directed in the axial direction), the piezoelectric elements of the power generation units 100 experience the resulting input impact, including the time of impact, the impact acceleration level, peak impact acceleration (force) and the total impact impulse. As a result, the exact moment of impact can be detected and/or calculated by the processor 208 from the output of the power generation unit 100 .
In addition, when desired, lateral impact time, level and total impulse may be similarly detected by employing at least one such piezoelectric based power generation unit 100 in the lateral directions, noting that at least two piezoelectric power sources directed in two different directions in the lateral plane are required to provide full lateral impact information. Alternatively, a single power generation unit 100 can be provided which is aligned offset from an axial direction so as to have a vibration component in the axial direction and a vibration component in the lateral direction. Such laterally directed power sources are generally preferable for harvesting lateral vibration and movements, such as those generated by small yawing and pitching motions of the round.
Hard and Soft Target Detection
When the munition impacts the target, ground or another object, the munition's deceleration profile can be measured from the piezoelectric element output voltage during the impact period and peak deceleration level, impact duration, impact force and total impulse can then be calculated as previously described using the processor 208 . This information can then be used to determine if a relatively hard or soft target has been hit, noting that the softer the impacted target, the longer would be the duration of impact, peak impact deceleration (force). The opposite will be true for harder impacted targets. This information is very important since it can be used by the fuzing system to make a decision as to the most effective settings.
It is worth noting at this point that the hard or soft target detection and decision making, in fact all the aforementioned detection and decision making processes, are expected to be made nearly instantly by the power source electrical energy collection and regulation electronics or the fuzing electronics by employing, for example, threshold detecting switches to set appropriate flags.
Time-Out Signal for Unexploded Rounds
Once a munition has landed and is not detonated, whether due to faulty fuzing or other components or properly made decision against detonation, the piezoelectric based power generation unit 100 will stop generating electrical energy once its initial vibratory motion at the time of impact has died out. The electrical power harvesting electronics and/or the fuzing electronics can utilize this event, if followed by target impact, to initiate detonation time-out circuitry. For example, the power source and/or fuzing electronics can be equipped with a time-out circuit that would disable the detonation circuitry and/or components to make it impossible for the round to be internally detonated. The time-out period can be programmed, for example, while loading fuzing information before firing, and/or may be provided by built-in leakage rate from capacitors assigned for this purpose.
Wake-Up Signal Detection and Detection Beacon Provision
Consider the situation in which a round has landed without detonation and its detonation window has timed-out. Then at some point in time, a recovery crew may want to attempt to safely recover the unexploded rounds. The present piezoelectric based power generation unit 100 can readily be used to transmit an RF or other similar beacon signals for the recovery crew to use to locate the projectile. This may, for example, be readily accomplished through the generation of acoustic signals that are produced by the dropping or hammering of weights on the ground or by detonating small charges in the suspect areas. The acoustic waves will then cause the piezoelectric elements of the power source to generate a small amount of power to initiate wake-up and transmission of the RF or similar beacon signal. The beacon signal/RF signal transmitter is considered to be part of the processor for purposes of simplicity, but can be separately provided.
When appropriate, the acoustic signal being transmitted by the recovery crew could be coded, such as with location information from a GPS receiver integral with the processor 208 . A GPS receiver can be integral with the processor (as shown) or separate therefrom. In addition, this feature of the power generation unit 100 provides the means for the implementation of a variety of tactical detonation scenarios. As an example, multiple rounds could be fired into an area without triggering detonation, awaiting a detonation signal from a later round, which is transmitted by a coded acoustic signal during its own detonation.
While there has been shown and described what is considered to be preferred embodiments of the invention, it will, of course, be understood that various modifications and changes in form or detail could readily be made without departing from the spirit of the invention. It is therefore intended that the invention be not limited to the exact forms described and illustrated, but should be constructed to cover all modifications that may fall within the scope of the appended claims. | A method is provided for recovering and/or exploded an unexploded munition. The method including: providing the munition with a power supply having a piezoelectric material for generating power from an induced vibration; inducing a vibration; monitoring an output from the power supply after the power supply has stopped generating power from a firing of the munition; and generating a beacon signal or detonation signal upon the detection of the output. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/094,134, filed on Sep. 4, 2008. The entire disclosure of the above application is incorporated herein by reference.
FIELD
The present disclosure relates to a reconfigurable multimedia collaboration system that implements SIP functionality and XML functionality in hardware, such as a field programmable gate array (FPGA).
BACKGROUND
Session Initiation Protocol (SIP) and Extensible Markup Language (XML) are among the most adopted standards in the telecommunications and IT industries. SIP is used to establish multimedia sessions with multiple participants through the Internet. It is used substantially with Voice over IP (VoIP) and provides the basis for several standards including IP Multimedia Systems (IMS). It is used presently to control the communication sessions of multiple participants in regards to the exchange of audio and video packets and via its extensions to control the Instant Messages exchanges.
XML is used significantly for web services, content publishing and forms the basis for standards related to Voice over IP (VoIP) applications like Presence Information Data Format (PIDF, and VoiceXML. When coupled together SIP and XML offer numerous multimedia and communication features including: (a) VoIP call establishment (b) Instant Messaging, (c) Presence, (d) paging, (e) audio and video conferencing and (f) voicemail. Many other extensions to the way people communicate can be added to the above. For a good period of time, the W3C organization, OASIS, and other world-wide organizations worked intensively to setting-up an Internet infrastructure through which enterprises can do business supported by automated processes governed by computers. The internal mechanisms are all XML based and form what is presently known as Publisher-Subscriber infrastructures.
All the processes, protocol, and algorithms form a layered software infrastructure for the control and transport of media and data related Internet present and next generation services. Some of these software processes might impede on the delay implied by processing these layers in software. It is therefore, a need to move all possible computational processes in a corresponding hardware in order to save time during sessions.
This disclosure presents a high level description of an embedded system referred to as a Reconfigurable Multimedia Collaborative System (RMCS). The RMCS acts as a processor performing SIP and XML related tasks at the hardware level, which presently are all implemented in software servers or gateways. The hardware implementation of the combined SIP and XML computational processes is unique. The implementation of the RMCS relieves the computers and computer communication networks from a series of computational processes, as they are executed in the RMCS hardware, while its applications are multifold from an industrial and commercial point of view. The RMCS can be deployed or inserted into any VoIP or unified communication related system such as consumer devices, servers and gateways. With the RMCS embedded in VoIP systems, the telecommunications industry will benefit from augmented performance, scalability and device interoperability. It is also noteworthy that RMCS can serve as a central part of an IP Multimedia Subsystem (IMS) which is considered one of the important wireless standards, initially defined by 3G IP forum.
One example of the RMCS is a nursing home equipped with RFID sensors and patients wearing small devices that are SIP and RFID enabled. When patients move around the nursing home, their presence (i.e. location) is updated through a WLAN when it changes. This simple technology where RFID, SIP and XML are coupled can offer caregivers an efficient, cost effective and fast methodology to monitor the locations of multiple patients simultaneously and provide urgent medical care as needed. The RMCS could also be implemented in small WLAN paging devices that can be used in restaurants or retail stores. As customers arrive to a busy restaurant, the customer is given a mini-pager and is asked to browse the mall until a seat is available which will be communicated through the WLAN pager.
Another usage of the RMCS is in the core of an IP Multimedia Subsystem (IMS). The IMS tasks are related to the delivery of the IP Multimedia to the mobile users. As of now there is not yet an appealing IMS implementation due to incomplete deployment of a series of protocols specified by various forums and their projects related to IMS such as 3GPP, GPRS, TISPAN, etc. Under these considerations, RMCS can accelerate the deployment of the needed set of protocols which will allow a more flexible access and usage to multimedia and especially voice applications over the fixed and mobile devices in a unitary way.
This section provides background information related to the present disclosure which is not necessarily prior art.
SUMMARY
A reconfigurable multimedia collaboration system is provided. The system includes: a SIP engine implemented in hardware that executes functions defined by Session Initiation Protocol (SIP); a XML engine implemented in hardware that executes functions defined by Extensible Markup Language (XML); and an interface that manipulates a set of registers used to communicate with a software component and coordinates functions executed by the SIP engine and the XML engine. The system is preferably implemented in a reconfigurable hardware platform, such as FPGA.
This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features. Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DRAWINGS
FIG. 1 is a diagram illustrating how a reconfigurable multimedia collaboration system (RMCS) interacts with other components in a network environment.
FIG. 2 is a block diagram depicting the high level architecture of the RMCS.
FIG. 3 is a diagram further depicting a software component of the RMCS.
FIG. 4 is a sequence diagram illustrating various commands invoked by the software component of the RMCS.
FIG. 5 is a block diagram depicting a high level architecture for the hardware interface (XSI) to the RMCS.
FIG. 6 is a diagram of a finite state machine describing a portion of functionality of the XSI.
FIG. 7 is a block diagram depicting components of the XSI command module.
FIG. 8 is a diagram of a finite state machine describing the functionality of the XSI Command Module Packet Processor.
FIG. 9 is a diagram of a finite state machine describing the functionality of the XSI Command Module XML reader.
FIG. 10 is a diagram of a finite state machine describing the functionality of the XSI Command Module XML Configuration component.
FIG. 11 is a block diagram depicting components of the XSI Parser module.
FIG. 12 is a diagram of a finite state machine describing the functionality of the XSI Parser module SIP data analyzer component.
FIG. 13 is a diagram of a finite state machine describing the functionality of the XSI Parser module SIP data processor.
FIG. 14 is a diagram of a finite state machine describing the functionality of the XSI Parser module XML and IM Data Processors.
FIG. 15 is a diagram illustrating the XSI Registers data path.
FIG. 16 is a diagram illustrating the XSI Parser data path.
FIG. 17 is a diagram demonstrating the operation of establishing a multimedia session in accordance with SIP.
FIG. 18 is a diagram demonstrating the operation of exchanging presence information in SIP.
FIG. 19 is a diagram demonstrating the operation of exchanging instant messages in SIP.
FIG. 20 provides an example of a SIP INVITE packet with a SDP session description.
FIG. 21 provides an example of a 200 OK packet.
FIG. 22 provides an example of an ACK packet.
FIG. 23 provides an example of a BYE packet.
FIG. 24 provides an example of a SUBSCRIBE packet.
FIG. 25 provides an example of a SIP NOTIFY packet with a PIDF message.
FIG. 26 provides an example of a MESSAGE packet.
FIG. 27 illustrates computing layer in which RMCS can be embedded into.
FIG. 28 is a diagram illustrating how RMCS can be integrated with different types of network devices.
FIG. 29 is a diagram illustrating how RMCS can be integrated within consumer devices.
FIG. 30 is a diagram illustrating how RMCS can be deployed within network gateways and servers.
FIG. 31 is a block diagram depicting a high level architecture of the SIP Engine.
FIG. 32 is a block diagram depicting the components of the SIP data module in the SIP Engine.
FIG. 33 is a diagram of a finite state machine describing the functionality of the interface for the SIP Engine.
FIG. 34 is a block diagram depicting components of the SIP Packet Generator for the SIP Engine.
FIG. 35 is a diagram illustrating the data path of the database components in the SIP generator.
FIG. 36 is a block diagram depicting components of the control unit of the database components in the SIP generator.
FIG. 37 is a diagram illustrating the data path of the SIP character generator.
FIG. 38 is a block diagram depicting components of the control unit for the SIP character generator.
FIG. 39 is a diagram of a finite state machine describing the functionality of the interface for the SIP character generator.
FIG. 40 is a diagram of a finite state machine used to generate four characters by the SIP character generator.
FIG. 41 is a diagram of a finite state machine used to generate three characters by the SIP character generator.
FIG. 42 is a diagram of a finite state machine used to generate two characters by the SIP character generator.
FIG. 43 is a diagram of a finite state machine used to generate one character by the SIP character generator.
FIG. 44 demonstrates an example of the Presence Information Data Format (PIDF).
FIG. 45 is a block diagram illustrating a high level architecture of the XML Engine.
FIG. 46 is a block diagram depicting the components of the XML Parsing Processor.
FIG. 47 is a block diagram depicting the components of the XML Validator.
FIG. 48 is a diagram of a finite state machine describing the functionality of the XML Parsing Processor.
FIG. 49 is a diagram of a finite state machine describing the functionality of the XML Token Writer.
FIG. 50 is a diagram of a finite state machine describing the functionality of the Token Reader.
FIG. 51 is a diagram of a finite state machine describing the functionality of the XML Serializer.
The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure. Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION
FIG. 1 illustrates how a RMCS 12 interacts with other elements in an end-to-end SIP communications system 10 . The RMCS 12 resides on a reconfigurable hardware platform 14 and is used by SIP services 16 to execute SIP functionality as further described below. Services may include, but are not limited to, hardware blocks implementing high level functionality like P2P networking, publisher/subscribe semantics and IP Multimedia Subsystems (IMS) services as defined in IMS literature. Other types of services are also contemplated by this disclosure. Lower layer communications protocols 18 may be used by the RMCS 12 to communicate with other RMCS 12 residing in the computer network environment. In a preferred embodiment, the reconfigurable hardware platform 14 is a field programmable gate array (FPGA). However, other hardware implementations, such as a System on Chip (SoC) with an application specific integrated circuit, are also contemplated.
SIP functionality is briefly described below in order to provide some context for setting forth the RMCS architecture in detail. FIG. 17 illustrates the operation of establishing a multimedia session in accordance with SIP. One participant transmits an INVITE message to another participant. Session information is described in the payload of the INVITE message using the Session Description Protocol (SDP). If the second participant wishes to accept the request a session a 200 OK message is sent back to the first participant. The first participant responds with an ACK (acknowledgement) message and the session is now established. Either participant may terminate the session by sending a BYE message that must be acknowledged with a 200 OK message. Examples of INVITE, 200 OK, ACK and BYE messages are shown in FIG. 20 , FIG. 21 , FIG. 22 and FIG. 23 respectively.
Presence information may also be exchanged with SIP as shown in FIG. 18 . A SUBSCRIBE message is transmitted by an individual wanting to know the presence information of another SIP user. If the SUBSCRIBE request is accepted a 200 OK message is transmitted back to the user. Every time the presence is updated a NOTIFY message is transmitted to all individuals who successfully sent SUBSCRIBE messages. All NOTIFY messages must be acknowledged with a 200 OK message. Examples of SUBSCRIBE and NOTIFY messages are shown in FIG. 24 and FIG. 25 respectively.
Similarly, Instant Messages (IM) may be exchanged in SIP with MESSAGE commands as shown in FIG. 19 . Every MESSAGE must be acknowledged with a 200 OK message. Participants may exchange IMs at any time with MESSAGE commands. An example of a MESSAGE command is shown in FIG. 26 .
SIP is an ASCII based protocol with data separated among several lines. Each line is terminated with a consecutive carriage return and line feed (CRLF). The SIP header is separated from the payload by an extra CRLF. The payload may be represented in various formats depending on the type of SIP command. An INVITE command has a Session Description Protocol (SDP) payload. The payload of a MESSAGE command is directly interpreted as an instant message. A NOTIFY message commonly has a Presence Information Data Format (PIDF) payload. PIDF is an XML based standard for describing all the presence information of a given participant. Examples of SIP messages noted above are based on examples available in “Internet Communications Using SIP: Delivering VoIP and Multimedia Services with Session Initiation Protocol, Second Edition” by Henry Sinnreich and Alan B. Johnston. Further details about the SIP specification may be found in RFC 3261. While the following description is provided with reference to SIP, it is envisioned that broader aspects of the RMCS and this disclosure are applicable to other types of signaling protocols, such as H.323 protocol, SS7 protocol, etc.
FIG. 2 illustrates an exemplary high level architecture for the RMCS 12 . The RMCS is comprised generally of a software component 20 and a hardware component 30 . The software component 20 of the RMCS is used to communicate with a SIP entity regarding configuration and feedback. The software component 20 communicates through a separate communication protocol for exchanging information. The software component 20 is comprised generally of a message processing service 21 and UDP or TCP sockets 22 . The message processing service 21 receives data packets formatted in accordance with SIP and generate commands for manipulating a set of registers 23 , 24 in response thereto. Sockets 22 may be used by the software component 22 to establish connections with remote devices and thereby exchange data over a computer network. The hardware component 30 of the RMCS 12 is used for performing the majority of processing and generation with respect to SIP based data packets as further described below.
The functionality of the software component 22 is further described in relation to FIG. 3 . Messages are received from graphical user interfaces 41 or external users 42 (such as other RMCS) through either UDP sockets 43 or TCP sockets 44 . This information is processed to determine its destination and is forwarded unaltered. RMCS commands and text based messages may be sent through TCP connections. This information is processed and may result in RMCS interaction to retrieve or manipulate relevant data. Responses are sent back to the appropriate party through TCP. This allows RMCS to communicate with either a hardware or software implementation of IMS, respectively SIP servers or clients.
With continued reference to FIG. 2 , data and status registers 23 , 24 comprise the interface to the hardware component 30 . Information is read from both status and data registers 23 , 24 while data is written to the RMCS through data registers 23 alone. The functionality of the hardware component 30 of the RMCS may be further divided into three modules: a SIP engine 31 , a XML engine 32 and an XML and SIP Interface 33 (XSI). The SIP and XML engines perform the functionality for SIP and PIDF, respectively, to generate and process the appropriate information. Both modules share a common interface so data can be successfully transferred to and from software. This interface is implemented as a separate module and is referred to herein as XSI 33 . The XSI 33 manipulates the data and status registers 23 , 24 used to communicate with the software component 20 of the RMCS. Separate memory components 34 , 35 , 36 are used to store SIP, IM and SDP data. These memory components are accessible to and manipulated directly by the XSI 33 and the SIP engine 31 .
Upon receipt of a data packet by the software component 20 , interaction between the XSI, SIP Engine, XML Engine and various memory components is illustrated in FIG. 4 . Numerous commands may be invoked from the software component 20 in response to receipt of a data packet. First, a reset command is written to the XSI 33 which is turn issues resent commends directly to each of the components. The SIP Engine 31 and XML Engine 32 are further configured through separate commands which provide necessary data to the engines before SIP packets are processed. Various read commands are also issued by the software component 20 to retrieve different types of data including status, XML, SIP, IM and SDP data. In each case, the XSI receives the read command, invokes the applicable module (when necessary), retrieves the data and passes it to the software component.
Next, the packet data is written to a buffer inside the XSI 33 for processing by the SIP engine 31 . All other written data is configuration data of the SIP engine 31 or the XML Engine 32 . When the command to process SIP data is sent from the software component 20 , the XSI 33 invokes the SIP engine 31 to begin parsing SIP packet data. The SIP engine 31 writes parsed data into SIP memory 34 and passes the SIP packet type to the XSI 33 when it has been discovered. If the SIP engine 31 is parsing a NOTIFY packet, the payload is presumed to be a PIDF document (see FIG. 25 ) and is written to the XML engine 32 for further processing. When the SIP packet type is a MESSAGE packet, the payload is presumed to be an Instant Message (see FIG. 26 ) and is written to IM memory 35 . Likewise, an INVITE packet should contain an SDP payload (see FIG. 20 ) so it is written to SDP memory 36 . In one embodiment, payloads for other packet types are not processed; whereas, in other embodiments, XSI may be extended to process other packet types.
FIG. 5 describes the high level architecture of the XSI 33 . It is divided into a control unit 51 and data path 52 responsible for high level logic and holding data respectively. The control unit 51 is a collection of finite state machines containing all the logic of the XSI 33 . The interface 53 is used to interact directly with software by receiving and interpreting high level commands. Those commands are translated into lower level equivalents and sent to a command module 54 . The command module 54 acts as the main coordination module of all the functionality that occurs in the RMCS. It is used to generate status values after every operation is complete and concurrently interact with all other modules to ensure that commands are properly executed. A parser module 55 is implemented as a separate component of the control unit and it is used for verifying data before it is send to the SIP and XML modules. Certain errors may be detected by the parser before data is sent to other modules, saving processing time.
The data path is divided into three major components. Data and status registers are stored in the Registers component 56 of the data path. When data is received from software it is directed to the Packet Data component 57 and subsequently to the Parser Data component 58 , if necessary. Configuration data may also be sent directly to the XML engine 32 without being parsed but no such data is necessary for the SIP module.
A finite state machine describing the functionality of the XSI control unit interface 53 is described in FIG. 6 . The interface 53 occupies an idle state when no commands are performed. When a read or write command is invoked to the RMCS, the address is saved and the interface 53 makes a transition to the state where the address is verified. If no errors are detected the command module is enabled to execute the appropriate sequence of actions. The interface 53 enters a wait state while the command module is operational and makes a transition to its idle state once all actions are complete.
The command module 54 is divided into several modules as shown in FIG. 7 . The packet processor 74 is used to manipulate the XSI parser module 55 , SIP engine 31 and XML engine 32 so a SIP packet can be processed as efficiently as possible. The SIP presence reader 73 is used to read a PIDF document from the XML engine 32 while the SIP presence configuration module 74 is used to write configuration data into the XML engine 32 .
FIG. 8 describes the functionality of the packet processor 72 with a finite state machine diagram. The parser module 55 (described in the next section) is activated by the packet processor 72 to parse the SIP (or header) component of the packet. Once the parsing is complete feedback is sent to the packet processor 72 to indicate that the SIP component is syntactically correct or incorrect. The packet processor 72 immediately occupies an idle state when a syntactical error has occurred and proceeds to activate the SIP engine 31 for data processing in the absence of an error. When the SIP data type has been detected (INVITE, MESSAGE, NOTIFY, etc.) feedback is sent to the packet processor 72 allowing for the invocation of the appropriate module for payload data parsing while SIP data is being processed. In this manner the header and payload components of the header can be processed simultaneously. Once both the SIP and payload components have been successfully parsed and processed the packet processor 72 occupies its idle state.
The functionality performed by the payload processing state depends on the SIP data type detected. NOTIFY packets contain XML based PIDF data, MESSAGE packets contain instant messages and INVITE packets have SDP payloads. Separate functionality is invoked in each case to process the payload properly. Furthermore the detection of any payload with other SIP data types automatically generates an error and the deletion of the entire packet.
FIG. 9 describes the finite state machine for the SIP presence reader 73 . SIP presence information is read sequentially and stored in memory so it can be transferred to software through the XSI 33 . The memory address is incremented after every read operation. After all SIP presence information has been read the state machine transitions to its idle state.
FIG. 10 describes the state machine of the SIP presence configuration module 74 . All previous data is first cleared, and then all configuration data is written sequentially into the XML engine. The memory address of the XML engine 32 is continuously incremented as data as long as data is available and the XML memory space has not been exceeded. Once all available data has been transferred to the XML engine 32 the state machine occupies its idle state.
The XSI parser module 55 represents a subset of functionality required to preprocess all data before it is written to memory and processed by the SIP and XML engines. Due to its complexity it is implemented as a separate component and further divided into several modules as shown in FIG. 11 . Two modules are used to process SIP data. A SIP data analyzer 113 processes a SIP packet on a character by character basis and determines the current state of the packet given its current values and previous values. The data processor 112 performs an arbitrary sequence of actions with the SIP data based on the state determined by the analyzer 113 . These actions were separated so the RMCS may have its SIP implementation policy altered as easily as possible with minimal changes required in design and implementation. SDP information is parsed in an analogous manner with a data analyzer 115 and data processor 114 . Data processors 116 , 117 were also implemented for Instant Messages (IM) and XML data, however no analyzers were necessary because IMs are interpreted directly by the user and the XML engine 32 performs serialization and validation.
FIG. 12 illustrates the finite state machine for the SIP data analyzer 113 . SIP data is processed character by character. From the second line onward, each line is separated into two strings separated by a colon followed by at least one space. The first line contains three strings separated only by spaces. As SIP data is analyzed character by character, the SIP data analyzer is used to determine which string or separator is currently being analyzed and to establish when the end of a line or all SIP data has been reached. The sequence of states described in FIG. 12 demonstrates the events causing transitions between various states. A syntactical error can occur at any time while SIP data is being analyzed. Therefore a global transition to an error state occurs when an unacceptable character sequence has been found. The exact sequence causing the error varies from state to state
FIG. 13 demonstrates the finite state machine of the SIP data processor 112 . It is used with the SIP data analyzer 113 to manipulate SIP data immediately after it has been analyzed. When the command to process SIP data is received the data analyzer 113 is reset and its state is transferred to the processor so the appropriate sequence of actions may take place. Valid characters for a first, second or third string are immediately saved in the appropriate locations, the end of a line causes the SIP line memory location to be updated at an external memory module and separator characters are ignored. The next character is then retrieved so the data analyzer can update its state and further processing can occur. When an error is detected all processing stops and the finite state machine occupies its idle state.
FIG. 14 demonstrates the finite state machine used to process both IM and XML payload data. Both types of data are manipulated directly by the SIP and XML modules, respectively. Therefore, the only functionality required is to collect and write the data into the appropriate memory locations. Although the functionality of the finite state machine is identical in both cases, the modules are implemented separately due to different memory locations and addressing mechanisms.
Data is read character by character until a full word of data (i.e. 32 bits from 4 characters) has been assembled. The word is written directly to the correct memory location and the address is updated. When no more data is available the unsaved data is written to memory and the state machine is idle.
This section describes the data path modules of the XSI illustrated in FIG. 5 . The packet data module is a relatively simple FIFO (first in, first out) data structure used to write SIP and payload data into the RMCS in a sequential manner. Packet data is read sequentially before it is processed by the control unit.
FIG. 15 describes the XSI Registers data path module 56 . Separate registers (Denoted R) are used to hold values for the address, writedata (data written into the RMCS from software) and readdata (data read from the RMCS to software) signals. Data inputs to the address and writedata registers are external signals connecting the RMCS to software. The input to the readdata register is multiplexed so all relevant data types can be transferred from the RMCS to software using the appropriate address. Those data types include SIP data, XML data, Instant Message and RMCS status updates. All registers have independent control signals so data can be written and reset as required.
FIG. 16 demonstrates the main components of the XSI parser data path 58 . The output of the packet data module 57 is multiplexed so data can be separated into individual characters. Each character is sent to the input of four registers (Denoted R) for storage and a comparator to determine its value. A counter is used to iterate through characters so they may be processed in a sequential manner. A separate comparator indicates when all the characters for a single word have been processed so the register data may be saved to a separate location and the counter may be reset. The address for string data is updated through a counter so the correct location for SIP data is used at all times. Separate control signals are used to manipulate all the registers and counters. No control signals are required for the comparators. Other miscellaneous registers are also used for the XSI parser data path 58 but are not shown in FIG. 16 for the sake of simplicity. Data saved in other registers includes status values and memory addresses for the XML engine 32 .
A high level description of the SIP engine 31 is provided in FIG. 31 . Most of the SIP Engine's functionality is implemented in two modules: the packet generator 312 and packet parser 316 . The SIP Packet Generator 312 is used to generate a SIP packet in its entirety. The header is written to the SIP memory component 34 while the payload is written to SDP or IM memory 35 , 36 as required. When presence information is required it is produced by the XML engine 32 described later in this document. As the packet is generated information is saved to a Generated Data module 314 when necessary so a 200 OK packet can be correctly verified when it is received. The SIP Packet Parser 316 takes a preprocessed (i.e. syntactically correct) SIP packet from memory, analyzes its contents, writes data to the Received Data Module 317 and generates a response if necessary. A response to a SIP packet will be a 200 OK message (not requiring a payload) or an error depending on the packet contents.
FIG. 32 illustrates the SIP Data Module 315 . The Data Module 315 is composed of databases for various types of information (users, field names, header types, etc), a string generator, an integer-to-ASCII converter and registers for configuration information.
FIG. 33 illustrates the finite state machine of the interface for the SIP Engine 31 . Three high level functions are provided by the SIP Engine 31 : generating a packet, parsing a packet and writing configuration data. Packet generation and configuration data manipulation require no other operations when they are complete. Parsing a packet requires the generation of a 200 OK packet as a response, unless an OK packet is being parsed.
FIG. 34 demonstrates the structure of the SIP Packet Generator 312 . It contains an interface and one finite state machine to generate every line of a SIP packet. The outputs of the finite state machines are multiplexed so the correct output can be written to the SIP character generator in the right sequence. The SIP data module 315 provides a description of the packet contents so the right sequence of state machines is enabled.
The database components in FIG. 32 have two search functions. A database may be searched for a string given a unique identifier (index) and conversely it can be searched for the index corresponding to a given string. The data path of these databases is shown in FIG. 35 . Strings are stored in the Data ROM. The string length and offset in data ROM are stored in the Length ROM and Offset ROM components of the data path. Various counters, registers and comparators are used to methodically search data as required. The status of the most recent search is saved in a register after an operation is complete.
The data base control unit is illustrated in FIG. 36 . Basic states are used to write a search index, search string or reset the search string before a major search is performed. When an index-based search is performed, the necessary values from Length and Offset ROM are read and saved before Data ROM is accessed. Once the Data ROM component has been read the control unit occupies its idle state. This operation must be performed until the entire string has been read. When the last part of the string is read, an index-based search will not produce further data until the index has been reset.
When a string-base search is performed the necessary counters are reset before data from all ROM and RAM modules are read. The length and offset values are saved before a word of data is read from the Search String RAM component of the data path. Strings are compared one word at a time until a match has occurred after having searched the entire search string and database entry. If these conditions have not been met a new database entry or word of data is read to continue the search as required. The string-based search terminates when the index is out of bounds, indicating that the entire database has been searched with no success.
The SIP character (abbreviated as char in the figures) generator 313 interacts directly with the SIP memory component 34 to write a SIP packet as efficiently as possible. Multiple characters are written to SIP memory as often as possible depending on the amount of data available. SIP packets are generated one thirty-two bit word at a time and the following convention is used to describe the four characters: When referring to the location of new characters the first character contains the eight most significant bits while the second, third and last characters contain decreasingly significant bits. When describing the position of the last written character (denoted by the numbers zero, one, two and three) zero refers to the character with the least significant bits while numbers one, two and three describing characters with increasingly significant bits.
The database for the SIP character generator 313 is shown in FIG. 37 . Inputs to all registers (denoted R) are multiplexed so that any combination of four characters can be written at any time. The correct combination of characters to be written is determined by the last character saved and the number of characters to be written (one, two, three or four). Data must be saved into the registers before it is written to SIP memory.
FIG. 38 demonstrates a high level description of the SIP character generator 313 control unit. Its functionality is divided into five finite state machines. One finite state machine acts as an interface while the others implement the functionality to write one, two, three or four characters of SIP data. The SIP character generator 381 interface is shown in FIG. 39 . The interface merely activates the appropriate finite state machine to generate data and waits until it is complete before occupying its idle state.
Functionality to write four characters of SIP data is illustrated in FIG. 40 . Data must be written to registers and SIP memory every time four characters are written. The sequence is determined by the last character of data. When writing three characters of SIP data only three scenarios involve writing directly to SIP memory. There is insufficient data in the data registers when writing from the first character as shown in FIG. 41 . This trend continues when writing two and one characters of SIP data as illustrated in FIG. 42 and FIG. 43 respectively. SIP memory need not be accessed when writing small amounts of data from the first, second or third registers. The last character must be updated after every operation.
In the RMCS, the XML Engine 32 main task is to process the XML-based part of the transmitted/received SIP packet. A typical example of an XML-based SIP data is the SIP presence having a PIDF format. Note that PIDF stands for Presence Information Data Format and encodes presence information in XML according to IETF RFC-3863 specification. FIG. 25 shows an example of a PIDF SIP presence.
The block diagram of the XML Engine 32 is shown in FIG. 45 . There are three main processors that make up the most essential parts of the XML Engine: (1) XML Parsing Processor 451 , (2) XML Validator 453 , and (3) XML Serializing Processor 454 . Each of these processors is described below.
The architecture of the XML Parsing Processor 454 is highlighted in FIG. 46 . While an XML-based document (e.g. SIP Presence of a PIDF format) is being received, a memory controller writes the data to one port of the dual-port XML memory 450 . The other port of the memory is reserved to the XML Serializing Processor 454 to write XML-based data. Once the writing process ends, the XML Parsing Processor 451 is ready to start parsing upon the reception of a parsing command from the XSI. The memory controller reads 32 bits of XML data which are then passed to a collection of four FIFOs. Each FIFO handles 8 bits of data. A FIFO Control module identifies any XML tag that comes out of each of the four FIFOs outputs and sends its findings to two modules: the XML Parsing State Machine and the Validator. Accordingly, the XML Parsing State Machine makes its parsing state transition and sends back its decision to the FIFO Control module for synchronizing purposes. The Validator forwards the data to the Tokenizer module after it finishes its validation process. Based on the state of the XML Parsing State Machine and the data received from the Validator, the Tokenizer sends the parsed tokens to its Token writer module preparing the tokens to be written by the memory controller of the dual-port Token memory. The other port of the memory is reserved for the serialization process.
The block diagram of the XML Validator 453 is illustrated in FIG. 47 . The main component of the validator is the Content-Addressable-Memory (CAM). Before the parsing process begins, the CAM is configured through XSI with selected XML characters depending on the application for which the parsing is to be performed. For example, in the case of SIP presence, the CAM is configured with XML characters that represent a “skeleton” of the XML-based PIDF presence format. The skeleton of a PIDF document includes XML tags and presence keywords such as “<pre”, which is the first four characters of the starting XML root tag “<presence”, and “</pr” which is the first four characters of the end tag “</presence>”. The CAM includes matching logic to ensure that the received XML data conform to the skeleton configured in the CAM. If any string is matched, it will be given an ID which will be used in further processing tasks, instead of the original matched data, in order to boost the parsing performance. Similarly, a skeleton of an XML Schema can be used as well to configure the CAM in order to parse the corresponding XML Schema as a first stage, before parsing the XML document that must conform to this specific schema. The FIFO CAM IF, in FIG. 47 , is an interface module that includes the logic to seize the data coming from the outputs of the FIFOs and to pass the data to the CAM for matching. The Validator classifies the data as “valid” if successfully matched, “unmatched” if there was no hit but may still be valid, or “ignored” if the data were invalid. The Validator control decision outputs are sent to the XML Parsing State Machine, and the classified data are sent to the Tokenizer for further processing. Moreover, the Validator logic keeps track partially of the well-formedness of the XML data. The responsibility of further checking the well-formedness of the XML data, especially for the data classified as “unmatched”, is accomplished via the XML Parsing State Machine.
The XML Parsing State Machine is depicted in FIG. 48 . Starting from its initial state, the state machine makes a transition to StartPI state upon the reception of the first valid XML data event. This is the beginning of the processing instruction of an XML document. The six subsequent states ensure the well-formedness of the whole processing instruction that includes the XML version and encoding attributes according to the requirements of the PIDF specifications. A transition to the StartDelimiter state occurs on the detection of “<” character, while the detection of “>” character leads to a transition to the EndDelimiter state. The detection of a string right after the “<” allows a transition to the StartTAG state, while the presence of “/” after “<” leads to the EndTAG state. If an additional string is detected while the current state is StartTAG, a transition is made to the GetToken state in order to get the name of the attribute. Subsequently, the state machine gets to the GetValue state in order to seize the value of the attribute. The outputs of the XML Parsing State Machine are then forwarded to the Tokenizer for further processing. During the time of each state, a signal is sent to the FIFO Control module for synchronization purposes.
The Tokenizer represents the last stage of the parsing process, and performs a three-fold role. First, it processes the classified data coming from the Validator. Second, it ensures that all tokens do not violate the PIDF specification for SIP presence. Finally, it sends the parsed data in an organized fashion to the memory controller of the dual-port Token memory for final writing execution. The Tokenizer tasks are done by means of a state machine as illustrated in FIG. 49 . The first six states of the Tokenizer state machine, just coming after the initial state, make sure that the XML-based object being parsed conforms to the PIDF specifications. This is particularly referring to the “presence” keyword and the “entity” attribute that must be included. The value of this attribute represents the URL of the entity—called PRESENTITY—that is publishing its presence (FIG. 44 —3 rd line). The next state is “WAIT_TUPLE_ID” where the state machine waits until the parser's detection of a “tuple” which is a PIDF keyword. If no tuple is detected, the state machine steps to the “END_PRESENCE” state providing no notes are included. According to the PIDF specification, if a tuple exists, it must have an ID as well as a “status” element. Once the parser delivers the tuple ID value, the Tokenizer state machine makes transitions to two consecutive states to capture the ID data and send it to the token memory for writing. The next three states are used to capture the presence status “basic” element that can be typically either “open” or “closed”.
When XSI sends its command to the XML engine to generate an XML-based SIP presence, the XML engine starts the serialization process. The aim of this process is to serialize SIP presence information into XML-based PIDF format. The Token Reader module, which represents the first stage of the serialization process, is illustrated in FIG. 50 as a state machine. The main task of the Token Reader is to pick up all the SIP presence information that has been updated. The update information was originally sent by XSI to the XML engine. When the XML engine received the update information, it stored it in its token memory. The states of the Token Reader indicate the status of the reading process, using the memory controller of the token memory. The read data are then sent to the serializer for processing.
The serializer main task is to organize the sparse SIP presence data into well-formed XML according to the PIDF format. The serialization state machine is illustrated in FIG. 51 . The functionality of the serializer can be viewed as the reverse process of parsing. More specifically, XML start and end tags are added to the presence information received from the Token Reader. The transitions from a state to another are highly controlled by the status of the Token Reader. During the serialization process, the serialized data are written into the dual-port XML memory. Once the serialization process is finished, the XML engine reports the end of the process to the XSI. At its convenience, the XSI reads the XML serialized data and includes them in the corresponding SIP packet.
The RMCS is an embedded system for establishing sessions with multiple users through the Internet for multimedia VoIP or video communications. Sessions may be established with an arbitrary number of users and communication may take place using audio, video or text data. In addition to session management, basic text based communication is available through text messaging. Users may also exchange presence information with other session participants when there are changes in location or state. The RMCS can also be used to develop more sophisticated embedded applications for sophisticated multimedia communication requiring the aforementioned features.
The RMCS focuses on the areas of multimedia communications with audio, video and text-based data, and has potential to be embedded with the categories of products illustrated in FIGS. 27 and 28 . These products include: consumer devices (i.e. Cell phones, PDAs, iPods, set-top boxes, PCs, etc.) or any device that is IP enabled and can connect to a communication network; edge and proxy servers (i.e., devices that are servers that can re-route or re-distribute traffic among other network devices); gateways (i.e., devices that are network systems can perform translation or mapping between two different networks; as well as application or service servers which are usually used to host services or application for the consumer devices.
In one exemplary implementation, the RMCS is integrated directly with the motherboard so that it can interact directly with a network via the NIC to receive and send SIP and XML content as shown in FIG. 29 . This scenario allows for minimal software use and increases the consumer device performance. This configuration also allows the RMCS to interact with a sound module where a DSP can be used to handle voice calls. Significant performance improvements will be noticed on the small consumer devices like iPods, PDAs, cell phones and set-top boxes.
Highly scalable servers or gateways have multiple processors (CPUs) that are dedicated for certain functionality as shown in FIG. 30 . In this scenario, the RMCS can be part of a separate application card or module dedicated to processing SIP and XML content. In this manner, server scalability is increased through the addition of more application cards. Furthermore, in the case of gateways, application cards allow more interoperability with dissimilar networks.
Below is a partial list of further benefits that the RMCS brings and addresses:
a) Augmenting performance in the area of consumer devices b) Augmenting performance in the area of communication networking by implementing in hardware processes that are presently implemented in software packages, alleviating in this way the computational burden from the host device c) Allowing peer to peer communication on any of the peer to peer architectures d) Allowing scalability and predictability for engineering the servers and gateways. e) Improving interoperability by allowing gateways to easily connect dissimilar networks. f) Largely reducing the foot-space required for servers and gateways, and thus reducing power consumption on the network devices making the network “green”. g) Increasing the ROI as the price of purchasing gateways and servers is lower due to the usage of RMCS. h) Increasing portability by allowing multiple RMCSs to be used if necessary.
The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the invention, and all such modifications are intended to be included within the scope of the invention.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms “a”, “an” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed. | A system for multimedia communications implemented with reconfigurable technology is disclosed. The system includes: a SIP engine implemented in hardware that executes functions defined by Session Initiation Protocol (SIP); a XML engine implemented in hardware that executes functions defined by Extensible Markup Language (XML); and an interface that coordinates functions executed by the SIP engine and the XML engine. A standard set of features are provided for robust communications while permitting the addition of more features to enhance the multimedia communications experience. For example, audio and video communication, instant messaging and presence can be provided by the system while P2P and IP Multimedia Systems (IMS) can be provided through expansion. Reconfigurable technology allows the system to achieve optimal performance in performing various tasks. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to clamping sets and more particularly, to a clamping set for transmitting torque and/or axial forces.
2. Discussion of the Related Art
German Offenlegungsschrift 3,444,608 discloses a clamping set similar to that of the present invention. According to this reference, a thread is made on the thin-walled end of an inner taper ring, and a screw ring, which has a radially outwardly projecting peripheral collar, grips behind a radially inwardly projecting peripheral collar of the outer taper ring. The outer taper ring is slightly extended radially and elastically in order to facilitate engagement. When the clamping set is fastened, the outer taper ring, with its end face bearing against the screw ring, is pressed up onto the inner taper ring toward the thick-walled end thereof. During disengagement, an undercut portion is used, which is located at the peripheral collars of the screw ring and the outer taper ring.
A peripheral collar which is brought into engagement on this undercut while one of the taper rings extends elastically can only have a small height. Accordingly, the tensile force which can be applied through such a peripheral collar is limited. The generall small step tends to deform under high surface pressures. Further, at self-locking taper angles, which are usually necessary to produce high clamping forces, the release forces are virtually as large as the clamping forces. Therefore, the clamping set disclosed in German Offenlegungsschrift 3,444,608 is suitable only for limited torque applications.
Moreover, a disadvantage of this conventional clamping set is that the screw ring is essentially located in front of the front end of the outer taper ring, i.e. axially outside the taper rings, and thus increases the overall axial length of the clamping set.
European preliminary published specification 007,217 discloses a congeneric clamping set in which the arrangement of the thread relative to that of the taper surfaces is the same, but the screw ring has a cylindrical extension which reaches across the end of the outer taper ring and, with an inwardly projecting collar, engages into an outer peripheral groove in the outer taper ring. Here, too, engagement is produced under elastic deformation of at least one part of the combination, and the engagement height at the undercut is accordingly limited. The clamping set is fastened when the front end of the extension bears against a flank of the groove in the outer taper ring. As a result, when the axial pressure forces for fastening are applied, there is a risk of buckling and other deformations because the extension tends to deform when producing engagement and because of the resulting thinness of the wall of the extension.
SUMMARY OF THE INVENTION
Accordingly it is an object of the invention to provide a clamping set wherein larger clamping forces are possible.
The foregoing and additional objects are attained by providing a clamping set wherein elastic deformation of the peripheral collars is no longer necessary to produce engagement of the same. The screw ring can be pushed across the cylindrical outer peripheral surface of the outer taper ring until its inwardly projecting peripheral collar bears against the outwardly projecting peripheral collar of the outer taper ring. These can then be pushed together across the inner taper ring from its thin-walled end until the inner thread of the screw ring comes into contact with the external thread of the inner taper ring and fastening begins. The screw ring can, of course, also be pushed across the already joined inner and outer taper rings. All interacting parts can, thus, be designed to be substantially more robust, since they no longer need to be deformed to produce engagement. Accordingly, the forces which can be applied are also greater.
If the interacting taper surfaces of the inner and outer taper ring have a taper angle which is in the self-locking range, the clamping set does not release itself automatically after the screw ring has been released. On the contrary, forces opposed to the release direction have to be applied in order once again to push the outer taper ring away from the inner taper ring.
The screw ring can also be tightened to the extent to which torque can be applied by available means. The peripheral collars then bear against one another with a certain force, and a certain fastened state is achieved. However, final fastening then follows hydraulically by actuating piston/cylinder units and pulling the outer taper ring further onto the inner taper ring.
This principle can also be used to release the clamping set by piston/cylinder units which act against the component sitting on the cylindrical outer peripheral surface of the outer taper ring. In this way, a pressure force is produced which is transmitted via the screw ring to the inner taper ring and has the effect of pushing the taper rings away from one another.
The clearance is provided so that no friction occurs at the inner periphery of the inwardly projecting peripheral collar of the screw socket during tightening. Also, the screw connection permits axial adjustment of the outer component and is particularly convenient where the securing of outer components to vertical bars or columns is concerned.
In an alternative embodiment, the inner taper ring is doubled, and the remaining clamping elements are also doubled. This enables a shaft or pipe coupling to be formed, the shaft ends being inserted from the two ends into the double taper ring until the front ends face one another in the center. The two screw rings can then be tightened independently of one another.
In order to use the area of the peripheral collar of the outer taper ring to transmit radial clamping forces, beveling is provided, which leads to radial force components from the axial forces of the screw ring.
In order to ensure that the largest possible proportion of the longitudinal forces produced by the screw ring will be converted into radial clamping forces and prevent an unacceptable loss in deformation energy for overcoming the clearance, the taper rings may be provided with a longitudinal slot.
Although the invention is not restricted to self-locking taper angles, in the preferred embodiment such taper angles are provided so that the highest possible torque can be transmitted. The release forces then required can be applied either by additional screws or by screwing the screw ring itself.
When the screw ring is tightened, the inner taper ring generally does not slip so that no special means are needed for rotatably securing this part on the shaft or the inner component. However, according to an alternative embodiment, in order to be independent of the adhesion of the inner taper ring on the shaft and also to bring about a torque conversion, a turning tool supported on the outer component may be provided. When the clamping set is fastened, the torque then is applied only to forces remaining with the clamping arrangement so that slipping is no longer caused.
In another embodiment, the turning tool comprises a pinion having a pitch circle diameter which is substantially smaller than the diameter of the screw ring. If the screw ring is turned at the pinion by, for example, a wrench or a crank, a torque conversion takes place in accordance with the diameter ratio. The mating teeth for the pinion can be provided directly on the outer periphery of the screw ring or on a special tool which can be rotatably fixed on the screw ring and whose outer periphery then forms the tooth system.
The tool can generally only be slipped onto the screw ring from the side, which screw ring then has a polygonal actuating periphery onto which the tool can be placed in various angular positions. The tooth system, thus, does not need to extend over the entire periphery, but needs only to cover a circular arc corresponding to the angular difference between two different positions of the tool on the screw ring.
It is also possible to mount and support the pinion on the outer component, in which arrangement the pin can be rotatable in the bore or, when the pinion is rotatable about the pin, can sit in the bore.
Torque supports may be used if the torque limit is exceeded, that is, if the clamping set slips. Depending on the direction of rotation, these supports lead either to the release of the screw ring, in order to avoid damage to the shaft and the inner taper ring, or alternatively, to firmer tightening of the screw ring and, thus, the clamping set.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a view, partly in longitudinal section, of a first embodiment of a clamping set according to the present invention;
FIG. 2 shows a partial view from FIG. 1 with a convenient modification;
FIG. 3 shows a view as in FIG. 1 of a second embodiment of the present invention;
FIGS. 4 and 5 show views, as in FIG. 1, of further embodiments of the present invention;
FIG. 6 schematically shows the function of a turning tool;
FIG. 7 shows a partial view from the left according to FIG. 6;
FIGS. 8 and 9 show partial views corresponding to FIG. 7 of further embodiments of the turning tool; and
FIGS. 10 and 11 show views in accordance with FIGS. 7 and 6, respectively, of an embodiment with a torque support.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIG. 1, the present invention contemplates a clamping set, designated generally by the reference numeral 100, which serves firmly to clamp an outer component 3 on a shaft 1 having a cylindrical outer peripheral surface 2. The component 3 is in the form of a gear having a recess with a cylindrical inner peripheral surface 4 which is at a radial distance from the outer peripheral surface 2. The right hand end (according to FIG. 1) of the clamping set 100 reaches into the radial space between the cylindrical surfaces 2 and 4.
The clamping set 100 comprises an inner taper ring 10 which, with its cylindrical inner peripheral surface 5, rests on the cylindrical outer peripheral surface 2 of the shaft 1. The inner taper ring 10 also has a tapered outer peripheral surface 6 in the self-locking range. Adjoining the thick-walled end of the inner taper ring 10, i.e. the end situated on the left in FIG. 1, is a radially outwardly projecting peripheral margin 7 which has a thread 8 on the outer periphery thereof. Below the thread 8, withdrawal threads 9 are formed which are distributed over the periphery in the part of the peripheral margin 7 projecting radially beyond the thick-walled end of the taper surface 6. These withdrawal threads allow a fastened clamping set to be released.
Arranged on the outer taper surface 6 of the inner taper ring 10 is an outer taper ring 20 which has a tapered inner peripheral surface 11 of the same taper angle as the outer taper surface 6 and has a cylindrical outer peripheral surface 12 which bears against the inner peripheral surface 4 of the outer component 3.
Provided at the thin-walled end of the outer taper ring 20 is a radially outwardly projecting peripheral collar 13 which protrudes beyond the cylindrical outer peripheral surface 12. The bearing surface 14 of the outer peripheral surface 12, which faces the thick-walled end and is perpendicular to the axis of the shaft 1, is freely accessible to a ring which may be pushed on from the thick-walled end.
The peripheral collar 13 of the outer taper ring 20 is surrounded by a screw ring 30 which at one end has an internal thread 15 which interacts with the external thread 8 on the outer periphery of the peripheral margin 7. The inside diameter of the internal thread 15 is larger than the outside diameter of the peripheral collar 13 so that the screw ring 30 can be pushed from the right, according to FIG. 1, across the outer taper ring 20 and the internal thread 15 can pass over the peripheral collar 13.
At the other end, the screw ring 30 has a radially inwardly projecting peripheral collar 17 which grips radially behind the peripheral collar 13 on the side remote from the threads 8, 15 and bears on the bearing surface 14 of the peripheral collar 13 with a bearing surface 16 which is perpendicular to the axis of the shaft 1. The inner peripheral surface 18 of the peripheral collar 17 is cylindrical and defines a slight clearance relative to the outer peripheral surface 12 of the outer taper ring 20 in order to avoid friction therebetween.
When the clamping set 100 is assembled, the outer taper ring 20 can be pushed on to the inner taper ring 10 and the screw ring 30 can then be pushed across from the right according to FIG. 1 and brought into engagement at the threads 8, 15. The outer taper ring 20 is pulled from the left onto the inner taper ring 10 by tightening the screw ring 30, as a result of which, radial expansion of the outer taper ring 20 and, thus, fastening against the inner peripheral surface 4 takes place.
To avoid excessive losses of axial clamping force applied by the screw ring 30, the outer taper ring 20 has a continuous radial slot at one location, which is indicated by the lack of hatching, whereas the inner taper ring 10 is slotted in the area of the outer surface 6 at several locations distributed uniformly over the periphery thereof.
To release the clamping set 100 provided with self-locking taper surfaces 6, 11, withdrawal screws are screwed into the tapped withdrawal holes 9, which withdrawal screws are set in front of the end face 19, opposite the bearing surface 14, of the peripheral collar 13 of the outer taper ring 20. However, the screw ring 30, with its front end which faces the outer component 3, can also be brought to bear against this outer component 3 and release of the clamping set 100 can be effected by screwing further in this direction.
When the clamping set 100 in FIG. 1 is fastened, the outer component 3, which is secured in place on the shaft 1, tends to follow the axial displacement of the outer taper ring 20 relative to the inner taper ring 10 sitting firmly on the shaft 1. In many cases this is of no importance. However, if it is desirable for the outer component 3 to remain stationary in the axial direction of the shaft 1 during fastening of the clamping set 100, an arrangement according to FIG. 2 can be selected. Here, the outer component 3 has an extension 3' which projects radially inwardly toward the front end 21 of the inner taper ring 20 situated at the thin-walled end thereof and is supported either directly against the end face 21 or against the end face 21 via an intermediate ring 22. When the outer taper ring 20 according to FIG. 2 is displaced to the left, the outer component 3 is no longer carried along relative to the shaft 1.
In order to facilitate application to the screw ring 30 of the torque necessary for fastening, axially parallel grooves 23 are provided over the periphery of the screw ring 30, which grooves are engageable by an appropriate turning tool.
In the clamping set 200 in FIG. 3, parts which correspond in function are identified by the same reference numerals.
The difference between the clamping set 200 and the clamping set 100 is that, in the clamping set 200, a plurality of small piston/cylinder units 24 are distributed over the periphery of the bearing surface 16 and act parallel to the axis of the shaft 1, of the peripheral collar 17 of the screw ring 30. The pistons 25 of the piston/cylinder units 24 are advanced out of the associated cylinder bore 26 in the peripheral collar 17 toward the bearing surface 14 of the peripheral collar 13 when a hydraulic pressure medium is introduced via the connecting passages 27. The outer taper ring 20 is thereby drawn up to the left according to FIG. 3 onto the inner taper ring 10. The force is transmitted to the inner taper ring 10 via the screw ring 30 and the threads 8, 15. The pistons 25, in retracted position, may protrude slightly from the bearing surface 16, or may be completely concealed beneath the bearing surface 16.
Thus, according to the embodiment of FIG. 3, the screw ring 30 can be tightened manually until it is fastened to a certain extent, whereupon further fastening takes place hydraulically through the pistons 25.
The clamping set 200 can be released by similar piston/cylinder units 28, which, however, act on the other side of screw ring 30 and bear against the outer component 3 clamped in place on the outer taper ring 20. When pressure is exerted against the left hand side (according to FIG. 3) of the outer component 3, slipping will occur at the taper surfaces 6, 11 and the clamping set 200 will thus be released.
At the beginning of fastening, when the inner taper ring 10 is not yet firmly seated on the shaft 1, bores 29 in the peripheral margin 7 may be used with a suitable turning tool to counteract the torque applied to the screw ring 30.
In FIG. 3, as an alternative, broken lines indicate that the recess 4, instead of being provided with a smooth, cylindrical inner peripheral surface, can also be provided with an internal thread 31 which is screwed onto an external thread 32 on the right hand end, (as shown in FIG. 3) i.e., the thick-walled end, of the outer taper ring 20. The outer component 3 can be axially adjusted within a certain area. When the clamping set 200 is fastened, the outer component 3 is secured in position on the outer taper ring 20.
Referring now to FIG. 4, a clamping set 300 is shown which is designed in mirror image relative to a center plane 33 at right angles to the axis of the shaft 1. The double taper ring 10' consists of two inner taper rings 10 in accordance with FIG. 1 which are integrally connected to one another along their peripheral margins 7. The remaining elements are also doubled. The clamping set 300 serves as a shaft coupling. Two shafts 1 engage end-to-end from opposite sides into the double taper ring 10' and are separately connected to the double taper ring 10' by actuating the clamping rings 30, 30. In this case, the "outer components 3" are thick-walled clamping rings which merely apply the peripheral stress for producing the needed radial clamping force.
In this embodiment, the bearing surfaces 14, 16 of the outer taper ring 20 and the screw ring 30, respectively, are not perpendicular to the axis of the shaft, as in the embodiment in FIGS. 1 and 3, but instead are inclined, i.e. tapered.
In the embodiment shown in FIG. 4, the angle 8 of the bearing surfaces relative to the axis of the shaft 1 is about 45°. Consequently, a certain radial contact pressure is also applied to the outer taper ring 20 in the area of the peripheral collar 13, thereby contributing to the torque which can be transmitted.
FIG. 5 shows an exemplary embodiment in which the outer component 3 is designed as a coupling flange which can be fixed in the end area of a shaft 1 by means of the clamping set 400. In the clamping set 400, the bearing surfaces 14, 16 also have the inclination mentioned with reference to FIG. 4.
A common feature of the clamping sets 300, 400 in FIGS. 4 and 5 is that the screw rings 30 are of a hexagonal configuration on the outer periphery, like a nut, in order to be engaged by a turning tool.
To tighten the screw ring 30, a special turning tool can also be provided according to FIGS. 6 to 9. In the embodiment in FIGS. 6 and 7, the screw ring 30, has a tooth system 35 on its outer periphery with which the tooth system of a pinion 40 meshes. The pinion 40 with a pin 41 is rotatably mounted in an axially parallel bore 42 defined in the outer component 3. At the other end of the pinion is an extension 43 with flats on which a crank or a wrench can act. In the shown embodiment, the diameter of the pitch circle of the tooth system of the pinion 40 is only about one quarter of the pitch circle of the tooth system 35 so that, at a certain torque for turning the pinion 40, about four times the torque is applied to the screw ring 30.
An alternative embodiment is shown in FIG. 8. A tool 50 is provided which has a wrench jaw 51 which fits onto an outer hexagon 52 of the screw ring 30. On the side remote from the jaw 51, the tool 50 has a tooth system 53 with which the tooth system of the pinion 40 meshes. When the pinion 40 is turned at the hexagonal socket 44, the screw ring 30 is also turned, as in the embodiment in FIGS. 6 and 7. The advantage of this embodiment is that the tool 50 can be slipped from the side onto the screw ring 30 and therefore no open end of the shaft 1 is required. Also, only one tooth system 53 need be provided, namely on the tool 50, whereas in the embodiment in FIGS. 6 and 7 every individual screw ring requires a tooth system.
When, during tightening of the screw ring 30 according to FIG. 8, the pinion has arrived at the end of the tooth system 53 which extends only over an angle of about 90°, the tool 50 is accordingly transposed on the screw ring 30.
The tool 60 in FIG. 9 differs from the tool 50 in that, instead of the external tooth system 53, a circular recess 61 having a tooth system 63 made on the radially outer boundary is provided, with which tooth system the pinion 40 meshes from the inside. The circular recess 61 of the tool 60 is of such a width that the pinion 40 meshes with the outer tooth system 63 and, due to the inner boundary of the circular recess 61, cannot jump out.
FIGS. 10 and 11 show a torque support 70 which is attached to the fully fastened clamping set 6, 7, 30. In the shown embodiment, the screw ring 30 has an external hexagon 52, and the torque support 70 is designed as a plate having a wrench jaw 51 which fits onto the external hexagon 52. A perforation 71 is provided at right angles to the plate plane, through which a screw 72 into a tapped hole 73 in the outer component 3. The torque support 70 thus rotatably fixes the screw ring 30 to the outer component 3. More importantly, however, if the torque limit of the clamping set is exceeded, that is, if the clamping set starts to slip on the shaft 1, the outer component carries the torque support 70 and thus the screw ring 30 along with it in the direction of the torque. As a result, depending on the arrangement of the threads, the taper rings 6, 7 either loosen or tighten to a greater extent. Loosening can be desired in order to effect immediate relief in the event of excessive torque and to prevent the interacting cylindrical surfaces of the shaft 1 and the taper ring 7 from being ruined. On the other hand, tightening can be desired in order to absorb the increased torque by immediate tightening of the clamping set to a greater extent. In the same direction of rotation, the effect of the torque support 70 can be changed by the clamping set being turned around and by the torque support 70 being attached on the other axial side of the outer component 3.
A torque support can also be realized by leaving the tool 50 (FIG. 8, for example) on the screw ring 30 after tightening and connected to the outer component 3 in such a way as to be rotatably fixed by means of a screw which is attached outside the wrench jaw 51 and passes through the bore 71' (indicated by a broken line).
The thickness of the torque support, however, should not be too small so that the screw ring can also be reliably gripped in the longitudinal direction at different positions.
It should become obvious to those skilled in the art that the present invention is not limited to the preferred embodiments shown and described. | A clamping set is provided wherein elastic deformation of the peripheral collars is no longer necessary to produce engagement of the same. The screw ring can be pushed across the cylindrical outer peripheral surface of the outer taper ring until its inwardly projecting peripheral collar bears against the outwardly projecting peripheral collar of the outer taper ring. These can then be pushed together across the inner taper ring from its thin-walled end until the inner thread of the screw ring comes into contact with the external thread of the inner taper ring and fastening begins. All interacting parts can, thus, be designed to be substantially stronger, since they no longer need to be deformed to produce engagement. Accordingly, the forces which can be applied are also greater. | 8 |
BACKGROUND OF THE INVENTION
The present invention refers to a device in hearing aids intended for interconnecting an implant acting as a first coupling member and being anchored in the skull bone of a person with impaired hearing and a second coupling part interconnectable therewith and being provided on a vibration exciting apparatus, whereby said coupling parts are constituted by a substantially cup-shaped female part and a male part, which is insertable therein under mutual flexing.
For this purpose there are earlier known different embodiments of interconnection devices. Such skull bone anchored implants are often made as a titanium fixture, in which a metallic, first coupling part is arrestable. To this first coupling part, which thus is arrestable in the fixture, is connectable a second coupling part cooperating therewith and being connected to the vibration exciting part of the hearing aid.
The second coupling part has also been made in metal and in order to provide a sufficiently stable interconnection of the two coupling parts and a safely (distortion free) signal transferring contact between the metal surfaces engaging each other, it has been necessary to machine these metallic coupling parts to a rather high accuracy, which in view of the metallic materials, which can be used, has been connected to rather high costs.
At earlier embodiments the coupling parts often have been made as a female coupling part and a male coupling part, wherein the male part usually has been made as an at least partially ball-shaped body, whereas the female part has been constituted by a cup-shaped body, the wall of which has been made sufficiently elastic to permit the male part to be snapped-in, in that the edge portion has been made sufficiently thin, or more often, has been provided with axially extending slots. In another embodiment the coupling parts have been designed as a bayonet coupling.
In all these cases the male part has been designed as a form stiff body, whereas the female part has been designed to be able to flex, or has been provided with flexing means for making it possible to effect interconnection and disconnection of the coupling parts manually.
At skin penetrating implants it is desirable that the side (the outer side) of the implant facing the soft tissue is kept as clean as possible. An obvious drawback with a skin penetrating implant where the male part is fitted to the patient, thus is that the female part of the hearing aid, which is often coated with dirt (germs), etcetera, transfers these to the outer side of the implant and the risk for spreading to the skin penetration area is obvious. As the skin thickness at the penetration area varies from one patient to another and at certain patients grows with time, there is always the risk that direct contact between the female part and the skin may occur, which with the highest probability results in skin irritation/skin infection. In order to minimize this risk it is required a male part, which with margin projects out from the skin, which in turn means an increased risk for outer and unwanted physical influence of the implant.
Another drawback at the coupling device comprising two cooperating metallic parts is that at use of external, electrically driven equipment, for patient safety reasons specialized equipment must be used, e.g. in form of protective transformer in order not to risk that the bearer is subjected to harmful current levels via the hearing aid, and the electrically conductive coupling device. Today this is required for permitting plugging in of a tape recorder/WALKMAN.
SUMMARY OF THE INVENTION
The purpose of the present invention is to provide a device of the type described in the introduction, by which the above mentioned drawbacks are eliminated, and this has been obtained by the features defined in the accompanying claims.
Hereinafter the invention will be further described with reference to an embodiment shown in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows in a transversal section a coupling device according to the invention in coupling position.
FIG. 2 is an illustration of a skull bone implanted coupling device according to the invention with a hearing aid connected thereto, with coupling device and skull bone shown in cross section.
FIG. 3 shows in larger scale and in cross section an alternative embodiment of the second part of the coupling device shown in FIG. 1.
FIG. 4 is a cross section in bigger scale of the first coupling part of the coupling device shown in FIG. 1, and
FIG. 5 shows in a view corresponding to FIG. 3 a further alternative of the second coupling part forming part of the coupling device according to the invention.
FIGS. 6-8 show schematically in end view the second coupling part and different types of recesses formed therein for increasing its flexibility.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows in cross section a coupling device 1 according to the invention, which incorporates a flange fixture 2 formed as an implant, intended to be inserted by an operation, preferably in the skull bone of the bearer of the hearing aid. The flange fixture or the implant 2 is manufactured from metal and preferably from titanium and it is provided with a substantially cylindrical attachment part 3, which adjacent one of its ends is equipped with a radial flange 4, arranged in implanted position to engage with one of its annular surfaces against the skull bone. In the cylindrical portion of the flange fixture there is provided a threaded blind hole 5, which is adapted and intended to receive a spacer screw 6 which is arrestable in thread engagement therewith. The spacer screw 6 is arranged to anchor to the flange fixture 2 a first coupling part 7, in form of substantially cup-shaped male part made from metal, preferably titanium, and having a centrum through-bore 8, through which the stem of the spacer screw 6 extends, and which with the edge of the screw head engaging an annular seat 9 around the bore 8 creates an anchoring of the first coupling part 7 to the flange fixture 2. On the side of the first coupling part 7 turned away from the flange fixture 2, this part is equipped with an axial outwardly tapering annular side wall 10 at a distance from the annular seat 9, with an annular external end surface 10a and an inwardly projecting concentric annular bead 11 adjacent the external end surface 10a.
The head of the screw 6 thus protrudes upwards inside the space formed by the side wall 10 in the first coupling part, whereby the head of the screw does not completely fill out this space thus that a annular space is formed. In the area nearest to base of the side wall 10 this space is filled to a substantial part of the lower portion of a cap-formed covering washer 12 arranged over the screw head and which in its upper potion however has smaller diameter and there leaves an annular slot 13, which extends from the outer end of the conically flaring side wall 10 and beyond its inwardly directed annular bead 11. As the first coupling part 7 is designed as a rigid metal structure made from a high-quality material it has substantially no resiliency whatsoever, not even at the outer end of its conically flaring side wall 10. The covering washer 12 is preferably manufactured from plastic material, and is used mainly for aesthetic reasons.
The coupling device according to the invention also incorporates a second coupling part 14, which, as can be seen from FIG. 2, in a proper, not further shown manner with a shaft portion 15 is connected to a hearing apparatus 20, of a type known per se, and in FIG. 2 is also shown how the implant 2 penetrates the skin 21 and is anchored in the skull bone 22.
This second coupling part 14 is made as a male part with a recess 16 arranged in the forward portion thereof and concentric therewith, and being of a size, permitting that the recess is brought down over and with clearance encloses the screw head or the covering washer 12 in the upper portion thereof.
The second coupling part or the male part 14 at its recess-provided end is equipped with a circumferential groove 17 with an engagement surface 17a formed at the free edge and adapted to form a seat for the annular bead 11 when the male part 14 is introduced into the annular slot 13 in the first coupling part or the female part 7. The male part 14 is also provided with a radial, circumferential flange 18, which when the annular bead 11 is situated against the engagement surface 17a in the groove 17 in the male part on one hand and on the other hand engages the end surface 10a on the female part 7. Hereby the annular engagement surfaces between the end surface 10a and the flange 18 and also between the edge of the annular bead 11 and the engagement surface 17a, form signal transferring surfaces between the first 7 and second 14 parts of the coupling device.
The portion of the second coupling part--the male part 14 --having the inner recess 16, is made resilient in order to permit simple snap-in introduction of the male part 14 into the annular slot 13 in the female part 7.
This resiliency can be obtained in different manners, e.g. in that the male part is provided with axial slots 19 in the material around the recess 16, and/or that the entire male part 14 is made in an elastic material, e.g. plastic. It hereby is essential that the dimensioning and the choice of material will provide sufficient axial stiffness.
As the male part 14 may be manufactured from plastic material in a moulding tool the manufacturing cost will be rather low.
By choosing an elastic material for the male part 14, it thus is possible, with or without slots, to obtain a sufficient resiliency for allowing an easy snapping-in of the male part 14 into the female part 7, thus that a satisfactory signal transferring contact is obtained in the coupling. Surprisingly this also has proven itself to be achievable also when the male part is made of plastic material.
By making the male part from an electrically non-conducting material, such as plastic material it is further achieved that the risk for transfer of electric current to the skull bone from external auxiliary apparatuses, such as tape recorders and the like is eliminated. This has not been possible to achieve earlier with both coupling parts made from an electrically conductive material.
FIG. 3 shows in bigger scale and in cross section the second coupling part 14--the male part--in order to give a clear picture of its design in separate position.
In FIG. 4 is shown in bigger scale the implant 2 and the first coupling part 7 in accordance with FIG. 1.
FIG. 5 shows in a view corresponding to FIG. 3 a further alternative embodiment of the second coupling part 14'--the male part--in this case made from an elastically resilient material, such as plastics, and for this reason the male part 14' in this case is made without axial slots.
FIG. 6 shows in a schematical end view a variant of the second coupling part, i.e. the male part 14a with resiliency increasing recesses in the form of a T-shaped slot or notch 23.
FIG. 7 is a view corresponding to FIG. 6 with a cross-formed recess 24 provided in the male part 14b.
FIG. 8 finally illustrates in a view corresponding to FIGS. 6 and 7 how a male part 14c has been equipped with a recess 25 substantially corresponding to the recess according to FIG. 3, i.e. with a centrally disposed recess and with radial slots arranged through the annular wall.
All these schematically illustrated recesses, like several other not shown alternatives give a good radial resiliency to the male part.
By using an electrically non-conductive material, such as plastics, it is also achieved that the hearing aid can be connected to external electric aids without need of connecting protective transformer or the like.
Due to the design according to the invention described hereinbefore it is achieved that the patient part of the implant consists of a cylindrical, bored titanium socket having an continuous external surface, within which the radially resilient male part engages.
The invention is not limited to the embodiments illustrated in the accompanying drawings and described in connection thereto, but modifications and variations are possible within the scope of the accompanying claims. | A device for interconnecting an implant (2) anchored in the skull bone of a person with impaired hearing, which acts as or supports a first coupling part (7) and a second coupling part (14) interconnectable therewith and connected to a vibration exciting apparatus, whereby said coupling parts are constituted by a substantially cup-shaped female part (7) and a male part (14), which is insertable therein under mutual flexing, the female part (7) being designed as a rigid cup-shaped seat, whereas the male part (14) is designed to be resilient in radial direction in order to permit a snap-in introduction into the female part (7). | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a process for forming a semiconductor device on a transparent dielectric substrate such as a sapphire substrate, more particularly to the formation of a reflective film on the transparent dielectric substrate to enable the substrate to be recognized optically.
[0003] 2. Description of the Related Art
[0004] Semiconductor integrated circuits formed in silicon films grown on sapphire substrates are advantageous for applications in environments in which radiation poses a hazard. Such silicon-on-sapphire (SOS) integrated circuits are generally formed by use of conventional fabrication equipment of the type that creates semiconductor integrated circuits in semiconductor substrates. In conventional fabrication processes, the fabrication equipment often uses optical sensors to detect the position of the semiconductor substrate. The position of a sapphire substrate cannot be detected in this way because sapphire is transparent: light passes straight through the substrate instead of being reflected back to the sensor. One known solution to this problem is to coat the sapphire substrate with a light-reflecting film.
[0005] Japanese Patent Application Publication No. 7-283383 and the parent U.S. Pat. No. 5,877,094, for example, describe a sapphire substrate coated on its backside with a layer of polycrystalline silicon (polysilicon) at least about two micrometers (2 μm) thick, which reflects light and can be detected optically. Phosphorous ions are also implanted into selected regions of the polysilicon film to form conductive doped regions that can be detected electrically.
[0006] One problem with this substrate is that forming a polysilicon layer at least about 2 μm thick is a time-consuming and therefore expensive process. Moreover, in reflow and other subsequent heating steps, the large difference in thermal expansion coefficients between sapphire and polysilicon may cause the sapphire substrate to warp. Such warping interferes with the fabrication process and may lead to the formation of cracks in the sapphire substrate, particularly if the sapphire substrate is thin, which is the current trend.
[0007] Japanese Patent Application Publication No. 11-220114 describes an SOS substrate having an optically reflecting polysilicon coating 0.5 μm to 3.0 μm thick on its backside. A pattern of cuts is formed in the reflective coating so that the difference in thermal expansion coefficients does not cause the substrate to warp or crack. The thickness of the polysilicon coating must be at least 0.5 μm because a thinner film would lack the necessary reflectivity, as pointed out in paragraph 0009 of the above disclosure.
[0008] Due to the trend toward thinner sapphire substrates, there is a continuing need for still thinner reflective films.
SUMMARY OF THE INVENTION
[0009] An object of the present invention is accordingly to provide a semiconductor device having a transparent dielectric substrate with a reflective coating film that can be thinner than 0.5 μm and still provide adequate reflectivity for optical detection.
[0010] The term ‘semiconductor device’ as used herein refers to an electronic device such as a semiconductor integrated circuit chip or to a wafer from which such electronic devices may be manufactured.
[0011] The invented semiconductor device has a dielectric substrate transparent to light, a first film disposed on the back surface of the dielectric substrate, a second film disposed on the first film, and a third film disposed on the second film. The first film and the second film have different reflective characteristics, enabling one film to reflect light not reflected by the other film.
[0012] The first, second, and third films combine to form a triple-layer light-reflecting film that has a higher reflectance than the conventional single-layer light-reflecting film and can be made thinner than the conventional single-layer light-reflecting film.
[0013] One method of fabricating the invented semiconductor device includes:
[0014] preparing a dielectric substrate that is transparent to light and has a front surface and a back surface;
[0015] forming a first film on the back surface of the dielectric substrate;
[0016] forming a second film on the first film;
[0017] heating the second film; and
[0018] forming a third film on the heated second film.
[0019] Another method of fabricating the invented semiconductor device includes:
[0020] preparing a dielectric substrate that is transparent to light and has a front surface and a back surface;
[0021] forming a first film on the back surface of the dielectric substrate;
[0022] forming a second film on the first film by heating the first film; and
[0023] forming a third film on the second film.
[0024] In one aspect of both methods, the second film has a lower refractive index than the first and third films.
[0025] In another aspect of both methods, the first, second, and third films have an aggregate thickness less than 0.5 μm.
[0026] In another aspect of both methods, the first film includes polysilicon, the second film includes silicon oxide, and the third film includes polysilicon.
[0027] In a further aspect of the preceding aspect, the first film is 42 nanometers thick, the second film is 110 nanometers thick, and the third film is 42 nanometers thick.
[0028] In another aspect of both methods, the dielectric substrate includes sapphire.
[0029] Another aspect of both methods also includes exposing the front surface of the dielectric substrate.
[0030] Another aspect of both methods also includes forming a fourth film on the front surface of the dielectric substrate.
[0031] The fourth film may include polysilicon.
[0032] Another aspect of both methods also includes forming a fifth film on the fourth film.
[0033] The fifth film may include silicon oxide.
[0034] In another aspect of both methods the dielectric substrate has side surfaces; this aspect also includes forming a sixth film covering the side surfaces of the dielectric substrate.
[0035] The sixth film may include polysilicon and silicon oxide.
[0036] When the second film includes silicon oxide (SiO 2 ), the above fabrication processes improve the crystalline structure of the silicon oxide. An attendant advantage is that in further fabrication steps involving etching by hydrofluoric acid, there are fewer crystal lattice defects through which the hydrofluoric acid can invade the silicon oxide film.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] In the attached drawings:
[0038] FIG. 1 is a sectional view of a semiconductor device according to the present invention;
[0039] FIG. 2 is a graph indicating the reflectance of a wafer with a triple-layer reflective coating as a function of wavelength;
[0040] FIG. 3 is a graph indicating the reflectance of a wafer with another triple-layer reflective coating as a function of wavelength;
[0041] FIG. 4 is a more detailed sectional view showing an example of the structure of the substrate in FIG. 1 ;
[0042] FIG. 5 is a more detailed sectional view showing another example of the structure of the substrate in FIG. 1 ;
[0043] FIG. 6 is a more detailed sectional view showing yet another example of the structure of the substrate in FIG. 1 ;
[0044] FIGS. 7 to 11 illustrate steps in a fabrication process for the semiconductor device in FIGS. 1 and 6 ; and
[0045] FIGS. 12 to 16 illustrate steps in another fabrication process for the semiconductor device in FIGS. 1 and 6 .
DETAILED DESCRIPTION OF THE INVENTION
[0046] Embodiments of the invention will now be described with reference to the attached drawings, in which like elements are indicated by like reference characters.
FIRST EMBODIMENT
[0047] Referring to FIG. 1 , the first embodiment is a semiconductor device or wafer having a silicon-on-sapphire (SOS) substrate 101 , the major surfaces of which are a front surface and a back surface 101 a . The back surface 101 a and side surfaces 101 b of the SOS substrate 101 are covered with reflective films 102 , 103 , 104 to permit optical sensing by wafer sensing light. The second reflective film 103 has a lower refractive index than the first and third reflective films 102 , 104 . The first reflective film 102 is, for example, a polysilicon film formed on the back and side surfaces of the SOS substrate 101 . The second reflective film 103 is, for example, a silicon oxide film formed on the first reflective film 102 . The third reflective film 104 is, for example, a polysilicon film formed on the second reflective film 103 .
[0048] Next the determination of the film thicknesses of the reflective films will be described.
[0049] Let the refractive index of the space through which the wafer sensing light travels before entering the SOS substrate 101 be n 0 , the refractive index of the sensed material be n x , and the refractive index of the space on the far side of the sensed material, through which the light travels if it passes through the sensed material, be n s . In order for the sensed material to have high reflectance, its refractive index n x must be the higher than the space indices n 0 and n s .
[0050] If the refractive index of the sensed material is higher than the space indices and the sensed material comprises a triple-layer film consisting of a first reflective film 102 , second reflective film 103 , and third reflective film 104 , a reflectance close to unity can be achieved for the triple-layer film as a whole if the refractive index of the second reflective film 103 is lower than the refractive index of the first reflective film 102 and third reflective film 104 .
[0051] Let the wavelength of the wafer sensing light be λ and the refractive indices of the first reflective film 102 , second reflective film 103 , and third reflective film 104 be n 1 , n 2 and n 3 , respectively. If the wafer sensing light impinges normal (at a 90° angle) to the front surface of the SOS substrate 101 , then to achieve still higher reflectance, the thickness d of each film, the wavelength λ of the wafer sensing light, and the refractive index n of the film must satisfy the following equation (1) for some integer N:
( 2 N + 1 ) π 2 = 2 π n d λ ( 1 )
[0052] A reflectance as close as possible to unity is achieved when the thicknesses and refractive indices n 1 , n 2 and n 3 of all three films satisfy this equation (1) and the refractive indices also satisfy the relationship mentioned above (n 2 <n 1 and n 2 <n 3 ).
[0053] If the wavelength of the wafer sensing light is six hundred forty nanometers (λ=640 nm) and the first and third reflective films 102 , 104 are polysilicon films, their refractive indices are both 3.80 (n 1 =n 3 =3.80). If the second reflective film 103 is a silicon oxide film, its refractive index at this wavelength is 1.45 (n 2 =1.45). In order to achieve the minimum film thickness, N should be equal to zero (N=0). The thickness of the first and third reflective films 102 , 104 can then be calculated from the above equation (1) as d=42.1 nm, while the film thickness of the second reflective film 103 can be calculated as d=109.8 nm. If the first and third reflective films 102 , 104 are polysilicon films and the second reflective film 103 is a silicon nitride (SiN) film, then its refractive index is 2.02 (n 2 =2.02), the film thickness of the first and third reflective films 102 , 104 is still d=42.1, and the thickness of the second reflective film 103 is d=79.2 nm from equation (1) with N=0.
[0054] The reflectance of the wafer as a whole to the wafer sensing light can be calculated from the following equation (2), where as above, no is the refractive index of the space through which the wafer sensing light travels before entering the SOS substrate 101 , n 1 , n 2 , and n 3 , are the refractive indices of the first, second, and third reflective films 102 , 103 , 104 , and n s is the refractive index of the space behind the third reflective film 104 , assuming that the wafer sensing light impinges onto the front surface of the semiconductor substrate at a normal
R = ( n 0 n s n 2 2 - n 1 2 n 3 2 n 0 n s n 2 2 + n 1 2 n 3 2 ) 2 ( 2 )
[0055] In the above example, as the dielectric substrate is transparent, its refractive index may be set equal to the refractive index (n 0 ) of the space through which the wafer sensing light travels before entering the SOS substrate 101 . Equation (2) indicates that in order to achieve higher reflectance than that can be achieved by a single-layer light-reflecting film made from a high-index material, the first and third reflective films 102 , 104 should be made from a material with a comparatively high refractive index, while the second reflective film 103 should be made from a material with a relatively low refractive index.
[0056] The refractive index n of each material varies according to the wavelength λ of the wafer sensing light, so from equation (2), the reflectance R of the wafer as a whole also varies according to the wavelength. A plot of the reflectance R of the wafer as a whole versus the wavelength λ of the wafer sensing light is shown in FIG. 2 for the case in which the first and third reflective films 102 , 104 are polysilicon films, and the second reflective film 103 is a silicon oxide film.
[0057] If the wafer must have a reflectance R not less than 0.8 in order to be recognized by the wafer sensing light, the wavelength λ of the sensing light should be about 640 nm±100 nm. The corresponding thickness of the first and third reflective films 102 , 104 can be calculated from equation (1) as d=42.1±6.6 nm (hereinafter referred to as about 42 nm). This can be taken as the allowable thickness range of the first and third reflective films 102 , 104 . The thickness of the second reflective film 103 can be calculated from equation (1) as d=109.8±17.2 nm (hereinafter referred to as about 110 nm). This can be taken as the allowable thickness range of the second reflective film 103 .
[0058] A plot of the reflectance R of the wafer as a whole versus the wavelength λ of the wafer sensing light is shown in FIG. 3 for the case in which the first and third reflective films 102 , 104 are polysilicon films, and the second reflective film 103 is a silicon nitride film. If the requirement for recognition of the wafer is relaxed to a reflectance R not less than 0.7, the wavelength λ of the sensing light should again be about 640 nm±100 nm. The thickness of the first and third reflective films 102 , 104 can again be calculated as d=42.1±6.6 nm (about 42 nm) from equation (1), the thickness of the second reflective film 103 can be calculated as d=79.2±12.4 nm (hereinafter referred to as about 80 nm), and these can the taken as the allowable thickness ranges of the respective films.
[0059] Next, the structure of the SOS substrate 101 will be described. The SOS substrate 101 is fabricated by depositing various films on a sapphire substrate. In this embodiment, the SOS substrate 101 may be of any one of the following three types.
[0060] The first type of SOS substrate 101 , shown in FIG. 4 , comprises a sapphire substrate 105 (dielectric substrate) and a device formation film 106 (a fourth film) formed on the sapphire substrate 105 . The sapphire substrate 105 in FIG. 4 is six hundred micrometers (600 μm) thick; the device formation film 106 formed on the sapphire substrate 105 is 100 nm thick. The device formation film 106 can be made from silicon, which is the material from which transistors are typically made.
[0061] The second type of SOS substrate 101 , shown in FIG. 5 , comprises a sapphire substrate 105 , a device formation film 106 formed on the sapphire substrate 105 , and a silicon oxide film 107 (a fifth film) formed on the device formation film 106 . The sapphire substrate 105 in FIG. 5 is 600 μm thick, the device formation film 106 formed on the sapphire substrate 105 is 100 nm thick, and the silicon oxide film 107 formed on the device formation film 106 is 10 nm thick. The device formation film 106 may again be made of silicon. The SOS substrate 101 shown in FIG. 5 has the advantage that the silicon oxide film 107 protects the device formation film 106 during wafer processing steps performed prior to the formation of circuit elements, resulting in less variation in the electrical characteristics of the circuit elements.
[0062] The third type of SOS substrate 101 , shown in FIG. 6 comprises the sapphire substrate 105 , device formation film 106 , and silicon oxide film 107 described above, and a protective film 108 (a sixth film) covering the side surfaces of the device formation film 106 and silicon oxide film 107 and the back surface of the sapphire substrate 105 . The sapphire substrate 105 in FIG. 6 is 600 μm thick, the device formation film 106 is 100 nm thick, the silicon oxide film 107 is 10 nm thick, and the protective film 108 is 700 nm thick. The device formation film 106 may again be made of silicon. The protective film 108 may be made from a combination of a silicon nitride film and polysilicon. The SOS substrate 101 in FIG. 6 has the same advantages as the SOS substrate 101 in FIG. 5 , and the additional advantage that the sides of the device formation film 106 can be protected from invasion by hydrofluoric acid, thus preventing flaking of the device formation film 106 and silicon oxide film 107 . Furthermore, this structure can prevent unwanted diffusion during doping steps in the formation of circuit elements.
[0063] Any one of the three types of SOS substrate 101 described in FIGS. 4 to 6 can be used, according to the needs of the particular application.
[0064] Because of its triple-layer structure, the light-reflecting film of a semiconductor device according to the first embodiment of the invention can be thinner than a conventional single-layer light-reflecting film. Semiconductor chips can be fabricated by coating part or all of a wafer with a light-reflecting film according to the invention, forming circuit elements on the semiconductor substrate and interconnecting them by using conventional semiconductor fabrication equipment, and then dicing the wafer into individual chips. If the wafer sensors in the fabrication equipment illuminate only selected parts of the wafer, the triple-layer light-reflecting film only has to cover the selected parts. For example, the triple-layer light-reflecting film may cover only the peripheral parts of the wafer. Then after the wafer is divided into chips, none of the chips includes any portion of the light-reflecting film, so the thickness of the semiconductor chips can be further reduced.
[0065] Next, a process for fabricating a semiconductor device of the above type will be described with reference to FIGS. 7 to 11 .
[0066] Among the SOS substrates shown in FIGS. 4 to 6 , a fabrication process using the SOS substrate shown in the FIG. 6 will be described. For numerological consistency, the component parts are numbered as shown in FIG. 7 . The SOS substrate 201 in FIG. 7 comprises a transparent dielectric sapphire substrate 205 , a device formation film 206 formed on the sapphire substrate 205 as a silicon film, a silicon oxide film 207 formed on the device formation film 206 , and a protective film 208 formed on side surfaces of the sapphire substrate 205 , the device formation film 206 and the silicon oxide film 207 , and the back surface of the sapphire substrate 205 .
[0067] Next, the fabrication process of the SOS substrate 201 will be summarized. First, a sapphire substrate 205 is obtained and a silicon film is formed thereon by chemical vapor deposition (CVD). Next, the part of the silicon film near the interface with the sapphire substrate 205 is transformed into amorphous silicon by an implantation process. Then the silicon close to the interface is crystallized by heating in an oxygen atmosphere to form the device formation film 206 , and the silicon oxide film 207 is formed by oxidizing the remaining silicon film simultaneously. Next, the circumference is coated with a polysilicon CVD film; then the circumference is coated with a silicon nitride film. Next, the silicon oxide film 207 is exposed and the protective film 208 is formed to complete an SOS substrate 201 of the same type as shown in FIG. 6 .
[0068] The SOS substrate 201 can have various structures other than the structure described above. For example, a substrate comprising the sapphire substrate 205 and the device formation film 206 , or a substrate comprising the sapphire substrate 205 , the device formation film 206 and the silicon oxide film 207 can be used. A silicon-on-insulator substrate comprising fused silica instead of sapphire is also usable instead of an SOS substrate, but the following description will continue to assume an SOS substrate.
[0069] As shown in the FIG. 8 , a first reflective film 202 is formed to cover all sides and surfaces of the SOS substrate 201 . The first reflective film 202 is a film comprising polysilicon formed by CVD, and has a film thickness adjusted to 42 nm.
[0070] Referring to the FIG. 9 , a second reflective film 203 is formed to cover the first reflective film 202 . The second reflective film 203 is a silicon oxide film formed by CVD, and has a film thickness adjusted to 110 nm. Next, the second reflective film 203 is heated in a nitrogen (N 2 ) atmosphere at 950° Celsius for 20 minutes. The CVD process used to form the second reflective film 203 forms a silicon oxide film with poor crystallization, containing much vapor, which could be easily invaded by hydrofluoric acid during wet etching steps. The subsequent heating step, however, readily eliminates the vapor from the silicon oxide film, giving the silicon oxide film an improved crystalline structure that prevents invasion by hydrofluoric acid.
[0071] Referring to the FIG. 10 , a third reflective film 204 is formed, covering the second reflective film 203 . The third reflective film 204 is a polysilicon film formed by CVD, and having a film thickness adjustable to 42 nm by the time the light-reflecting film is needed for wafer detection. That is, if the thickness of the third reflective film 204 will be reduced by fabrication steps carried out after the formation of the three films 202 , 203 , 204 , the third reflective film 204 may originally be made thicker than 42 nm in order to obtain the desired film thickness of 42 nm at the time of wafer detection.
[0072] Referring to the FIG. 11 , the silicon oxide film 207 of the SOS substrate 201 is exposed by removing the first, second, and third light-reflecting films 202 , 203 , 204 from the front surface of the substrate. The first, second, and third light-reflecting films may be removed by dry etching.
[0073] The above process fabricates a semiconductor wafer device according to the second embodiment of the invention. After the triple-layer light-reflecting film has been formed, semiconductor integrated circuit devices can be fabricated by using conventional semiconductor IC fabrication equipment with optical wafer sensors to form any desired circuitry in and on the device formation film 206 , and then dicing the wafer into chips.
[0074] In a variation of the second embodiment, the triple-layer light-reflecting film does not cover the entire back surface of the wafer. In particular, if the optical wafer sensors illuminate only selected parts of the wafer, the triple-layer film can be removed from the other parts of the wafer to reduce the thickness of the chips.
[0075] In the fabrication process of the second embodiment, the heating step improves the crystalline structure of the second light-reflecting film. Furthermore, the problem of unintended detachment of the third light-reflecting film can be avoided. This problem occurs when a triple-layer light-reflecting film is formed by sequentially depositing a first light-reflecting film, a second light-reflecting film, and a third light-reflecting film made from polysilicon, silicon oxide and polysilicon, respectively, on the back surface of a dielectric substrate by CVD. In this method, in subsequent steps using hydrofluoric acid, the acid reacts with the silicon oxide film material of the second light-reflecting film, thereby invading the silicon oxide film. If the invasion proceeds far enough, eventually the third light-reflecting film becomes detached. By avoiding this problem, the second embodiment maintains the desired optical properties of the light-reflecting film and prevents detached fragments of film from contaminating the fabrication equipment.
[0076] Next, a semiconductor device fabrication process according to a third embodiment of the invention will be described with reference to FIGS. 12 to 16 . Steps similar to steps in the second embodiment will not be described in detail.
[0077] Referring to FIG. 12 , an SOS substrate 301 comprising a sapphire substrate 305 , a device formation film 306 , a silicon oxide film 307 , and a protective film 308 is obtained. A detailed description of this step will be omitted, as the SOS substrate 301 is similar in structure and fabrication to the SOS substrate described in the second embodiment, or any of the SOS substrates described in the first embodiment.
[0078] Referring to FIG. 13 , a first reflective film 302 is formed to cover all sides and surfaces of the SOS substrate 301 . The first reflective film 302 is a polysilicon film formed by CVD. Part of the first reflective film 302 will become a silicon oxide film as described below. To allow for a doubling of the thickness of this part when the polysilicon is oxidized, the thickness of the first reflective film 302 is reduced to 100 nm.
[0079] Referring to FIG. 14 , a second reflective film 303 is formed covering the first reflective film 302 . The second reflective film 303 is formed by heating the first reflective film 302 at 950° Celsius in an oxygen atmosphere for an appropriate length of time to oxidize substantially the outer 58 nm of the first reflective film 302 . The oxidization process approximately doubles the thickness of the oxidized material, creating a second reflective film 303 substantially 110 nm thick. A second reflective film 303 formed in this way has a better crystal lattice structure than a silicon oxide film formed by CVD, and can better prevent invasion of hydrofluoric acid in subsequent wet etching steps. The remaining part of the first reflective film 302 is substantially 42 nm thick.
[0080] Referring to FIG. 15 , a third reflective film 304 is formed covering the second reflective film 303 . This step will not be described in detail because it is similar to the corresponding step described in the second embodiment.
[0081] Referring to FIG. 14 , the device formation film 306 of the SOS substrate 301 is exposed. This step is also similar to the corresponding step in the second embodiment, and will not be described in detail.
[0082] This completes the fabrication of a semiconductor wafer device according to the third embodiment of the invention. As in the second embodiment, semiconductor integrated circuit devices can be fabricated by forming desired circuitry in and on the device formation film of the SOS substrate, using conventional semiconductor fabrication equipment with optical wafer sensors, and then dicing the wafer into individual chips. As noted in the second embodiment, before the circuitry is formed, the triple-layer light-reflecting film can be removed from parts of the wafer not illuminated by light from the optical wafer sensors, to reduce the thickness of the chips.
[0083] The third embodiment has effects similar to those of the second embodiment, and the additional advantage of reduced cost, compared to the second embodiment, because the second light-reflecting film is formed by heating in an oxygen atmosphere, so one CVD step can be omitted from the process described in the second embodiment.
[0084] The invention is not limited to a silicon-on-sapphire substrate. It is applicable to a semiconductor device with any type of transparent dielectric substrate, and may include any type of semiconductor material.
[0085] Those skilled in the art will recognize that further variations are possible within the scope of the invention, which is defined in the appended claims. | A semiconductor device has a transparent dielectric substrate such as a sapphire substrate. To enable fabrication equipment to detect the presence of the substrate optically, the back surface of the substrate is coated with a triple-layer light-reflecting film, preferably a film in which a silicon oxide or silicon nitride layer is sandwiched between polycrystalline silicon layers. This structure provides high reflectance with a combined film thickness of less than half a micrometer. | 7 |
TECHNICAL FIELD
[0001] The present invention relates to a coding apparatus, a decoding apparatus, a coding method, and a decoding method for implementing scalable coding (layer coding).
BACKGROUND ART
[0002] Mobile communication systems are required to compress and transmit speech signals at a low bit rate, in order to effectively utilize radio wave resources. At the same time, the mobile communication systems are required to improve the quality of telephone speech and provide telephone services enabling vivid communication. To achieve this, it is desirable to not only improve the quality of speech signals but also encode, with high quality, even signals other than the speech signals, such as music signals having a wider bandwidth.
[0003] A promising technique for approaching these two contradictory requirements involves hierarchically integrating a plurality of coding techniques. This technique uses a hierarchical combination of a first layer and a second layer: the first layer encodes an input signal at a low bit rate on the basis of a model suited to a speech signal, and the second layer encodes a differential signal between the input signal and a decoded signal of the first layer on the basis of a model suited to signals other than the speech signal. Such technique of hierarchical coding is generally referred to as scalable coding (layer coding) because a bit stream obtained by a coding apparatus exhibits scalability, or a property that a decoded signal can be obtained even from information on part of the bit stream.
[0004] Such scalable coding system can flexibly deal with communication between networks having different bit rates in its nature, and thus can be regarded as suitable for future network environments in which variety of networks will be integrated through IP protocols.
[0005] A technique is disclosed in NPL 1 as an example in which the scalable coding is implemented using a technique standardized by Moving Picture Experts Group phase-4 (MPEG-4). This technique uses, in a first layer, code excited linear prediction (CELP) coding suited to a speech signal, and in a second layer, transform coding, such as advanced audio coder (AAC) or transform domain weighted interleave vector quantization (TwinVQ), is performed on a residual signal obtained by subtracting a first layer decoded signal from the original signal.
[0006] With the use of such a scalable configuration, the quality of speech signals and the quality of music signals and other such signals having a wider bandwidth than that of the speech signals can be improved.
[0007] In the case where the transform coding is applied to at least one layer in the layer coding as described above, coding distortion that is caused by the transform coding at the start point (or the end point) of the speech signal propagates over an entire frame, and this coding distortion unfavorably decreases the sound quality. The coding distortion caused at this time is referred to as pre-echo (or post-echo).
[0008] FIG. 1 shows a state where a decoded signal is generated in the case of encoding and decoding the start point of a speech signal with the use of scalable coding including two layers. Here, the first layer adopts CELP in which an excitation signal is encoded for each sub-frame of 5 ms, and the second layer adopts transform coding performed for each frame of 20 ms.
[0009] In the case as the first layer where the time length of a signal as a coding target is as short as 5 ms, the coding interval is short, and hence such a case is hereinafter referred to as “the temporal resolution is high”. In the case as the second layer where the time length of a signal as a coding target is as long as 20 ms, the coding interval is long, and hence such a case is hereinafter referred to as “the temporal resolution is low”.
[0010] In the first layer, a decoded signal can be generated on a 5-ms basis, and hence the propagation of coding distortion falls within merely 5 ms (see FIG. 1( a )). On the other hand, in the second layer, coding distortion propagates in a wide range of 20 ms. Originally, the first half part of this frame corresponds to inactive speech, and a second layer decoded signal needs to be generated only in the latter half part of this frame. Nevertheless, if the bit rate cannot be made sufficiently high, a waveform appears also in the first half part due to the coding distortion (see FIG. 1( b )). In general, in order to obtain high coding efficiency in the transform coding, the frame length needs to be set to 20 ms or more. Accordingly, the temporal resolution is lower than that of CELP, which is disadvantageous.
[0011] When a final decoded signal is calculated by adding the first layer decoded signal to the second layer decoded signal, the coding distortion remains in section A of the decoded signal (see FIG. 1( c )), resulting in a decrease in sound quality. Such a phenomenon occurs at the start point of a speech signal (or a music signal), and this coding distortion is referred to as pre-echo. Note that similar coding distortion occurs also at the end point of a speech signal (or a music signal), and this coding distortion is referred to as post-echo.
[0012] A method for avoiding the occurrence of such pre-echoes involves detecting the start point of a speech signal and switching, if the start point is detected, to a process of making the frame length (analysis length) of transform coding shorter. PTL 1 discloses a start point detecting method in which: the start point of a speech signal is detected on the basis of a temporal change in gain information of CELP in a first layer; and information on the detected start point is reported to a second layer.
[0013] In this way, the temporal resolution is increased by making the analysis length at the start point shorter. As a result, the propagation of coding distortion can be suppressed to be low, and the occurrence of pre-echoes can be avoided.
[0014] The above-mentioned method, however, requires switching of the analysis lengths, a frequency transforming method suited to the two analysis lengths, and a quantization method for transform coefficients, and hence the complexity of processing is unfavorably increased.
[0015] In addition, PTL 1 does not disclose a specific method for avoiding pre-echoes using information on the detected start point, and hence the pre-echoes cannot be avoided.
[0016] Meanwhile, PTL 2 discloses a method for avoiding the occurrence of pre-echoes, the method in which an amplification factor by which each decoded signal is to be multiplied is obtained on the basis of an energy envelope relation of the decoded signals of a first layer and a second layer; and each decoded signal is multiplied by the obtained amplification factor.
CITATION LIST
Patent Literature
[0000]
PTL 1
Japanese Patent Application Laid-Open No. 2003-233400
PTL 2
National Publication of International Patent Application No. 2008-539456
Non-Patent Literature
[0000]
NPL 1
“All about MPEG-4” written and edited by Sukeichi MIKI, First Edition, Kogyo Chosakai Publishing Co., Ltd., Sep. 30, 1998, pp. 126-127
SUMMARY OF INVENTION
Technical Problem
[0023] Unfortunately, according to the method described in PTL 2 , part of the decoded signal of the second layer is significantly attenuated after encoding in the second layer, and hence part of encoded data of the second layer is wasted, which is not efficient.
[0024] The present invention has an object to provide a coding apparatus, a decoding apparatus, a coding method, and a decoding method for suppressing the occurrence of pre-echoes or post-echoes caused by a higher layer having low temporal resolution, to thereby implement coding and decoding with high subjective quality.
Solution to Problem
[0025] An aspect of the present invention provides a coding apparatus for scalable coding including: a lower layer; and a higher layer having temporal resolution lower than temporal resolution of the lower layer, the coding apparatus including: a lower layer coding section that encodes an input signal to obtain a lower layer encoded signal; a lower layer decoding section that decodes the lower layer encoded signal to obtain a lower layer decoded signal; an error signal generating section that obtains an error signal between the input signal and the lower layer decoded signal; a determining section that determines a start point or an end point of an active speech portion in the lower layer decoded signal; and a higher layer coding section that selects, if the determining section determines the start point or the end point, a band to be excluded from coding target bands, excludes the selected band to encode the error signal, and obtains a higher layer encoded signal.
[0026] An aspect of the present invention provides a decoding apparatus for decoding a lower layer encoded signal and a higher layer encoded signal that are encoded by a coding apparatus for scalable coding including: a lower layer; and a higher layer having temporal resolution lower than temporal resolution of the lower layer, the decoding apparatus including: a lower layer decoding section that decodes the lower layer encoded signal to obtain a lower layer decoded signal; a higher layer decoding section that excludes or processes a band selected on a basis of a preset condition to decode the higher layer encoded signal, and obtains a decoded error signal; and an adding section that adds the lower layer decoded signal to the decoded error signal to obtain a decoded signal.
[0027] An aspect of the present invention provides a coding method for scalable coding including: a lower layer; and a higher layer having temporal resolution lower than temporal resolution of the lower layer, the coding method including: a lower layer coding step of encoding an input signal to obtain a lower layer encoded signal; a lower layer decoding step of decoding the lower layer encoded signal to obtain a lower layer decoded signal; an error signal generating step of obtaining an error signal between the input signal and the lower layer decoded signal; a determining step of determining a start point or an end point of an active speech portion in the lower layer decoded signal; and a higher layer coding step of selecting, if the start point or the end point is determined in the determining step, a band to be excluded from coding target bands, excluding the selected band to encode the error signal, and obtaining a higher layer encoded signal.
[0028] An aspect of the present invention provides a decoding method for decoding a lower layer encoded signal and a higher layer encoded signal that are encoded by a coding method for scalable coding including: a lower layer; and a higher layer having temporal resolution lower than temporal resolution of the lower layer, the decoding method including: a lower layer decoding step of decoding the lower layer encoded signal to obtain a lower layer decoded signal; a higher layer decoding step of excluding or processing a band selected on a basis of a preset condition to decode the higher layer encoded signal, and obtaining a decoded error signal; and an adding step of adding the lower layer decoded signal to the decoded error signal to obtain a decoded signal.
Advantageous Effects of Invention
[0029] According to the present invention, it is possible to suppress the occurrence of pre-echoes or post-echoes caused by a higher layer having low temporal resolution, to thereby implement coding and decoding with high subjective quality.
BRIEF DESCRIPTION OF DRAWINGS
[0030] FIG. 1 is a diagram showing a state where a decoded signal is generated in the case of encoding and decoding the start point of a speech signal with the use of scalable coding including two layers;
[0031] FIG. 2 is a diagram showing a main part configuration of a coding apparatus according to Embodiment 1 of the present invention;
[0032] FIG. 3 is a diagram showing an internal configuration of a start point detecting section;
[0033] FIG. 4 is a diagram showing an internal configuration of a second layer coding section;
[0034] FIG. 5 is a diagram showing another main part configuration of the coding apparatus according to Embodiment 1;
[0035] FIG. 6 is a diagram showing another internal configuration of the second layer coding section;
[0036] FIG. 7 is a diagram showing still another main part configuration of the coding apparatus according to Embodiment 1;
[0037] FIG. 8 is a diagram showing still another internal configuration of the second layer coding section;
[0038] FIG. 9 is a block diagram showing a main part configuration of a decoding apparatus according to Embodiment 1;
[0039] FIG. 10 is a diagram showing an internal configuration of a second layer decoding section;
[0040] FIG. 11 is a diagram showing states of an input signal, first layer decoding transform coefficients, and second layer decoding transform coefficients according to a conventional method;
[0041] FIG. 12 is a chart for describing temporal masking as a human perceptual characteristic;
[0042] FIG. 13 is a diagram showing states of an input signal, first layer decoding transform coefficients, and second layer decoding transform coefficients according to the present embodiment;
[0043] FIG. 14 is a chart showing a state of backward masking when the first layer decoding transform coefficients are a masker signal;
[0044] FIG. 15 is a diagram showing an example in which the present invention is applied to post-echoes;
[0045] FIG. 16 is a diagram showing a main part configuration of a coding apparatus according to Embodiment 2 of the present invention;
[0046] FIG. 17 is a diagram showing an internal configuration of a second layer coding section;
[0047] FIG. 18 is a diagram showing an internal configuration of a second layer coding section according to Embodiment 3 of the present invention;
[0048] FIG. 19 is a block diagram showing a main part configuration of a decoding apparatus according to Embodiment 3;
[0049] FIG. 20 is a diagram showing an internal configuration of a second layer decoding section;
[0050] FIG. 21 is a diagram showing a main part configuration of a coding apparatus according to Embodiment 4 of the present invention;
[0051] FIG. 22 is a diagram showing an internal configuration of a second layer coding section;
[0052] FIG. 23 is a diagram showing an internal configuration of a second layer decoding section; and
[0053] FIG. 24 is a diagram showing a state of processing in an attenuating section.
DESCRIPTION OF EMBODIMENTS
[0054] Now, embodiments of the present invention will be described in detail with reference to the drawings.
Embodiment 1
[0055] FIG. 2 is a diagram showing a main part configuration of a coding apparatus according to the present embodiment. Coding apparatus 100 of FIG. 2 is assumed as a scalable coding (layer coding) apparatus including two coding layers as an example. Note that the number of layers is not limited to two.
[0056] Coding apparatus 100 shown in FIG. 2 performs a coding process on a predetermined time interval (frame; here, assumed as 20 ms) basis, generates a bit stream, and transmits the bit stream to a decoding apparatus (not shown).
[0057] First layer coding section 110 performs a coding process of an input signal, and generates first layer encoded data. Note that first layer coding section 110 performs coding with high temporal resolution. First layer coding section 110 adopts, as a coding method, for example, a CELP coding system in which each frame is divided into sub-frames of 5 ms and excitation is encoded on a sub-frame basis. First layer coding section 110 outputs the first layer encoded data to first layer decoding section 120 and multiplexing section 170 .
[0058] First layer decoding section 120 performs a decoding process using the first layer encoded data, generates a first layer decoded signal, and outputs the generated first layer decoded signal to subtracting section 140 , start point detecting section 150 , and second layer coding section 160 .
[0059] Delaying section 130 delays the input signal by an amount of time corresponding to a delay that occurs in first layer coding section 110 and first layer decoding section 120 , and outputs the delayed input signal to subtracting section 140 .
[0060] Subtracting section 140 subtracts, from the input signal, the first layer decoded signal generated by first layer decoding section 120 to thereby generate a first layer error signal, and outputs the first layer error signal to second layer coding section 160 .
[0061] Start point detecting section 150 detects, using the first layer decoded signal, whether or not the signal contained in the frame that is currently subjected to the coding process is the start point of an active speech portion such as a speech signal or a music signal, and outputs the detection result as start point detection information to second layer coding section 160 . Note that the detail of start point detecting section 150 is described later.
[0062] Second layer coding section 160 performs a coding process of the first layer error signal sent out from subtracting section 140 , and generates second layer encoded data. Note that second layer coding section 160 performs coding with temporal resolution lower than that of first layer coding section 110 . For example, second layer coding section 160 adopts a transform coding system in which transform coefficients are encoded on the basis of a unit longer than the processing unit of first layer coding section 110 . Note that the detail of second layer coding section 160 is described later. Second layer coding section 160 outputs the generated second layer encoded data to multiplexing section 170 .
[0063] Multiplexing section 170 multiplexes the first layer encoded data obtained by first layer coding section 110 with the second layer encoded data obtained by second layer coding section 160 to thereby generate a bit stream, and outputs the generated bit stream to a transmission channel (not shown).
[0064] FIG. 3 is a diagram showing an internal configuration of start point detecting section 150 .
[0065] Sub-frame dividing section 151 divides the first layer decoded signal into Nsub sub-frames. Here, Nsub represents the number of sub-frames. Hereinafter, description is given assuming that Nsub=2.
[0066] Energy change amount calculating section 152 calculates energy of the first layer decoded signal for each sub-frame.
[0067] Detecting section 153 compares the amount of change in this energy with a predetermined threshold value. If the amount of change exceeds the threshold value, detecting section 153 determines that the start point of the active speech portion is detected, and outputs 1 as the start point detection information. On the other hand, if the amount of change does not exceed the threshold value, detecting section 153 does not determine that the start point is detected, and outputs 0 as the start point detection information.
[0068] FIG. 4 is a diagram showing an internal configuration of second layer coding section 160 .
[0069] Frequency domain transforming section 161 transforms the first layer error signal into a frequency domain, calculates first layer error transform coefficients, and outputs the calculated first layer error transform coefficients to band selecting section 163 and gain coding section 164 .
[0070] Frequency domain transforming section 162 transforms the first layer decoded signal into a frequency domain, calculates first layer decoding transform coefficients, and outputs the calculated first layer decoding transform coefficients to band selecting section 163 .
[0071] If the start point detection information indicates 1, that is, if the signal contained in the frame that is currently subjected to the coding process is the start point of the active speech portion, band selecting section 163 selects a sub-band to be excluded from the coding targets of gain coding section 164 and shape coding section 165 at the subsequent stage. Specifically, band selecting section 163 divides the first layer decoding transform coefficients into a plurality of sub-bands, and excludes a sub-band whose energy of the first layer decoding transform coefficients is the smallest or a sub-band whose energy thereof is smaller than a predetermined threshold value, from the coding targets of second layer coding section 160 (gain coding section 164 and shape coding section 165 ). Then, band selecting section 163 sets each sub-band that remains without being excluded, as an actual coding target band (second layer coding target band).
[0072] Note that band selecting section 163 may divide the first layer decoding transform coefficients and the first layer error transform coefficients into a plurality of sub-bands, and may obtain a ratio (Ee/Em) of energy (Ee) of the first layer error transform coefficients to energy (Em) of the first layer decoding transform coefficients for each sub-band. Then, band selecting section 163 may select a sub-band whose energy ratio is larger than a predetermined threshold value, as a sub-band to be excluded from the coding targets of second layer coding section 160 . Alternatively, instead of the energy ratio, band selecting section 163 may obtain a ratio of the maximum amplitude value of the first layer error transform coefficients to the maximum amplitude value of the first layer decoding transform coefficients for each sub-band. Then, band selecting section 163 may select a sub-band whose maximum amplitude value ratio is larger than a predetermined threshold value, as a sub-band to be excluded from the coding targets of second layer coding section 160 .
[0073] Note that band selecting section 163 may adaptively use different threshold values in accordance with characteristics (for example, speech- or music-related, or stationary or non-stationary) of the input signal.
[0074] Note that band selecting section 163 may calculate a perceptual masking threshold value corresponding to backward masking, on the basis of the first layer decoding transform coefficients, and may calculate energy of the perceptual masking threshold value for each sub-band. Then, band selecting section 163 may exclude a sub-band whose calculated energy is the smallest or a sub-band whose calculated energy is smaller than a predetermined threshold value, from the coding targets of second layer coding section 160 .
[0075] Note that, instead of the first layer decoding transform coefficients, band selecting section 163 may use input transform coefficients obtained by transforming the input signal into a frequency domain, to thereby determine the coding target band. The configurations of coding apparatus 100 and second layer coding section 160 in this case are respectively shown in FIG. 5 and FIG. 6 .
[0076] Note that, without using the first layer decoding transform coefficients, band selecting section 163 may use only the first layer error transform coefficients, to thereby determine the coding target band. The configurations of coding apparatus 100 and second layer coding section 160 in this case are respectively shown in FIG. 7 and FIG. 8 . This configuration can produce an effect of the present embodiment without using the first layer decoding transform coefficients, for the following reason.
[0077] That is, first layer coding section 110 performs perceptual weighting to thereby perform such a coding process that spectral characteristics of the error signal between the input signal and the first layer decoded signal approach spectral characteristics of the input signal. This perceptual weighting is performed in order to obtain an effect that makes the error signal difficult to hear perceptually. In other words, first layer coding section 110 performs such spectral shaping that the spectral characteristics of the error signal approach the spectral characteristics of the input signal. As a result, because the spectral characteristics of the error signal approach the spectral characteristics of the input signal, the effect of the present embodiment can be produced even if the error signal is used instead of the first layer decoded signal. For example, a method in which a perceptual weighting filter having characteristics close to inverse characteristics of a spectral envelope of the input signal is used on the basis of linear predictive coding (LPC) coefficients can be applied to the perceptual weighting process of first layer coding section 110 .
[0078] In addition, this configuration does not need frequency domain transforming section 162 , and thus can produce another effect that reduces the amount of calculation.
[0079] In this way, band selecting section 163 selects a band to be excluded from the coding targets of second layer coding section 160 , and outputs information (coding target band information) indicating each band (second layer coding target band), which is other than the selected sub-band and corresponds to the coding target, to gain coding section 164 , shape coding section 165 , and multiplexing section 166 .
[0080] Gain coding section 164 calculates gain information indicating the magnitude of the transform coefficients contained in each sub-band (second layer coding target band) reported by band selecting section 163 , and encodes the gain information to thereby generate gain encoded data. Gain coding section 164 outputs the gain encoded data to multiplexing section 166 . Gain coding section 164 also outputs decoding gain information obtained together with the gain encoded data, to shape coding section 165 .
[0081] Shape coding section 165 generates, using the decoding gain information, shape encoded data indicating the shape of the transform coefficients contained in each sub-band (second layer coding target band) reported by band selecting section 163 , and outputs the generated shape encoded data to multiplexing section 166 .
[0082] Multiplexing section 166 multiplexes the coding target band information outputted by band selecting section 163 , the shape encoded data outputted by shape coding section 165 , and the gain encoded data outputted by gain coding section 164 with one another, and outputs the multiplexed data as the second layer encoded data. Note that multiplexing section 166 is not indispensable, and the coding target band information, the shape encoded data, and the gain encoded data may be outputted directly to multiplexing section 170 .
[0083] FIG. 9 is a block diagram showing a main part configuration of a decoding apparatus according to the present embodiment. Decoding apparatus 200 of FIG. 9 decodes the bit stream outputted by coding apparatus 100 that performs the scalable coding (layer coding) including the two coding layers.
[0084] Separating section 210 separates the bit stream inputted through the transmission channel, into first layer encoded data and second layer encoded data. Separating section 210 outputs the first layer encoded data to first layer decoding section 220 , and outputs the second layer encoded data to second layer decoding section 230 . Unfortunately, a part (second layer encoded data) or the entirety of the encoded data may be discarded in some cases depending on conditions of the transmission channel (for example, the occurrence of congestion). At this time, separating section 210 determines whether the received encoded data contains only the first layer encoded data (layer information is 1) or contains both the first layer encoded data and the second layer encoded data (layer information is 2), and outputs the determination result as the layer information to switching section 250 . If the entire encoded data is discarded, separating section 210 performs predetermined error concealment processing, and generates an output signal.
[0085] First layer decoding section 220 performs a decoding process of the first layer encoded data, generates a first layer decoded signal, and outputs the generated first layer decoded signal to adding section 240 and switching section 250 .
[0086] Second layer decoding section 230 performs a decoding process of the second layer encoded data, generates a first layer decoding error signal, and outputs the generated first layer decoding error signal to adding section 240 .
[0087] Adding section 240 adds the first layer decoded signal to the first layer decoding error signal to thereby generate a second layer decoded signal, and outputs the generated second layer decoded signal to switching section 250 .
[0088] On the basis of the layer information given by separating section 210 , if the layer information is 1, switching section 250 outputs the first layer decoded signal as a decoded signal to post-processing section 260 . On the other hand, if the layer information is 2, switching section 250 outputs the second layer decoded signal as a decoded signal to post-processing section 260 .
[0089] Post-processing section 260 performs post-processing such as post-filtering on the decoded signal, and outputs the processed signal as an output signal.
[0090] FIG. 10 is a diagram showing an internal configuration of second layer decoding section 230 .
[0091] Separating section 231 separates the second layer encoded data inputted by separating section 210 into shape encoded data, gain encoded data, and coding target band information. Then, separating section 231 outputs the shape encoded data to shape decoding section 232 , outputs the gain encoded data to gain decoding section 233 , and outputs the coding target band information to decoding transform coefficients generating section 234 . Note that separating section 231 is not an indispensable component. The second layer encoded data may be separated into the shape encoded data, the gain encoded data, and the coding target band information in the separation process of separating section 210 , and the separated pieces of data and information may be given directly to shape decoding section 232 , gain decoding section 233 , and decoding transform coefficients generating section 234 , respectively.
[0092] Shape decoding section 232 generates a shape vector of decoding transform coefficients with the use of the shape encoded data given by separating section 231 , and outputs the generated shape vector to decoding transform coefficients generating section 234 .
[0093] Gain decoding section 233 generates gain information on decoding transform coefficients with the use of the gain encoded data given by separating section 231 , and outputs the generated gain information to decoding transform coefficients generating section 234 .
[0094] Decoding transform coefficients generating section 234 multiplies the shape vector by the gain information, and places the shape vector that has been multiplied by the gain information, in a band indicated by the coding target band information, to thereby generate decoding transform coefficients. Then, decoding transform coefficients generating section 234 outputs the generated decoding transform coefficients to time domain transforming section 235 .
[0095] Time domain transforming section 235 transforms the decoding transform coefficients into a time domain to thereby generate a first layer decoding error signal, and outputs the generated first layer decoding error signal.
[0096] Next, with reference to FIG. 11 , FIG. 12 , and FIG. 13 , problems to be solved by the present invention and effects obtained thereby are described. Note that description is given below of an example case where coding apparatus 100 performs coding for each frame of an L sample. As described above, first layer coding section 110 performs coding with high temporal resolution, and second layer coding section 160 performs coding with low temporal resolution. Accordingly, description is given below of an example case where first layer coding section 110 adopts a CELP coding system in which excitation is encoded on a sub-frame basis of the L/2 sample and where second layer coding section 160 adopts a transform coding system in which transform coefficients are encoded on a frame basis of the L sample.
[0097] FIG. 11 shows states of an input signal, first layer decoding transform coefficients, and second layer decoding transform coefficients when scalable coding and decoding are performed according to a conventional method.
[0098] FIG. 11(A) shows the input signal of the coding apparatus. As is apparent from FIG. 11(A) , a speech signal (or a music signal) is observed in the middle of the second sub-frame.
[0099] First, the coding process is performed on the input signal by the first layer coding section, so that the first layer encoded data is generated. The decoding transform coefficients (first layer decoding transform coefficients) of the decoded signal generated by decoding the first layer encoded data have twice as high temporal resolution as that of the second layer coding section. In the n th sample to the (n+L/2−1) th sample, a spectrum (see FIG. 11(B) ) corresponding to an inactive speech section is generated. In the (n+L/2−1) th sample to the (n+L−1) th sample, a spectrum (see FIG. 11(C) ) corresponding to an active speech section is generated.
[0100] Then, the transform coefficients are encoded by the second layer coding section on a frame basis of the L sample, so that the second layer encoded data is generated. Accordingly, the second layer encoded data is decoded, whereby the second layer decoding transform coefficients corresponding to the n th sample to the (n+L−1) th sample are generated (see FIG. 11(D) ). Then, the second layer decoding transform coefficients are transformed into a time domain, whereby the second layer decoded signal is generated in a section corresponding to the n th sample to the (n+L−1) th sample. As a result, in the n th sample to the (n+L/2−1) th sample, the spectrum of the final decoded signal is a spectrum obtained by adding FIG. 11(B) to FIG. 11(D) . In the (n+L/2−1) th sample to the (n+L−1) th sample, the spectrum thereof is a spectrum obtained by adding FIG. 11(C) to FIG. 11(D) .
[0101] At this time, even in the n th sample to the (n+L/2−1) th sample, which should be an inactive speech section originally, the spectra shown in FIGS. 11(B) and (D) unfavorably occur. Because signal components in (B) of FIG. 11 are ignorable, substantially, the decoded signal based on the spectrum in FIG. 11(D) is generated. This signal is perceived as pre-echoes, and leads to a decrease in quality of the decoded signal.
[0102] In the present embodiment, the decrease in quality of the decoded signal is avoided by utilizing temporal masking as a human perceptual characteristic. The temporal masking here refers to masking that occurs when two sounds, that is, a masked signal (maskee signal) and a masking signal (masker signal) are successively given. Humans have difficulty in perceiving a feeble sound existing before or after a strong sound, and a maskee signal is hindered by a masker signal to become difficult to hear.
[0103] In such temporal masking, a phenomenon in which a maskee signal preceding a masker signal is masked is referred to as backward masking, and a phenomenon in which a maskee signal following a masker signal is masked is referred to as forward masking. Note that a phenomenon in which a masker signal and a maskee signal occur in a given time zone and the maskee signal is masked by the masker signal is referred to as simultaneous masking.
[0104] FIG. 12 shows an example of the masking level of a masker signal masking a maskee signal in each of such backward masking, forward masking, and simultaneous masking as described above.
[0105] In the present embodiment, the perceptual decrease in quality caused by pre-echoes is avoided by utilizing the backward masking of the temporal masking.
[0106] Specifically, the following principle is utilized. In a band having large energy of a decoding spectrum of a lower layer, pre-echoes occurring in a higher layer become more difficult to hear by a human perceptual sense owing to the backward masking effect. In contrast, in a band having small energy of the decoding spectrum of the lower layer, the backward masking effect cannot be obtained, and hence the pre-echoes become easier to hear. That is, in the present invention, with the utilization of this principle, a spectrum of the higher layer that is contained in the band having small energy of the decoding spectrum of the lower layer is excluded from the coding targets of the higher layer, whereby the decoding spectrum of the higher layer is not generated in the band in which the pre-echoes are easily heard. As a result, the pre-echoes occur only in the band having large energy of the decoding spectrum of the lower layer, where the backward masking effect can be obtained, and hence the perceptual decrease in quality caused by the pre-echoes can be avoided.
[0107] FIG. 13 shows states of an input signal, first layer decoding transform coefficients, and second layer decoding transform coefficients when scalable coding and decoding are performed according to the present embodiment.
[0108] FIG. 13(A) shows the input signal of coding apparatus 100 . Similarly to FIG. 1(A) 1 , a speech signal (or a music signal) is observed in the middle of the second sub-frame.
[0109] First, the coding process is performed on the input signal by first layer coding section 110 , so that the first layer encoded data is generated. The decoding transform coefficients (first layer decoding transform coefficients) of the decoded signal generated by decoding the first layer encoded data have twice as high temporal resolution as that of second layer coding section 160 . In the n th sample to the (n+L/2−1) th sample, a spectrum (see FIG. 13(B) ) corresponding to an inactive speech section is generated. In the (n+L/2−1) th sample to the (n+L−1) th sample, a spectrum (see FIG. 13(C) ) corresponding to an active speech section is generated.
[0110] In the present embodiment, frequency domain transforming section 162 transforms the first layer decoded signal obtained by first layer decoding section 120 having high temporal resolution, into a frequency domain, to thereby calculate the first layer decoding transform coefficients, and band selecting section 163 obtains a band having small energy of the spectrum (see FIG. 13 (C)), from the calculated first layer decoding transform coefficients. Then, band selecting section 163 selects the obtained band as a band (exclusion band) to be excluded from the coding targets of second layer coding section 160 , and sets each band other than the exclusion band as the second coding target band. Then, second layer coding section 160 performs the coding process on the second coding target band ( FIG. 13(D) ).
[0111] As a result, in the case where the first layer decoding transform coefficients in FIG. 13(C) serve as a masker signal and where pre-echoes occurring in second layer coding section 160 serve as a maskee signal, the pre-echoes become difficult to hear by a human auditory sense owing to the backward masking effect, in the band having large energy of the first layer decoding transform coefficients. Thus, even if the second layer decoding transform coefficients of the pre-echoes is placed in the second coding target band having a large backward masking effect, the decoded signal (pre-echoes) become difficult to perceive. That is, the pre-echoes occurring from the n th sample to the start point of the speech become difficult to hear, and hence the decrease in quality of the decoded signal can be avoided.
[0112] FIG. 14 shows a backward masking characteristic when the first layer decoding transform coefficients serve as a masker signal. As shown in FIG. 14 , as the first layer decoding transform coefficients are larger, the backward masking effect is larger. Hence, the coding target band of second layer coding section 160 is set to only a band whose first layer decoding transform coefficients are larger than a predetermined threshold value, whereby the pre-echoes are masked by the first layer decoding transform coefficients.
[0113] Hereinabove, how to avoid pre-echoes occurring at the start point of the speech is described, but the present invention can also be applied to post-echoes occurring at the end point of the speech.
[0114] FIG. 15 shows states of an input signal, first layer decoding transform coefficients, and second layer decoding transform coefficients when the present invention is applied to post-echoes.
[0115] With regard to the pre-echoes, the perception thereof is controlled by utilizing the backward masking, whereas, with regard to the post-echoes, the perception thereof is controlled by utilizing the forward masking. Specifically, an end point detecting section (omitted from the drawings) is used instead of start point detecting section 150 . The end point detecting section detects, using the first layer decoded signal, whether or not the signal contained in the frame that is currently subjected to the coding process is the end point of an active speech portion, and outputs the detection result as end point detection information to second layer coding section 160 . Then, if the signal contained in the frame that is currently subjected to the coding process is the end point of the active speech portion, band selecting section 163 obtains a band having small energy (see FIG. 15 (B)), from the first layer decoding transform coefficients obtained by first layer coding section 110 having high temporal resolution. Then, band selecting section 163 selects the obtained band as a band (exclusion band) to be excluded from the coding targets of second layer coding section 160 , and sets each band other than the exclusion band as the second coding target band. Then, second layer coding section 160 performs the coding process on the second coding target band ( FIG. 15(D) ). As a result, the perception of the post-echoes can be suppressed, and the decrease in quality of the decoded signal can be avoided.
[0116] As described above, in the present embodiment, start point detecting section 150 (or the end point detecting section) determines the start point (or the end point) of an active speech portion of a lower layer decoded signal. If the start point (or the end point) is determined, second layer coding section 160 selects a band to be excluded from the coding targets, on the basis of energy of the spectrum of the first layer decoded signal, and excludes the selected band to encode an error signal. In this way, the decrease in quality of the decoded signal can be avoided by utilizing temporal masking as a human perceptual characteristic, and the occurrence of pre-echoes (or post-echoes) caused by the higher layer having low temporal resolution can be suppressed, so that a coding system with high subjective quality can be provided.
[0117] In addition, because a band having small energy of the first layer decoding transform coefficients is excluded from the coding targets of second layer coding section 160 , the transform coefficients of the other bands can be expressed more accurately. For example, the number of pulses placed in the coding target band of second layer coding section 160 can be increased. In this case, the sound quality of the decoded signal can be improved.
[0118] Note that description is given above of an example method in which the band (exclusion band) to be excluded from the coding targets of second layer coding section 160 is selected in accordance with the magnitude of energy of the first layer decoding transform coefficients, but the present invention is not limited to this method. For example, the exclusion band may be selected in accordance with the magnitude of a relative value of sub-band energy to the maximum sub-band energy. According to this method, stable processing can be performed without depending on the signal level, and pre-echoes occurring at the start point of speech or post-echoes occurring at the end point of speech can be avoided, so that the sound quality can be improved.
[0119] In addition, because the coding target band of second layer coding section 160 is limited in accordance with the first layer decoding transform coefficients, the spectrum of the coding target band of second layer coding section 160 can be expressed more accurately by, for example, increasing the number of pulses in the coding target band, so that the sound quality can be improved.
Embodiment 2
[0120] In Embodiment 1, the band (exclusion band) to be excluded from the coding targets of the second layer coding section is determined using the first layer decoded signal. In the present embodiment, a linear predictive coding (LPC) spectrum (spectral envelope) is obtained using LPC coefficients obtained by the first layer coding section, and the exclusion band is determined using this LPC spectrum. Such use of the LPC spectrum can also produce an effect similar to that of Embodiment 1. Further, in the present embodiment, the LPC spectrum is used instead of the spectrum of the decoded signal, and hence the sound quality can be improved with a smaller amount of calculation, compared with Embodiment 1.
[0121] FIG. 16 is a block diagram showing a main part configuration of a coding apparatus according to the present embodiment. Note that, in coding apparatus 300 of FIG. 16 , components common to those of coding apparatus 100 of FIG. 2 are denoted by the same reference signs as those of FIG. 2 , and description thereof is omitted. Note that the configuration of a decoding apparatus according to the present embodiment is the same as that of FIG. 9 and FIG. 10 , and hence description thereof is omitted here.
[0122] First layer coding section 310 performs a coding process of an input signal, and generates first layer encoded data. Note that, in the present embodiment, first layer coding section 310 performs coding using the LPC coefficients.
[0123] First layer decoding section 320 performs a decoding process using the first layer encoded data, generates a first layer decoded signal, and outputs the generated first layer decoded signal to subtracting section 140 and start point detecting section 150 .
[0124] First layer decoding section 320 outputs decoding LPC coefficients generated in the decoding process for the first layer decoded signal, to second layer coding section 330 .
[0125] FIG. 17 is a diagram showing an internal configuration of second layer coding section 330 . Note that, in second layer coding section 330 of FIG. 17 , components common to those of second layer coding section 160 of FIG. 4 are denoted by the same reference signs as those of FIG. 4 , and description thereof is omitted.
[0126] LPC spectrum calculating section 331 obtains an LPC spectrum with the use of the decoding LPC coefficients inputted by first layer decoding section 320 . The LPC spectrum expresses a rough shape (spectral envelope) of the spectrum of the first layer decoded signal.
[0127] Band selecting section 332 selects a band (exclusion band) to be excluded from the coding target bands of second layer coding section 330 , with the use of the LPC spectrum inputted by LPC spectrum calculating section 331 . Specifically, band selecting section 332 obtains energy of the LPC spectrum, and selects a band whose obtained energy is smaller than a predetermined threshold value, as the exclusion band. Alternatively, band selecting section 332 may select a band whose ratio of energy to the maximum energy of the LPC spectrum is lower than a predetermined threshold value, as the exclusion band.
[0128] In this way, band selecting section 332 selects a band to be excluded from the coding targets of second layer coding section 330 , and outputs information (coding target band information) indicating each band (second layer coding target band), which is other than the selected band and corresponds to the coding target, to gain coding section 164 , shape coding section 165 , and multiplexing section 166 .
[0129] Subsequently, in the same manner as in Embodiment 1, second layer encoded data is generated by gain coding section 164 , shape coding section 165 , and multiplexing section 166 .
[0130] As described above, in the present embodiment, first layer coding section 310 performs the coding using the LPC coefficients, and second layer coding section 330 selects a band having small energy of the spectrum of the LPC coefficients, as the band to be excluded from the coding target bands. As a result, the band having small energy, that is, the band to be excluded from the coding target bands can be determined with a smaller amount of calculation compared with the case of calculating the spectrum of the first layer decoded signal.
[0131] Note that, in this case, the LPC spectrum and energy thereof may be calculated only for the limited number of frequencies, and the band to be excluded from the coding target bands may be determined using the energy thus calculated. In this way, frequencies (or bands) are limited to some extent, and the coding target band is determined, whereby the band can be determined with a still smaller amount of calculation.
Embodiment 3
[0132] In Embodiment 1 and Embodiment 2, the coding apparatus transmits, to the decoding apparatus, the coding target band information indicating the actual coding target band of the second layer coding section, the actual coding target band being set by the band selecting section. In the present embodiment, on the basis of information obtained commonly between the coding apparatus and the decoding apparatus, each apparatus sets the actual coding target band of the second layer coding section (second layer coding target band). This can reduce the amount of information transmitted from the coding apparatus to the decoding apparatus.
[0133] A main part configuration of a coding apparatus according to the present embodiment is similar to that of Embodiment 1, and hence description is given with reference to FIG. 2 . The present embodiment is different from Embodiment 1 in an internal configuration of the second layer coding section. Accordingly, in the following description, a second layer coding section according to the present embodiment is denoted by 160 A.
[0134] FIG. 18 is a diagram showing an internal configuration of second layer coding section 160 A according to the present embodiment. Note that, in second layer coding section 160 A of FIG. 18 , components common to those of second layer coding section 160 of FIG. 4 are denoted by the same reference signs as those of FIG. 4 , and description thereof is omitted.
[0135] If the start point detection information indicates 1, that is, if the signal contained in the frame that is currently subjected to the coding process is the start point of the active speech portion, band selecting section 163 A selects a sub-band to be excluded from the coding targets of gain coding section 164 and shape coding section 165 at the subsequent stage. Note that, in the present embodiment, band selecting section 163 A does not use the first layer error transform coefficients, but uses only the first layer decoding transform coefficients, and selects a sub-band to be excluded from the coding target bands. Specifically, band selecting section 163 A divides the first layer decoding transform coefficients into a plurality of sub-bands, excludes a sub-band whose energy of the first layer decoding transform coefficients is smaller than a predetermined threshold value, from the coding target bands of second layer coding section 160 A, and sets each sub-band that remains without being excluded, as an actual coding target band. Band selecting section 163 A outputs, to gain coding section 164 and shape coding section 165 , information (coding target band information) indicating each band (second layer coding target band), which is other than the sub-band selected as a band to be excluded from the coding targets of second layer coding section 160 A (gain coding section 164 and shape coding section 165 ) and corresponds to the coding target.
[0136] Note that band selecting section 163 A may adaptively use different threshold values in accordance with characteristics (for example, speech- or music-related, or stationary or non-stationary) of the input signal.
[0137] FIG. 19 is a block diagram showing a main part configuration of a decoding apparatus according to the present embodiment. Note that, in decoding apparatus 400 of FIG. 19 , components common to those of decoding apparatus 200 of FIG. 9 are denoted by the same reference signs as those of FIG. 9 , and description thereof is omitted.
[0138] First layer decoding section 410 performs a decoding process using the first layer encoded data, generates a first layer decoded signal, and outputs the generated first layer decoded signal to switching section 250 , start point detecting section 420 , second layer decoding section 430 , and adding section 240 .
[0139] Start point detecting section 420 detects, using the first layer decoded signal, whether or not the signal contained in the frame that is currently subjected to the coding process is the start point of an active speech portion, and outputs the detection result as start point detection information to second layer decoding section 430 . Note that start point detecting section 420 has a configuration similar to that of start point detecting section 150 of FIG. 3 , and operates similarly thereto, and hence detailed description thereof is omitted.
[0140] FIG. 20 is a diagram showing an internal configuration of second layer decoding section 430 . Note that, in second layer decoding section 430 of FIG. 20 , components common to those of second layer decoding section 230 of FIG. 10 are denoted by the same reference signs as those of FIG. 10 , and description thereof is omitted.
[0141] Separating section 431 separates the second layer encoded data inputted by separating section 210 into shape encoded data and gain encoded data. Then, separating section 431 outputs the shape encoded data to shape decoding section 232 , and outputs the gain encoded data to gain decoding section 233 . Note that separating section 431 is not an indispensable component. The second layer encoded data may be separated into the shape encoded data and the gain encoded data in the separation process of separating section 210 , and the separated pieces of data may be given directly to shape decoding section 232 and gain decoding section 233 , respectively.
[0142] Frequency domain transforming section 432 transforms the first layer decoded signal into a frequency domain, calculates first layer decoding transform coefficients, and outputs the calculated first layer decoding transform coefficients to band selecting section 433 .
[0143] If the start point detection information indicates 1, that is, if the signal contained in the frame that is currently subjected to the decoding process is the start point of an active speech portion, band selecting section 433 selects a sub-band to be excluded from the decoding targets of shape decoding section 232 and gain decoding section 233 at the subsequent stage. Note that, in the present embodiment, similarly to band selecting section 163 A, band selecting section 433 does not use the first layer error transform coefficients, but uses only the first layer decoding transform coefficients, and selects a sub-band to be excluded from the coding target bands. Note that band selecting section 433 is similar to band selecting section 163 A, and hence description thereof is omitted. Band selecting section 433 outputs, to decoding transform coefficients generating section 234 , information (coding target band information) indicating each band (second layer coding target band), which is other than the sub-band selected as a band to be excluded from the coding targets of second layer decoding section 430 and corresponds to the coding target.
[0144] In this way, in the present embodiment, band selecting section 163 A and band selecting section 433 respectively set actual coding/decoding target bands of second layer coding section 330 and second layer decoding section 430 with the use of the first layer decoding transform coefficients. In second layer decoding section 430 , the first layer decoding transform coefficients are obtained by transforming the first layer decoded signal into a frequency domain by frequency domain transforming section 432 . Accordingly, without the need to report the coding target band information from coding apparatus 300 to decoding apparatus 400 , decoding apparatus 400 can acquire information on the decoding target band, so that the amount of information transmitted from coding apparatus 300 to decoding apparatus 400 can be reduced.
Embodiment 4
[0145] In a decoding apparatus according to the present embodiment, if the start point or the end point of a speech signal is detected, the higher layer attenuates decoding transform coefficients located in a band having small energy of the spectrum of a decoded signal of the lower layer. This makes a decoding spectrum of the higher layer difficult to hear perceptually, the decoding spectrum occurring in the band having small energy of the decoding spectrum of the lower layer. That is, in the present embodiment, pre-echoes or post-echoes occurring in the higher layer are made difficult to hear on the decoding side by utilizing the temporal masking effect of the decoding spectrum of the lower layer. Accordingly, the pre-echoes or post-echoes do not need to be considered on the coding side, and a coding apparatus that performs general scalable coding can be used, so that the sound quality can be improved without particularly changing the configuration of the coding apparatus.
[0146] FIG. 21 is a block diagram showing a main part configuration of coding apparatus 500 according to the present embodiment.
[0147] First layer coding section 510 performs a coding process of an input signal, and generates first layer encoded data. First layer coding section 510 outputs the first layer encoded data to first layer decoding section 520 and multiplexing section 560 .
[0148] First layer decoding section 520 performs a decoding process using the first layer encoded data, generates a first layer decoded signal, and outputs the generated first layer decoded signal to subtracting section 540 .
[0149] Delaying section 530 delays the input signal by an amount of time corresponding to a delay that occurs in first layer coding section 510 and first layer decoding section 520 , and outputs the delayed input signal to subtracting section 540 .
[0150] Subtracting section 540 subtracts, from the input signal, the first layer decoded signal generated by first layer decoding section 520 to thereby generate a first layer error signal, and outputs the first layer error signal to second layer coding section 550 .
[0151] Second layer coding section 550 performs a coding process of the first layer error signal sent out from subtracting section 540 , generates second layer encoded data, and outputs the second layer encoded data to multiplexing section 560 .
[0152] Multiplexing section 560 multiplexes the first layer encoded data obtained by first layer coding section 510 with the second layer encoded data obtained by second layer coding section 550 to thereby generate a bit stream, and outputs the generated bit stream to a transmission channel (not shown).
[0153] FIG. 22 is a diagram showing an internal configuration of second layer coding section 550 .
[0154] Frequency domain transforming section 551 transforms the first layer error signal into a frequency domain, calculates first layer error transform coefficients, and outputs the calculated first layer error transform coefficients to gain coding section 552 .
[0155] Gain coding section 552 calculates gain information indicating the magnitude of the first layer error transform coefficients, and encodes the gain information to thereby generate gain encoded data. Gain coding section 552 outputs the gain encoded data to multiplexing section 554 . Gain coding section 552 also outputs decoding gain information obtained together with the gain encoded data, to shape coding section 553 .
[0156] Shape coding section 553 generates shape encoded data indicating the shape of the first layer error transform coefficients, and outputs the generated shape encoded data to multiplexing section 554 .
[0157] Multiplexing section 554 multiplexes the shape encoded data outputted by shape coding section 553 with the gain encoded data outputted by gain coding section 552 , and outputs the multiplexed data as the second layer encoded data. Note that multiplexing section 554 is not indispensable, and the shape encoded data and the gain encoded data may be outputted directly to multiplexing section 560 .
[0158] A main part configuration of the decoding apparatus according to the present embodiment is similar to that of Embodiment 3, and hence description is given with reference to FIG. 19 . The present embodiment is different from Embodiment 3 in an internal configuration of the second layer decoding section. Accordingly, in the following description, a second layer decoding section according to the present embodiment is denoted by 430 A.
[0159] FIG. 23 is a diagram showing an internal configuration of second layer decoding section 430 A according to the present embodiment. Note that, in second layer decoding section 430 A of FIG. 23 , components common to those of second layer decoding section 430 of FIG. 20 are denoted by the same reference signs as those of FIG. 20 , and description thereof is omitted.
[0160] Frequency domain transforming section 432 transforms the first layer decoded signal obtained by first layer decoding section 410 having high temporal resolution, into a frequency domain, to thereby calculate the first layer decoding transform coefficients, and band selecting section 433 A obtains a band whose energy of the spectrum is smaller than a predetermined threshold value, from the calculated first layer decoding transform coefficients. Then, band selecting section 433 A selects the obtained band as a band (attenuation target band) for which the second layer decoding transform coefficients are attenuated, and outputs information on the attenuation target band as selected band information to attenuating section 434 .
[0161] Attenuating section 434 attenuates the magnitude of the second layer decoding transform coefficients located in the band indicated by the selected band information, and outputs the second layer decoding transform coefficients after attenuation as second layer attenuated decoding transform coefficients to time domain transforming section 235 .
[0162] FIG. 24 is a diagram for describing processing in attenuating section 434 . The left chart of FIG. 24 shows the second layer decoding transform coefficients before attenuation, and the right chart of FIG. 24 shows the second layer decoding transform coefficients after attenuation (second layer attenuated decoding transform coefficients). As shown in FIG. 24 , the attenuating section attenuates the magnitude of the second layer decoding transform coefficients located in the band (attenuation target band) indicated by the selected band information.
[0163] As described above, in the present embodiment, if it is determined that the start point (or the end point) of an active speech portion of a lower layer decoded signal exists, second layer decoding section 430 A selects a band for which the decoding transform coefficients of the second layer decoded signal are attenuated, on the basis of energy of the spectrum of the first layer decoded signal, and attenuates the decoding transform coefficients of the second layer decoded signal in the selected band. As a result, even if the coding process is performed on the coding side without considering pre-echoes or post-echoes, because the relation between the first layer decoding transform coefficients and the second layer decoding transform coefficients corresponds to the relation between a masker signal and a maskee signal, the pre-echoes or post-echoes can be avoided.
[0164] Hereinabove, the embodiments of the present invention are described.
[0165] Note that the scalable coding including two coding layers is described above, but the present invention can also be applied to a scalable configuration including three or more coding layers.
[0166] In addition, in the above description, the bit stream outputted by coding apparatus 100 , 300 , 500 is received by decoding apparatus 200 , 400 , but the present invention is not limited thereto. That is, instead of the bit stream generated in the configuration of coding apparatus 100 , 300 , 500 , decoding apparatus 200 , 400 can also decode a bit stream outputted by a coding apparatus that can generate a bit stream containing encoded data necessary for decoding.
[0167] In addition, examples of the used frequency transforming section include discrete Fourier transform (DFT), fast Fourier transform (FFT), discrete cosine transform (DCT), modified discrete cosine transform (MDCT), and a filter bank. In addition, both a speech signal and a music signal can be applied as the input signal.
[0168] In addition, the coding apparatus or the decoding apparatus according to each of the above-mentioned embodiments can be applied to a base station apparatus or a communication terminal apparatus. In addition, in each of the above-mentioned embodiments, description is given of an example case where the present invention is configured in the form of hardware, but the present invention can be implemented in the form of software.
[0169] In addition, the respective functional blocks used in each of the above-mentioned embodiments are implemented typically as LSI as an integrated circuit. These functional blocks may be individually implemented on a chip, or may be partially or wholly implemented on a chip. The term LSI is used here, but the term IC, system LSI, super LSI, or ultra LSI may be suitably used depending on the degree of integration.
[0170] In addition, a technique of making an integrated circuit is not limited to LSI, and such integration may be implemented using a dedicated circuit or a general-purpose processor. It is also possible to utilize: field programmable gate array (FPGA) that can be programmed after LSI production; and a reconfigurable processor in which connection and settings of circuit cells inside of LSI can be reconfigured.
[0171] Moreover, if a technique of making an integrated circuit that can replace LSI appears along with progress in semiconductor technology or other related technology, as a matter of course, the functional blocks may be integrated using the technique. For example, application of biotechnology is possible.
[0172] The disclosure of Japanese Patent Application No. 2009-241617, filed on Oct. 20, 2009, including the specification, drawings and abstract, is incorporated herein by reference in its entirety.
INDUSTRIAL APPLICABILITY
[0173] The coding apparatus, the decoding apparatus, and the like according to the present invention are suitable for use in, for example, a cellular phone, an IP phone, and a video-conference.
REFERENCE SIGNS LIST
[0000]
100 , 300 , 500 Coding apparatus
110 , 310 , 510 First layer coding section
120 , 220 , 320 , 410 , 520 First layer decoding section
130 , 530 Delaying section
140 , 540 Subtracting section
150 , 420 Start point detecting section
160 , 160 A, 330 , 550 Second layer coding section
151 Sub-frame dividing section
152 Energy change amount calculating section
153 Detecting section
161 , 162 , 432 , 551 Frequency domain transforming section
163 , 163 A, 332 , 433 , 433 A Band selecting section
164 , 552 Gain coding section
165 , 553 Shape coding section
166 , 170 , 554 , 560 Multiplexing section
200 , 400 Decoding apparatus
210 , 231 , 431 Separating section
230 , 430 , 430 A Second layer decoding section
240 Adding section
250 Switching section
260 Post-processing section
232 Shape decoding section
233 Gain decoding section
234 Decoding transform coefficients generating section
235 Time domain transforming section
331 LPC spectrum calculating section
434 Attenuating section | Disclosed are an encoding device and a decoding device which suppress the occurrence of pre-echo artifacts and post-echo artifacts caused by a high layer having a low temporal resolution, and which implement high subjective quality encoding and decoding. An encoding device ( 100 ) carries out scalable coding comprising a low layer, and a high layer having a lower temporal resolution than that of the low layer. A start point detection unit (or end point detection unit) ( 150 ) determines the start point (or end point) of sections of the decoded low layer signal which have audio, and when the start point (or end point) is determined, a second layer encoding unit ( 160 ) selects a bandwidth to be excluded from encoding on the basis of the spectral energy from the decoded first layer signal, excludes the selected bandwidth, and encodes an error signal. | 6 |
CLAIM OF PRIORITY
This application is the U.S. National Phase of, and Applicants claim priority from, International Application Number PCT/CU2011/000005 filed Sep. 26, 2011 and Cuban Patent Application No. 2010-0188 filed Sep. 28, 2010, which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention falls within the field of veterinary medicine, in particular the control of ectoparasite infestations and their associated pathogens transmission. This control is achieved by using a peptide of the ribosomal protein P0 in the manufacture of vaccine compositions. The vaccine formulations comprising the peptide confer protection without generating autoimmunity in the host organism.
STATE OF THE PRIOR ART
Terrestrial bloodsucking ectoparasites such as mosquitoes, fleas and ticks are vectors for transmission of infectious agents causing diseases. Some of these diseases directly affect human and/or their affective animals, while others are causing great economic losses in the agricultural field. Examples of diseases transmitted by ectoparasites are malaria, leishmaniasis, dengue fever, ehrlichiosis and Lyme disease. Ticks are considered the second transmitter of diseases to humans after mosquitoes (P. Parola and D. Raoult, Clin. Microbiol. Infect. 2001, 7: 80-83). Haemoparasitic infections transmitted by ticks cause annual losses in the order of billions of U.S. dollars in the livestock industry, primarily affecting cattle production in tropical and subtropical areas. Among the diseases most important in this regard include anaplasmosis, babesiosis, Lyme disease (caused by Borrelia burdogferi ) and the so-called East Coast fever ( Theileria parva produced).
Ectoparasites known as sea lice ( Copepoda, Caligidae ) are the most widespread marine pathogen in the last 30 years in the salmon industry, ranging over the past 15 years other species of farmed fish and wild stocks of salmonids (Pike, A W and Wadsworth, S L Advances in Parasitology 2000, 44:233-337, Ragi, V. et al. Aquaculture 2004, 242: 727-733). The economic losses are caused by organisms of the genera Caligus and Lepeophtheirus . The so-called sea lice can cause physiological changes in their hosts, including the development of a stress response, reduced immune function, osmoregulation failure and death if untreated infection (Johnson, S C, et al. Zool Studies 2004, 43: 8-19). There is also some evidence to suggest that sea lice could be vectors for transmission of infections caused by viruses and bacteria to fish (Barker, E D, et al. Parasitology Research 2009, 105: 1173-1177).
A wide variety of chemicals and drugs have been used to control tick infestations and sea lice. The use of chemical pesticides as amidines, organophosphates, hydrogen peroxide and other currently constitutes the fundamental measure to control these ectoparasites. However, the intensive use of these chemicals has drawbacks as the contamination of food (fish, meat and milk), environmental pollution and development of resistance by ectoparasites (Y E Shahein Vet. Immunol. And Immunopathol. 2008, 121: 281-289, Denholm, I. Pest Manag Sci 2002, 58: 528-536, Bravo, S. et al. Aquaculture 2008, 282: 7-12, Lees et al. J. Fish Dis. 2008, 31: 947-951).
Vaccination is considered a promising alternative for controlling infestations by ectoparasites from the standpoint of efficacy, environmental safety and economic sustainability. The feasibility of using antigens produced by recombinant DNA techniques for this purpose has been demonstrated with Bm86-based commercial vaccines against Rhipicephalus microplus tick (TickGARD, Hoechst Animal Health, Australia, and Gavac marketed by Heber Biotec, Cuba). The latter has proven effective in field studies where the application is included within an integrated control program. In the case of sea lice there are some advances in the use of proteins as vaccine candidates, as is the case of akirin-2 of Caligus rogercresseyi , which is called my32. Challenging trials with my32 have been performed with promising results (Patent Application WO2008/145074 “Sequences of nucleic acids and amino acids, and vaccine for the control of infestations by ectoparasites in fish”).
Identification of novel protective antigens is the limiting step in increasing the effectiveness of these vaccines. Although emerging tick proteins have been identified recently, and have been proposed as potential protective molecules, only a limited number of them have been evaluated in vaccine trials as antigens produced by recombinant DNA techniques. In the case of sea lice which are ectoparasites that feed on mucus, skin and blood of the host and therefore have only limited contact with the host immune system (Boxaspen, K. ICES Journal of Marine Science 2006, 63: 1304-1316) have been investigated as vaccine candidates, the parasite immunomodulatory proteins that suppress the host immune response in the adhesion and feeding sites (Wikel, S K et al. “Arthropod modulation of host immune responses”. In: The Immunology of Host-Ectoparasiticide Arthropod Relationships. Editors: Wikel, S K, CAB Int, 1996, pp. 107-130). Have also studied other vitellogenin-like molecules and adhesion proteins to the host (Johnson, S C et al. Zool Studies 2004, 43: 8-19; Boxaspen, K. ICES Journal of Marine Science 2006, 63: 1304-1316) but due to poor knowledge of the mechanisms and pathology of the salmon infestation by sea lice, targets identification for prevention and treatment of this infection have not been successful. However, the research results in the evaluation of different vaccine candidates in immunization trials have shown that the combined use of several molecules involved in different physiological processes, is a feasible method to control ectoparasite infestations.
Eukaryotic ribosomes are composed of individual molecules of ribosomal RNA (rRNA) and more than 80 proteins organized into major and minor subunits. Most ribosomal proteins are basic (isoelectric point (pI)>8.5), but there is also a group of acidic proteins (pI=3.0 to 5.0) whichs form a stalk-like structure in the largest ribosome subunit. These acidic proteins are called P proteins (P0, P1 and P2), due to its ability to be phosphorylated, which plays a fundamental role in regulating translational activity of ribosomes (Wojda I. et al. Acta biochar. Pol. 2002, 49: 947-957). P proteins contain a conserved C-terminal region of about 17 amino acids, whose last six residues are highly conserved, which forms the basis of immunological cross-reactivity between them and the P proteins of other species. The P0 protein is essential for the assembly of 60S ribosomal subunit. P0 binds directly to P1, P2, 28S rRNA and the factor eEF2. Its absence leads to the generation of deficient ribosomes of the 60S subunit, which are inactive for protein synthesis, leading to cell death.
The P proteins are highly immunogenic and have been extensively studied in humans because of its association with autoimmune diseases and carcinogenesis. These applications of ribosomal proteins have been protected by patents by their respective authors. The ribosomal protein P0, in particular, is a promising vaccine candidate against several protozoa and bacteria. It was immunogenic as recombinant antigen (either using the whole protein or C-terminal region consisting of the last 11-16 amino acids) or by naked DNA immunization against Toxoplasma gondii, Neospora caninum (H. Zhang et al. Mol. Biochem. Parasitol 2007, 153: 141-148), Trypanosoma cruzi (Skeiky Y A et al. J. Immunol. 1993, 151: 5504-5515), Leishmania infantum (S. Iborra et al., Infect. Immunol. 2003, 71: 6562-6572 and 2005, 72: 5515-5521) and several species of Babesia (Terkawi M A et al., Vaccine 2007, 25: 2027-2035; Terkawi M A et al. Parasitol. Res 2007, 102: 35-40) and Plasmodium (S. Chatterjee et al. Infect. Immunol. 2000, 68: 4312-4318; Rajeshwari K. et al. Infect. Immunol. 2004, 72: 5515-5521). The immune response obtained in most of these experiments was characterized by the generation of high titers of specific antibodies, capable of conferring active and passive protection against infection, activation of T lymphocytes and the gamma interferon production (IFNγ) as part of a Th1 response pattern.
Its use as an immunogen against various bacteria and protozoa, without the report of autoimmune reactions in the host was due to the relatively low amino acid sequence identity of this protein between these microorganisms and mammals. The most striking case was the immunization of mice with a peptide consisting of the last 16 amino acids of P0ribosomal protein of Plasmodium falciparum (Rajeshwari K. et al., Infect. Immunol. 2004, 72: 5515-5521), which presents 68% identity with the C-terminus of this same protein in mice. However, the use of this whole protein or its C-terminal region as immunogens to control ticks and sea lice infestations is limited by the high degree of amino acid identity that exists for this antigen among ectoparasites and their host organisms.
Recent experiments with specific interference RNA silencing expression of this protein in Haemaphysalis longicornis ticks showed a significant decrease in weight gain of ticks, and a mortality of 96%, caused by structural level affectations of salivary gland and cuticle, suggesting that P0 ribosomal protein is necessary for the ingestion of blood and viability of ticks and possibly of other ectoparasites (Gong H et al. Vet. Parasitol. 2008, 151: 268-278). However, the development of a vaccine candidate based on this antigen has as drawbacks the high degree of identity between the reported sequences of host vertebrates and his ectoparasites such as ticks and sea lice, which is higher in the C-terminus of the protein. This can result in the induction of tolerance or the generation of autoantibodies in the host organism.
The intensive use of chemicals and drugs to control infestations of ticks and sea lice has drawbacks as the contamination of food with chemical residues, environmental pollution and the development of resistance by ectoparasites. Therefore, vaccination is considered a promising alternative and there is a need to identify new vaccine antigens that are capable of conferring protection by itself or can be incorporated into existing vaccines.
SUMMARY OF THE INVENTION
The present invention solves the above problem by providing a vaccine composition for the control of infestations by ectoparasites comprising a peptide of the P0 ribosomal protein of these ectoparasites. This composition comprises as antigen, an immunogenic region of the P0 ribosomal protein that is little conserved among ectoparasites and the organisms affected by them, according to results of a study to be disclosed in this invention, the first time. The region identified in the P0 ribosomal protein is between 267 and 301 amino acids of the same.
The presence of P0 protein in all organisms as a structural component of ribosomes and essential for cell viability is an advantage for the use of these sequences with the objective to obtain vaccine candidates against different species of ectoparasites. However, the use of this protein or its C-terminal region as immunogen to control infestations of ticks and sea lice is limited by the high degree of amino acid identity that exists for this antigen among ectoparasites and their host organisms.
This situation is avoided for the first time in this invention, by identifying highly immunogenic regions within the protein, which coincide with areas of low sequence similarity between these groups of organisms. By bioinformatics' predictions, it was found that this region coincides with an area of low hydrophobicity and high degree of accessibility of protein, which makes likely this amino acid sequence to be exposed.
Complementary DNAs (cDNA) were generated by reverse-transcription starting from total RNA of Rhipicephalus microplus and R. sanguineus larvae and adult sea lice from Caligus rogercresseyi specie. The nucleotide sequences encoding P0 ribosomal protein of these ticks (SEQ ID NO. 1 and SEQ NO. 2) and that sea lice were amplified by Polymerase Chain Reaction (PCR) using these cDNAs and specific oligonucleotides.
The polypeptide sequences for P0 protein of ectoparasites R. microplus and R. sanguineus were identical between them, and were designated as SEQ ID NO. 3. This sequence and that of the C. rogercresseyi's P0 showed a sequence identity greater than 70% with the P0 proteins of its host organisms, while still higher for the last 16 amino acids of the C-terminal, described as the most immunogenic within the protein. The lesser similarity area in amino acid sequence, which in turn is likely to be exposed and be immunogenic, was detected in all cases in the region between amino acids 267 and 301 (SEQ ID NO.4, peptide corresponding P0 protein of Rhipicephalus microplus [pP0] SEQ ID NO.6, peptide corresponding P0 protein of Ixodes scapularis [pP0Is] SEQ ID NO.8, peptide corresponding P0 protein of Caligus clemensi [pP0Cc], SEQ ID No.9, peptide corresponding P0 protein of L. salmonis [pP0Ls] and SEQ ID NO.10, peptide corresponding P0 protein of C. rogercresseyi [pP0Cr]).
Therefore, in one embodiment of the invention, the vaccine composition comprises a peptide with an amino acid sequence identified as SEQ ID NO. 4, SEQ ID NO. 6, SEQ ID NO. 8, SEQ ID NO. 9 or SEQ ID NO. 10, a fragment of those sequences, or a peptide or polypeptide that exhibits at least 70% identity with such sequences. The present invention relates also to those vaccine compositions where the indicated P0 peptide is fused, is combined or co-administered with another molecule, to increase their immunogenicity or enhance their protective effect. Such molecules are carrier proteins and immune-carriers. In one embodiment of the invention, this molecule is selected from the group consisting of hemocyanin, T-cell epitopes, the proteins that form virus-like particles, Bm86 protein from the R. microplus tick, the Rs86 protein from the R. sanguineus tick and my32 protein of C. rogercresseyi or L. salmonis . sea lice.
The peptides identified as SEQ ID NO. 4, 6, 9 and 10, between 35 and 36 amino acids, and 20 amino acids fragments of these were obtained by chemical synthesis and conjugated to hemocyanin (Keyhole Limpet Hemocyanin English, abbreviated as KLH) of Megathura crenulata , to enhance immunogenicity. Immunization experiments with challenge under controlled conditions were conducted with these conjugates to assess their protective capabilities. P0 peptide (pP0-SEQ ID NO. 4) was tested against R. sanguineus and R. microplus in rabbits and cattle, respectively. pP0Is (SEQ ID NO. 6) was evaluated against I. scapularis in rabbits. For its part, the peptides pP0Ls and pP0Cr (SEQ ID NO. 9 and SEQ ID NO.10, respectively) were evaluated against L. salmonis and C. rogercresseyi , respectively, both in Salmo salar.
Immunization of rabbits and cattle with the vaccine formulation containing the protein conjugate (pP0-KLH) and adjuvant Montanide 888 was able to induce a strong specific humoral immune response against the peptide in both cases. There was no evidence of the occurrence of an autoimmune specific response in experimental animals used, which was triggered by the recognition and reactivity of the P0 protein of these mammals by the antibodies generated against the pP0 peptide. This was confirmed by an “in vitro” cross-reactivity test in the RK-13 cell line of rabbit kidney, using hyperimmune serum against the peptide obtained in mice. Vaccinations with pP0-KLH conjugate induced protection against infestations by R. sanguineus and R. microplus , causing structural damages and affected biological parameters in both species of ticks. In addition, similar results were obtained against I. scapularis ticks after immunization with the synthetic peptide of the P0 protein of this tick (pP0Is) conjugated to hemocyanin.
The vaccination of salmon with pP0Ls-KLH and pP0Cr-KLH conjugates induced protection against infestations by both species of sea lice, as evidenced by a significant decrease in the number of parasites per fish. Immunization experiments were also conducted with pP0 and pP0Cr obtained by recombinant techniques, fused to the T epitopes of tetanus toxin and the fusion protein of measles virus (Measles Virus Fusion English protein, abbreviated MVF) in the same gene construct. As a result of immunization experiments with these chimeric antigens, in the case of sea lice, we found that fusion to the promiscuous T epitopes significantly improves the protection in comparison with antigen conjugated to KLH.
The pP0 was also fused to virus-like particles (VLPs) of Rabbit Hemorrhagic Disease Virus (RHDV), and found further that when the P0 peptide is fused to Bm86 antigen, the protective effect of the peptide is enhanced. This could be due to the combined effect of the antibodies produced against both immunogens and/or the fact that the structural damage caused by antibodies directed against the Bm86 antigen, at the gut of ticks, facilitates the action of specific antibodies against the peptide of P0 ribosomal protein. On the other hand, pP0Cr was fused to the my32 protein in another gene construct, and in this case, the most relevant effects on damages to C. rogercresseyi were obtained, presumably by enhancing of the individual specific effect of the two antigens.
Thus, in the invention was demonstrated that the vaccine compositions based on the pP0 peptide are effective for controlling infestations by ectoparasites such as ticks and sea lice. Therefore, pP0 based compositions are also useful for controlling the transmission of pathogens associated with these ectoparasites.
This vaccine comprises immunologically effective amount of antigen in a pharmaceutically acceptable adjuvant, by which to control infestations by these pathogens. As stated, the antigen in this vaccine is a peptide of the P0 ribosomal protein of these ectoparasites, between 267 and 301 amino acids, which corresponds to the region of least similarity in the amino acid sequence of the ectoparasite protein with the same region of the protein in their respective host organisms. This peptide is obtained by recombinant techniques or by chemical synthesis. Fused polypeptides comprising the P0 peptide can also be obtained by recombinant techniques. As known to those versed in this field of technology, the production of such antigens by recombinant means can use an expression system in yeast, bacteria, plants, insect larvae, insect cells or mammalian cells.
In one embodiment of the invention, the vaccine compositions may further comprise a vaccine adjuvant. In the context of the invention, vaccine formulations were evaluated comprising an oily adjuvant type. However, as adjuvants can be used aluminum salts, liposomal vesicles, immune system related molecules such as cytokines, among others.
The compositions of the invention can be administered in many different ways. In one embodiment of the invention, the composition is administered by injection. In another embodiment, formulations are administered through feed. In the event that the compositions are administered to fish can be applied using immersion baths.
Another object of the present invention is a vaccine composition for controlling infestations by ectoparasites comprising nucleic acids encoding the peptide of P0 ribosomal protein of these ectoparasites, corresponding to the region between 267 and 301 amino acids of the protein, and generates an immune response against the peptide by immunization with naked DNA. In one embodiment of the invention, this peptide has an amino acid sequence identified as SEQ ID NO. 4, SEQ ID NO. 6, SEQ ID NO. 8, SEQ ID NO. 9 or SEQ ID NO. 10, or it is a fragment of those sequences, or a peptide or polypeptide that exhibits at least 70% identity with such sequences.
The invention also relates to the use of the region between 267 and 301 amino acids of P0 ribosomal protein of ectoparasites in the manufacture of a vaccine composition to control infestations by these parasites or pathogens associated to them. In one embodiment, said peptide has an amino acid sequence identified as SEQ ID NO. 4, SEQ ID NO. 6, SEQ ID NO. 8, SEQ ID NO. 9 or SEQ ID NO. 10, or it is a fragment of those sequences, or a peptide or polypeptide that exhibits at least 70% identity with such sequences.
Advantages of the Proposed Solution
The present invention demonstrates the protective capacity of a vaccine formulation, which contains a peptide between amino acids 267 and 301 of the P0 ribosomal protein of different ectoparasites, against ticks as R. microplus, R. sanguineus and I. scapularis , and ectoparasites known as L. salmonis and C. rogercresseyi sea lice, without the occurrence of cross-react with the same protein in the host organisms. In all immunizations, the pP0 was administered conjugated or fused to an immune-carrier molecule to enhance the immune response of animals. In the case of ticks, the application of this peptide (or fragments thereof) fused to the Bm86 protein or combined with it, induces a greater damage on the viability and biological parameters of these arthropods than the damages caused by antigens when used individually. Therefore, the application of this chimera protein or combination of them as part of an integrated control program, could result in greater control of infestations by these or other tick species as well as in reducing the incidence of tick borne haemoparasitic diseases. In the case of sea lice, the greatest damages was observed when the pP0Cr was fused to promiscuous T epitopes and my32 protein. The high conservation degree of the peptide amino acid sequence among most arthropod species and sea lice, and low identity of this sequence with the corresponding fragment of the protein in mammals and fish, makes this peptide of P0 ribosomal protein (or fragments thereof) an antigen for the development of vaccines against ectoparasites.
BRIEF FIGURE DESCRIPTIONS
FIG. 1 . Prediction of the accessibility degree of amino acid residues in the P0 ribosomal protein of R. microplus and R. sanguineus . The region corresponding to the sequence defined as SEQ ID NO.4 is marked with a circle.
FIG. 2 . Anti-P0 peptide specific IgG antibody response, detected by ELISA in serum of BALB/c mice immunized with the conjugate pP0-KLH. Data are expressed as the reciprocal of the antibody titer average, determined as the last serum dilution with an average optical density (OD) greater than three times the mean OD of negative serum. Standard deviations are represented by error bars in the positive direction. No antibody titers were detected for any animals on day zero.
FIG. 3 . Expression Pattern of P0 ribosomal protein of Rhipicephalus ticks in RK-13 rabbit cell line analyzed by Western blotting with polyclonal antibody generated in mice against P0. 1. Molecular weight standard, 2. Lysate of RK-13 cells transfected with pAdTrack-P0Rs plasmid under reducing conditions, 3. Lysate of RK-13 cells transfected with pAdTrack-P0Rs plasmid in non-reducing conditions, 4. Lysate of RK-13 cells non transfected under reducing conditions, 5. Polyacrylamide gel electrophoresis in the presence of sodium Dodecilosulfato (SDS-PAGE) under reducing conditions of the RK-13 cells lysate transfected with the plasmid pAdTrack-P0Rs.
FIG. 4 . Anti-KLH, anti-peptide P0 and anti-Bm86 IgG antibody responses detected by ELISA in serum from rabbits immunized with these antigens (Example 6). Data are expressed as the reciprocal of the average of antibody titer, determined as the last serum dilution with an average OD greater than three times the average OD of negative control groups according the case. Standard deviations are represented by error bars in the positive direction. Specific antibody titers against the antigens were not detected for any animals on day zero of the trial.
FIG. 5 . Recovery of R. sanguineus larvae, nymphs and adults in rabbits immunized in Example 6. Data are expressed as the average percentages of larvae, nymphs and adults recovered in the different experimental groups. The standard deviations of the groups are represented by error bars in the positive direction. Different letters represent statistically significant differences between the experimental groups (ANOVA and Bonferroni multiple comparison test [P<0.01]. For the analysis, proportions data were previously transformed to arcsine of its square root).
FIG. 6 . Newly molted nymphs of R. sanguineus from larvae fed on different experimental groups of Example 6. (A) Negative control group (B) Immunized with Bm86 (C) Immunized with the conjugate pP0-KLH and (D) Appearance of dead nymphs molted from larvae fed on rabbits immunized with pP0-KLH.
FIG. 7 . Aoves hatch percent of R. sanguineus from teleoginas fed on rabbits immunized in Example 6. Data are expressed as the mean per group. The standard deviations for each group are represented by error bars in the positive direction. Significant differences are indicated by an asterisk (ANOVA and Bonferroni multiple comparison test (p<0.05).
FIG. 8 . Anti-P0 peptide IgG antibody response (A) and survival of R. sanguineus larvae, nymphs and adult (B) for the rabbits immunized with variants of this peptide fused to different immune-carrier molecules. Standard deviations are represented by error bars in the positive direction.
FIG. 9 . Expression pattern of the Bm86-pP0 chimeric protein in the P. pastoris MP36 strain rupture precipitate analysed by Western blotting using hyperimmune sera generated against the peptide pP0 (A) and against the Bm86 protein (B). In both cases, line 1. Rupture precipitate under reducing conditions, 2. Rupture precipitate in non-reducing conditions, 3. Deglycosylated protein by digestion with the PNGase F enzyme.
FIG. 10 . Anti-peptide P0 and anti-Bm86 IgG antibody response, detected by ELISA in serum from cattle immunized with these antigens individually, combined or with the Bm86-pP0 chimeric protein. Data are expressed as the reciprocal of the antibody titer average, determined as the last serum dilution with an average OD greater than three times the OD average of negative control group. Standard deviations are represented by error bars in the positive direction. No antibody titers were detected for any groups at the beginning of the experiment.
FIG. 11 . Average weight of R. microplus aove and teleoginas fed over cattle immunized in the Example 8. The statistically significant differences between experimental groups and each group compared to negative control are represented by different letters (ANOVA and Newman-Keuls multiple comparison test [p<0.05]).
FIG. 12 . Anti pP0Is IgG antibodies response detected by ELISA in the serum of rabbits immunized with this antigen and subsequently challenged with I. scapularis . Data are expressed as the reciprocal of the antibody titer average, determined as the last serum dilution with an average OD greater than three times the average OD of negative control group. Standard deviations are represented by error bars in the positive direction. No antibody titers were detected for either group on day zero of the trial.
FIG. 13 . Behavior of the biological parameters of I. scapularis in rabbits immunized with pP0Is-KLH conjugate. The larvae viability and recovery of nymphs and adult are represented (A) and the percentage of hatching aoves (B). Data are expressed as the mean per group. Standard deviations are represented by error bars in the positive direction. Statistically significant differences with respect to the negative control group are represented by asterisks (ANOVA and Bonferroni multiple comparison test [p<0.05]).
DETAILED DESCRIPTION OF EMBODIMENTS
EXAMPLES
Example 1
Amplification and Cloning of the Nucleotide Sequences Coding for P0 Ribosomal Protein of R. microplus, R. sanguineus and C. rogercresseyi
Complementary DNAs (cDNAs) were obtained by reverse-transcription reaction from total RNA of R. microplus and R. sanguineus larvae and C. rogercressey adults. The reactions were carried out following the instructions in the “Reverse Transcription System” kit (Promega, USA # A3500). Nucleotide sequences that encode P0 ribosomal protein of R. microplus and R. sanguineus (SEQ ID No. 1 and SEQ ID No. 2) and P0 sequence of C. rogercresseyi were amplified by Polymerase Chain Reaction (PCR) from the obtained cDNAs. As PCR primers for ticks were used synthetic oligonucleotides designed from the nucleotide sequence reported in Genebank for the P0 protein of Haemaphysalis longicornis under the accession number EU048401:
(SEQ ID NO: 17)
Forward Oligonucleotide:
5′ ATGGTCAGGGAGGACAAGACCACCTGG 3′
(SEQ ID NO: 18)
Reverse Oligonucleotide:
5′ CTAGTCGAAGAGTCCGAAGCCCATGTCG 3′
As primers for amplification from C. rogercresseyi cDNA were used degenerate synthetic oligonucleotides designed from the nucleotide sequences reported in the Genebank for the P0 protein of different ticks species ( Haemaphysalis longicornis and Ixodes scapularis ) and insects ( Drosophila melanogaster, Culex quinquefasciatus and Aedes aegypti ):
Forward Oligonucleotides:
F1
5′ ATGGGCAAGAACAC(C/G)ATGAT(C/G)ACMC(G/A)GC 3′
F2
5′ ATGG(T/G)(T/C)AGGGAG(G/A)ACAA(G/A)(A/G)C
(C/A/T)(G/A)C(C/G)TGGAA 3 ′
Reverse Oligonucleotide:
R1
5′ TC(G/A)AA(A/C/G)AG(G/A/T)C(C/T)GAA(T/G/A)
CCCAT(A/G)TC(A/G)TC 3′
As a result of reactions with complementary DNA from ticks obtained a DNA band of approximately 957 bp in both cases, which were cloned into the commercial vector pGEM-Teasy (Promega, USA) for sequencing. For the PCR reaction from complementary DNA of C. rogercresseyi , we obtained a DNA band of approximately 780 bp for the combination of primers F1-R1 and a band of approximately 960 bp for the combination of oligonucleotides F2-R1. In both cases the bands were cloned into the commercial vector pGEM-Teasy (Promega, USA) for sequencing.
Example 2
Bioinformatic Analysis
Analysis of amino acid sequence identity were performed using BlastX and ClustalW programs. The deduced 318 amino acid sequences from the amplified DNA sequences of the ticks cDNA were identical between them (SEQ ID NO. 3) and showed a 95% and 93% identity compared to the sequences of P0 ribosomal protein of Haemaphysalis longicornis and Ixodes scapularis (Genebank, accession number DQ066213), respectively. This sequence also showed 96% identity with the polypeptide sequence deduced from partial reading frame included in the TC533 of the Amblyoma variegatum database, and 99% with those deduced from two open reading frames contained in the TC1424 and TC9038, the databases of ESTs from R. appendiculatus and R. microplus , respectively.
The polypeptide sequence corresponding to the P0 protein of R. sanguineus and R. microplus referred as SEQ ID NO. 3 also shows a sequence identity of 70% with the bovine P0 ( Bos taurus , AAX09097 Genebank accession number), being 87% for the last 16 amino acids of the C-terminal region, described as the most immunogenic in the protein. This sequence also shows a sequence identity of 71% with the dog P0 protein ( Canis familiaris , Genebank accession number XM535894).
In the case of the deduced P0 amino acid sequence from the cDNA sequence of C. rogercresseyi , we observed a high identity percentage with the reported sequences for other species of sea lice as C. clemensi and L. salmonis . As in the case of ticks and their hosts, there was a high sequence identity between the P0 of sea lice with respect to Salmo salar P0 (Genebank accession number ACI70184).
The high sequence identity between the P0 of these ectoparasites with respect to host P0 makes it very risky to use this molecules as a vaccine antigen to control their infestations, due to the possibility of generating autoimmunity against the protein of the host. This risk is increased for the use of C-terminal region (last 11-16 amino acids), which is highly conserved among all organisms.
The region of the P0 protein of both species of ticks that has less sequence similarity with mammalian P0 proteins is between amino acids 267 and 301 (SEQ ID NO.4). Using bioinformatics tools, it was found that this region of the protein coincides with an area of low hydrophobicity, which has high chances of being exposed in protein ( FIG. 1 ). Subsequently, we evaluated the immunogenicity of this peptide and its utility as a vaccine antigen to control infestations by these or other species of ticks.
By translating the sequence of the cloned gene that encodes the P0 protein of Caligus rogercresseyi sea lice, it was identified a similar peptide with low homology to Salmo salar P0 in the same region between amino acids 267 and 301 (SEQ ID NO. 10, pP0Cr). In addition, these were also identified the same regions of lower amino acid similarity (SEQ ID NO. 8 and 9, pP0Cc and pP0Ls) in reported P0 protein for Caligus clemensi (Genebank accession number ACO14779) and Lepeophtheirus salmonis (Genebank, accession number ACO12290).
Example 3
Synthesis of Peptides and Conjugation to the KLH
The peptides identified as SEQ ID NO. 4, SEQ ID NO. 9 and SEQ ID NO.10, and fragments of 20 amino acids of these peptides were obtained by chemical synthesis and purified by reverse phase chromatography using an HPLC system (High Pressure Liquid Chromatograph). We obtained 15 mg of each synthetic peptide with a purity of 99.3%. The molecular mass of each was verified by mass spectrometry.
In order to enhance the immunogenicity of the peptides were fused to the KLH protein. The conjugations of the synthetic peptides to KLH were performed using the soluble carbodiimide method. The succinic anhydride was used as spacer agent. The separation of the conjugates was performed by gel filtration chromatography. The final concentration of each conjugate was estimated by the bicinchoninic acid method.
Example 4
Obtaining Hyperimmune Mouse Serum Against the Peptide of P0 Ribosomal Protein of R. microplus and R. sanguineus (pP0)
Six Balb/c, male, 6 weeks old mice with body masses between 18 and 22 g were used in the experiment. They were immunized subcutaneously on days 0, 14, 21 and 28 with 250 μg of pP0-KLH conjugate (equivalent to 125 μg of peptide and 125 μg of KLH) in Freund's adjuvant. Blood draws were performed on days 0, 7, 14, 21, 40 and 65. The animals were bled on day 65 and sera were obtained by centrifugation for 10 minutes at 3500 rpm.
The antibody kinetic was monitored by an indirect ELISA. For the plate coating was used 1 ug per well of pP0 and detection was performed with an anti-mouse IgG conjugated to horseradish peroxidase at 1:15000 dilution. Developing was carried out using a substrate solution containing o-phenylenediamine 0.4 mg/mL in 0.1 M citric acid and 0.2 M Na 2 HPO 4 , pH 5.0 and 0.015% hydrogen peroxide. The reaction was stopped with 2.5 M H 2 SO 4 . The antibody titer was established as the reciprocal of the highest dilution at which mean OD of the serum in question is three times the mean OD of negative control serum.
The immunized animals showed specific antibody titers against the peptide from day 14 of the experiment, which came to be 1:10240 to two of the animals on day 65 ( FIG. 2 ). A mixture containing equal amounts of hyperimmune sera obtained from six immunized mice with the pP0-KLH conjugate was used as a polyclonal antibody in expression and cross-reactivity “in vitro” assays.
Example 5
Expression of the P0 Ribosomal Protein of Rhipicephalus Ticks in RK-13 Cell Line and Cross-Reactivity “In Vitro” Assay
The DNA sequence that codes for P0 ribosomal protein of R. sanguineus (SEQ ID NO.2) was cloned in the plasmid pAdTrack-CMV (9.2 kb), under the control of the immediate/early promoter/enhancer of the human cytomegalovirus (pCMVITh) and late termination/polyadenylation signal of the simian vesicular virus (SV40). This vector contains in its sequence the reporter gene encoding green fluorescent protein (GFP) and the gene conferring kanamycin resistance (He T C et al., Proc Natl Acad Sci U.S.A. 1998, 95: 2509-2514). The resulting plasmid was used to transfect RK-13 cell line of the rabbit kidney. Transfection was performed using lipofectamine (Invitrogen, USA) according to manufacturer's instructions. The transfection efficiency was determined after 24 hours, by observing the GFP expression at the optical microscope using ultraviolet light and a 40× magnification.
Cell lysis was performed after 48 h. Cell extracts were obtained and subjected to electrophoresis on 10% polyacrylamide gel (SDS-PAGE) using reducing and denaturing conditions as described by Laemmli (Laemmli U K, Nature 1970, 227: 680-685).
The expression pattern of P0 ribosomal protein of Rhipicephalus ticks was analyzed by Western blotting, using as primary antibody the polyclonal serum against the peptide obtained in mice (diluted 1:3000) and as secondary antibody an anti IgG-mouse conjugated to peroxidase in dilution 1:10000 ( FIG. 3 ). In the sample corresponding to plasmid transfected cells was detected a single band of the expected size for the P0 protein of approximately 35 kDa. The presence of a similar band in the sample run in non-reducing conditions indicated that this peptide is exposed in the three-dimensional protein structure. There was no detectable band in the lane corresponding to the negative control sample (untransfected rabbit RK-13 cells), indicating that the antibodies generated in mice against the 35 amino acids peptide of the P0 protein of Rhipicephalus ticks cannot recognize the peptide corresponding to the rabbit P0 protein. It showed the absence of cross-reactivity between tick immunogenic peptide and the peptide corresponding to the rabbit P0 ribosomal protein.
Example 6
Immunogenicity Determination of the pP0 Peptide of Rhipicephalus Ticks and their Protective Capacity Against Infestations of R. sanguineus Ticks
We proceeded to evaluate the usefulness of P0 ribosomal protein peptide of R. microplus and R. sanguineus as vaccine antigen against the R. sanguineus tick. To this end, 20 white New Zealand male rabbits aged between 12 and 14 weeks and body mass of 2.5 kg were randomized into three experimental groups of seven rabbits to groups immunized with Bm86 and pP0-KLH and 6 rabbits for the negative control group immunized with KLH. The immunogens contained in PBS1× were adjuvanted in VG Montanide 888 (prepared to 10% in mineral oil) in a 60/40 proportion of immunogen/adjuvant. The experimental groups were distributed as follows:
Group 1: Subcutaneous immunization with conjugate pP0-KLH at doses of 500 μg/animal (equivalent to 250 mg peptide/animal) on days 0, 21, 36 and 60.
Group 2 (negative control): Subcutaneous immunization with KLH in doses of 250 μg/animal on days 0, 21, 36 and 60.
Group 3 (positive control): Subcutaneous immunization with the R. microplus Bm86 protein in doses of 100 μg/animal on days 0 and 28.
The trial lasted 120 days. Serum samples were taken to the animals to measure the antibody response on days 0, 14, 21, 28, 36, 59, 73 and 87. The general behavior and body temperature of the animals were observed daily throughout the test. Three cameras were placed per animal on day 72 of the experiment and each animal was infested on day 73 with approximately 250 larvae, 100 nymphs and 50 adults (20 males and 30 females) of R. sanguineus tick. The collection, counting, weighing and molt analyze of ticks was performed between days 75 and 120. The larvae and nymphs collected were kept in an incubator at 28° C. with 80% relative humidity and a photoperiod of 12:12 h (light: dark). The engorged female teleoginas were kept immobilized in individual plastic plates until oviposition in the same conditions.
There was no change in normal behavior, or fever in any of the animals. The humoral response generated against each of the immunogens was assessed by indirect ELISA similar to that described above, coating the plates with 1 μg per well of each antigen. In this case, an IgG anti-rabbit conjugated to peroxidase (SIGMA) was used to develop ELISA in 1:10000 dilutions. The antibody titer mean was determined from individual values in each group. Specific titers against Bm86 were obtained only in animals of group 3 immunized with Bm86. Specific anti-peptide P0 (pP0) titers were obtained only in group 1, which the animals were immunized with pP0-KLH conjugate and specific anti-KLH titers were obtained in groups 1 and 2 immunized with the pP0-KLH conjugate and KLH alone, respectively ( FIG. 4 ).
To study the effect of the immunogens over R. sanguineus ticks, the behavior and biological parameters of them were analyzed. The mean feed time and recovery was analyzed in larvae, nymphs and adults. Molting and the capacity of later stage obtained to infesting a virgin animal were also examined in the case of larvae and nymphs. For adults, we studied also the engorged female weight, the egg weight and its hatching rate. The efficiency of conversion to eggs was calculated as described previously (G F Bennett et al.; Acarology 1974, 16: 52-61), the female weight percentage become to eggs. In general, larvae, nymphs and adults fed over Bm86 immunized rabbits took longer time to eat than the same stages fed over the control and vaccinated with the P0 peptide animals. The recovery of larvae, nymphs and adults among groups was compared by ANOVA and Bonferroni multiple comparisons test (p<0.01). In the cases of larvae and nymphs, survival or viability was analyzed as the final amount of the next stage that was able to infect naive animals with respect the number of larvae and nymphs molted. For adults, viability was measured as the final number of ticks capable of surviving after incubation with the capacity to lay eggs. The mean recovery of larvae showed no statistically significant differences between the experimental groups. In the case of nymphs recovery, despite a tendency to recover less nymphs fed on the groups immunized with both pP0-KLH and Bm86 than nymphs fed over the control group immunized with KLH, there were no statistically significant differences. In the case of adults, recovery showed statistically significant differences for the group vaccinated with the antigen pP0 relative to negative control and vaccinated with Bm86 groups ( FIG. 5 ).
There were serious effects on the viability and appearance of newly molted nymphs from larvae fed in groups vaccinated with both antigens (pP0-KLH and Bm86) compared to the control group collected. The group vaccinated with the pP0-KLH showed a high mortality of newly molted nymphs with a clear involvement of the morphology. Statistically significant differences were found in the viability between groups vaccinated with the PP0-KLH and Bm86 compared to negative control group. There are also significant differences in viability between the group vaccinated with Bm86 and the group vaccinated with pP0-KLH ( FIG. 6 ). Table 1 shows the mortality percentages in each experimental group.
TABLE 1
Mortality Percentages of newly molted nymphs from
larvae fed over the three experimental groups.
Stages
Mortality (%)
pP0-KLH
77.70 b
KLH
13.45 a
Bm86
44.70 c
Different letters mean statistically significant differences obtained by ANOVA followed by Bonferroni multiple comparison test (P < 0.001) of the transformed data.
The ability of newly molted nymphs and adults and newly hatched larvae from experimental groups to infect a new animal was determined by the infestation of virgin dogs with recovered, molted and viable specimens for each experimental group. No statistically significant differences were found for this parameter between the experimental groups.
Statistical analysis of teleogina and egg weight data was performed using ANOVA and Bonferroni multiple comparison test (p<0.05). No significant differences were found for both parameters between experimental groups. The efficiency of conversion to eggs was not significantly different between the vaccinated groups and control group. At this point, we note that 10% of adults fed on rabbits immunized with pP0-KLH did not lay eggs; about 3% in the control group immunized with KLH and 6% did not lay eggs in the group fed on rabbits immunized with Bm86. There were statistically significant differences (p<0.01) in % of eggs hatched in the group immunized with pP0-KLH respect to the control group immunized with KLH (FIG. 7 ). Although the eggs lay by teleoginas fed on the group immunized with Bm86 were hatching a percent lower than in the negative control group, these differences were not significant from a statistical point of view. Larvae hatched from the eggs of the three experimental groups were able to infest dogs and eat normally.
Experiments were conducted with results similar to those previously described in this example, immunizing rabbits with fragments of 20 amino acids of the pP0. The peptides tested have the following amino acid sequences: AAGGGAAAAKPEESKKEEAK (SEQ ID NO: 11) EYLKDPSKFAAAAAPAAGGG (SEQ ID NO: 13) and FAAAAAPAAGGGAAAAKPEE (SEQ ID NO: 12). These peptides were conjugated to KLH. The best results were obtained with the peptide corresponding to the last 20 amino acids of the pP0.
Example 7
Immunogenicity determination of R. microplus and R. sanguineus pP0 Fused to Different Immunopotentiator Molecules
The VP60 capsid protein of RHDV (strain AST/89) was obtained with high expression levels in the rupture supernatant of the Pichia pastoris yeast. This protein generated by recombinant techniques forms high molecular weight multimers with antigenic and structural features similar to the native viral particle (Farnós O. et al.; AntiVir. Res 2009, 81: 25-36). Taking advantage of the high immunogenicity of these virus-like particles (VLPs), a recombinant DNA construct for the pP0 exposed on the surface of the RHDV VLPs was generated. To this end, the nucleotide sequence encoding the 20 aa fragment from position 15 to 35 of the SEQ ID No.4 of this peptide (AAGGGAAAAKPEESKKEEAK) was inserted into the pNAOVP60 plasmid in the protruding domain position of VP60 protein gene. This construction allows the pP0 is expressed fused to the C-terminus of VP60, a region that is exposed to the outside after the assembly of VLPs. The recombinant plasmid obtained was used to transform the MP36 strain of P. pastoris . The VP60pP0 protein was obtained soluble in the breaking supernatant at levels of 350 mg/L. Exposure of the C-terminal region and the formation of VLPs were verified by a sandwich ELISA using an anti-RHDV hyperimmune sera and 6H6 and 1H8 monoclonal antibodies (kindly donated by Dr. Lorenzo Capucci Istituto Zooprofilattico Sperimentale della Lombardia, Brescia, Italy) which recognize epitopes present in the VP60 protein C-terminus and viral particles or VLPs assembled correctly (L. Capucci et al.; Virus. Res 1995, 37: 221-238). VP60pP0 VLPs were purified by HPLC on a TSK-G3000PW, obtaining a purity of approximately 50%.
The other recombinant construction was carried out with the same peptide of 20 aa P0 coupled to several promiscuous T cell epitopes. Specifically, we used tetanus toxoid ttP2 epitopes and T cell epitope of measles virus (TT-MVF). Multiple copies of the DNA sequence of 20 aa pP0 (AAGGGAAAAKPEESKKEEAK) (SEQ ID NO: 11) and promiscuous T antigen were inserted fused to the intein of Saccharomyces cerevisiae in the plasmid pTBY 12 under control of the T7 promoter and lac operon repressor that allows expression of the fusion protein only after induction with IPTG. The recombinant plasmid obtained was used to transform ER2566 E. coli strain. The TT-MVF-pP0-intein chimera peptide was detected in the breaking supernatant of this strain by the anti-pP0 mouse polyclonal serum. Expression levels were estimated at approximately 100 mg/L of culture. The peptide was purified by affinity on a column of chitin and auto-digested in the presence of thiol groups to release the peptide of interest.
An immunization experiment was conducted in rabbits to assess the immunogenicity of chimera variants obtained and the effects of these antibodies generated on the R. sanguineus larvae, nymphs and adults compared to the effect of the synthetic peptide of P0 ribosomal protein conjugated to hemocyanin. For this experiment, 28 New Zealand rabbits, white and male, were randomized into 4 groups of 7 animals each. The immunogens were adjuvanted in Montanide VG 888 and administered as follows:
Group 1: Subcutaneous immunization with pP0-KLH conjugate at doses of 500 μg/animal (equivalent to 250 μg peptide/animal).
Group 2 (negative control): Subcutaneous immunization with KLH in doses of 250 μg/animal.
Group 3: Subcutaneous immunization with VLPsVP60pP0 in doses of 250 μg protein/animal.
Group 4: Subcutaneous immunization with the TT-MVF-pP0 chimeric peptide in doses of 250 μg peptide/animal.
The trial lasted 90 days. Animals were immunized on days 0, 21 and 36. The sera extraction, the antibody titer determinations, tick infestation and collection were performed similarly as described in Example 6.
For statistical analysis, the recovery and viability of ticks were subjected to analysis of variance (ANOVA) and a Bonferroni multiple comparison test. The best anti-P0 peptide titers were detected in animals immunized with the chimera VLPsVP60pP0 from day 14 post-immunization. These antibody titers were higher than 1:5000 for VLPsVP60pP0 chimeric from day 21, and from day 28 for animals immunized with the TT-MVF-PP0 chimera. These titers were kept until the end of the experiment ( FIG. 8 A).
The mean viability of larvae and nymphs and the adult recovery showed significant differences (p<0.05) for the groups vaccinated with chimera P0 peptide variants with respect to the negative control group immunized with KLH. ( FIG. 8 B). Table 2 shows the diminution in the percentage of viability of larvae and the recovery percentage of nymphs and adults by experimental groups respect to the negative control group.
TABLE 2
Diminishing in the recovery percentage of ticks in each stage
with respect to the control group immunized with KLH.
Stage
pP0-KLH (%)
TT-MVF-pP0 (%)
VLPsVP60pP0 (%)
Larvae
30.00
28.00
34.00
Nymphs
38.00
16.00
42.00
Adults
36.67
30.00
36.67
Example 8
Protective Capacity Determination of the Bm86-pP0 Chimera Protein Respect to the pP0, Against R. microplus Tick Infestations
The Bm86 antigen from the R. microplus tick was expressed earlier in the MP36 P. pastoris strain (Valle M R et al., J. Biotech. 1994, 33: 135-146). In this construction were removed Bm86 gene fragments as the signal peptide and transmembrane region of the protein (SEQ ID NO. 5). To construct the chimera Bm86-pP0 protein, the nucleotide sequence of the Bm86 protein described above was inserted next the secretion signal of S. cerevisiae sucrose invertase (ssSUC2) in pPS10 plasmid under the control of AOX 1 promoter. The DNA sequence encoding the 35 amino acids peptide of R. microplus P0 ribosomal protein was fused to this Bm86 sequence. The MP36 P. pastoris strain was transformed with the resulting plasmid and transformants were selected by the reversal of the amino acid histidine auxotrophy. The clones obtained were induced with methanol after reaching an OD between 3 and 4 in cell culture. After 96 hours of induction, an expression analysis was carried out by Western blotting using the anti-pP0 mouse hyperimmune serum (referred in Example 4) and an anti-Bm86 polyclonal serum ( FIGS. 9A and 9B ). The recombinant protein was detected in the cell disruption precipitate at levels of 300 mg/L. This analysis showed a band of 100 kDa, corresponding to the glycosylated protein, which was reduced to a band of approximately 70 kDa, coinciding with the expected size for the protein after digestion with the PNGase F enzyme. There was no band in the sample analyzed in non-reducing conditions, suggesting the formation of multimeric structures, which were unable to enter the polyacrylamide gel. The presence of these protein aggregates of high molecular weight in the rupture precipitate was verified by electron microscopy. The chimera protein was purified by acid precipitation method, obtaining a purity of about 95%.
A cattle immunization test was conducted to compare the effects of pP0-KLH conjugate, Bm86 protein, Bm86-pP0 chimera protein and co-administration of pP0-KLH and Bm86 antigens as vaccine candidates on R. microplus ticks. For this experiment, 20 cattle free of ticks, more than 240 kg were randomized into five experimental groups of 4 animals each. The immunogens were administered in Montanide 888 VG (prepared to 10% in mineral oil) in 60/40 ratio of aqueous phase/oil phase. The experimental groups were designed as follows:
Group 1: Intramuscular immunization with pP0-KLH conjugate in doses of 500 μg of conjugate/animal (equivalent to 250 μg peptide/animal) with the scheme of 0, 4 and 7 weeks.
Group 2 (negative control): Intramuscular immunization with KLH in doses of 250 μg/animal with the scheme of 0, 4 and 7 weeks.
Group 3 (positive control): Intramuscular immunization with the R. microplus Bm86 protein in doses of 250 μg/animal with the scheme of 0, 4 and 7 weeks.
Group 4: Intramuscular immunization with the pP0-Bm86 chimeric protein in doses of 250 μg/animal with the scheme of 0, 4 and 7 weeks
Group 5: Intramuscular immunization with Bm86 protein and pP0-KLH conjugate in a dose of 250 mg of Bm86/animal and 500 μg of conjugate/animal with the scheme of 0, 4 and 7 weeks.
The trial lasted a total of 140 days. The animal serum samples were taken to measure the antibody response on days 0, 14, 28, 49, 70, 82, 120 and 140. Four cameras were placed per animal at day 82 of the experiment and were infested with 3000 larvae per chamber (12000 larvae per animal) of R. microplus ticks at a rate of 4000 daily between days 84 and 86. The collection, counting and weighing of ticks was performed between days 107 and 117. The engorged female teleoginas were kept in individual plastic plates at 28° C., 90% of relative humidity and a photoperiod of 12:12 h (light:dark).
The kinetic of anti-Bm86 and anti-pP0 antibodies was studied by ELISA, using in this case an anti-bovine conjugated peroxidase (Sigma) at 1:10000 dilutions. A specific IgG antibody response against Bm86 and against pP0 from day 14 was detected in all animals immunized with these antigens. These antibody titers were higher than 1:5000 after day 28 for the Bm86 antigen and between days 60 and 90 for the case of P0 peptide, which remained until the end of the experiment. No statistically significant differences were found for the titles of anti-Bm86 or anti-PP0 antibodies between groups inoculated with both antigens separately or in combination, or with respect to the group vaccinated with Bm86-pP0 chimera ( FIG. 10 ).
The effect of the antibodies generated in this experiment over the teleogina recovery, the teleogina and egg weight and hatching rate of R. microplus ticks was analyzed. Teleogina recovery significantly decreased in all vaccinated groups compared to negative control group of the experiment. The recovery of ticks respect the negative control group was decreased 32.6% for the group immunized with Bm86, 55.2% for the group immunized with pP0-KLH conjugate, 62.13% for the group immunized with two individual antigens and 65.2% for the immunization with Bm86-pP0 chimera. This parameter was significantly lower for the groups immunized with the Bm86-pP0 chimera and the combination of Bm86 with pP0-KLH respect to the groups where these antigens were applied individually. There were no significant differences in the group immunized with the chimera compared to the group immunized with the combination of the two antigens. The parameters of teleogina and eggs weight showed a significant affectation in the groups immunized with Bm86 relative to negative control group (ANOVA and Newman-Keuls multiple comparison test [p<0.05]). A significant decrease was observed for these biological parameters in the groups immunized with the chimera Bm86-pP0 and the combination of antigens, compared to groups vaccinated with the individual antigens ( FIG. 11 ). The percentage of hatching in the negative control group was 87.4%, while for the groups immunized with Bm86, pP0-KLH, the combination of Bm86 and pP0-KLH and Bm86-pP0 chimera was 75.1%, 64.6%, 54.8% and 55.9% respectively, showing a significant decrease in all groups compared to control. These results show that vaccination with a formulation containing the peptide of P0 ribosomal protein, object of this invention, fused to the protein Bm86 or combined with it leads to increased affectations on survival and biological parameters of R. microplus , which results in a more efficient control of infestations of this tick.
Example 9
Protective Capacity Determination of the P0 Peptide of Ixodes scapularis (pP0Is) Against I. scapularis Tick Infestations
The immunogenicity of the peptide between amino acids 267-302 of I. scapularis P0 ribosomal protein, homologous to the immunogenic peptide of the R. microplus and R. sanguineus P0 protein was evaluated. These peptides have a 68% of sequence identity among them. The chemical synthesis of I. scapularis peptide and conjugation to hemocyanin (KLH) was performed similarly as described in Example 3. Subsequently, 12 white New Zealand male rabbits were randomized into two experimental groups of six rabbits each, which were immunized and challenged with larvae, nymphs and adults of I. scapularis ticks. The immunogens were adjuvanted with Montanide 888 VG in a ratio 60/40 of immunogen/adjuvant and applied as follows:
Group 1: Subcutaneous immunization with pP0Is-KLH conjugate at doses of 500 μg/animal (equivalent to 250 μg peptide/animal).
Group 2 (negative control): Subcutaneous immunization with KLH in doses of 250 μg/animal.
Both groups were immunized on days 0, 21 and 36. Sera extractions were performed at days 0, 14, 21, 28, 36 and 60 of the experiment. The determination of anti-pP0Is antibody titers and infestation, collect, count and maintenance of ticks were performed similarly as described in Example 6.
There was no change in normal behavior, neither fever in any of the animals. Anti-pP0Is titers were detected in animals immunized with pP0Is-KLH conjugate from day 14 post-immunization. These antibody titers were higher than 1:3500 on day 36, which remained until the end of the experiment ( FIG. 12 ).
At 168 hours, all fed stages of the two groups had been collected. Recovery and viability of all stages of ticks, the weight of teleoginas and eggs and egg hatch % were compared between groups by ANOVA and Bonferroni multiple comparison test (p<0.05). The recovery of nymphs and teleoginas showed statistically significant differences in the group vaccinated with the pP0Is-KLH conjugate compared to negative control group. A high mortality of newly molted larvae fed over pP0Is-KLH immunized animals was found with statistically significant differences between groups ( FIG. 13 A). The weight of teleoginas and eggs was not shown statistically significant differences. The efficiency of conversion to eggs was 45.49% in the negative control group and 40.19% in the group immunized with the pP0Is-KLH conjugate. The percentage of hatching was 95.20% for negative control and 83.10% for the group immunized with the conjugate. This last parameter was significant when statistical analysis was performed ( FIG. 13 B).
Example 10
Protective Capacity Determination of the L. salmonis pP0 (pP0Ls)
To evaluate the usefulness of the pP0Ls as vaccine antigen, 80 salmon with an average weight of 80 g were distributed in 4 groups of 20 fish each. Two groups were injected intraperitoneally (ip) with pP0Ls-KLH conjugate at a dose of 10 μg conjugate/g body weight of salmon (equivalent to 5 μg pP0Ls/g salmon), formulated in Montanide 888 oil adjuvant. The other two negative control groups were immunized with KLH 5 μg/g body weight, adjuvanted in Montanide 888. After 500 arbitrary thermal units, the salmons were adapted to seawater and were infested with 2000±200 copepodites per pond. The challenge was carried out under dark conditions, constant aeration, support oxygenation, temperature (15-17° C.) and salinity (approx. 30 ppm) control. In order to avoid loss of copepodites and facilitate their attachment, the flow of water in the pond was closed and the replacement was done manually every 48 hours. In addition, 220μ sieves were installed in the sewer. The instant of the inclusion of copepodites was defined as day 0. These conditions were maintained for 40 days from the start of the challenge.
At day 40, the fishes were sacrificed by an anesthesia overdose, and the evaluation of the results proceeded by parasites counting. The results in the Table 3 showed a significant decrease in the number of parasites per fish in the groups vaccinated with pP0Ls-KLH, compared to negative controls immunized with KLH alone.
TABLE 3
Parasite count results at the end of the challenging experiment.
Vaccinated
Vaccinated
Parameters
group 1
group 2
Control 1
Control 2
# of parasites/fish
15 ± 6 a
16 ± 6 a
38 ± 9 b
37 ± 10 b
% of fish survival
95
90
95
85
% Infestation
60
56
—
—
inhibition
Different letters indicate significant differences. Dunn multiple comparison test was applied (p<0.001).
Salmon immunization experiments with 20 amino acid fragments of pP0Ls peptide were performed with similar results to those described in this example. The peptides with the sequence PAAGATKAAAAAPAKADEPE (SEQ ID NO: 14), SKFASVAAAPAAGATKAAAA (SEQ ID NO: 15) and EYLADPSKFASVAAAPAAGA (SEQ ID NO: 16) were tested conjugated to KLH. Although all peptides conferred protection, the best results were obtained with the peptide corresponding to the last 20 amino acids of pP0Ls.
Example 11
Protective Capacity Determination of the P0 Peptide of C. Rogercresseyi (pP0Cr) Fused to Promiscuous T Epitopes and Conjugated to KLH (pP0Cr-KLH)
Example 11
Protective Capacity Determination of the P0 Peptide of C. rogercresseyi (pP0Cr) Fused to Promiscuous T Epitopes and Conjugated to KLH (pP0Cr-KLH)
We assessed the immunogenicity of the pP0Cr-KLH conjugate and the pP0Cr fused to other immuno-carrier molecules such as promiscuous T epitopes. In this case, ttP2 epitopes of tetanus toxoid and T cell epitope of measles virus (TT-MVF) were used. The TT-MVF-pP0Cr chimera peptide was detected in the supernatant culture of MP36 P. pastoris strain transformed with a plasmid containing a copy of the coding sequence for pP0Cr fused at its N-terminus to two copies of the promiscuous T epitopes under the control of the promoter of alcohol oxidase 1 (AOX 1). All was preceded by the secretion signal of S. cerevisiae sucrose invertase (ssSUC2). Expression levels were estimated at approximately 150 mg/L of culture.
The usefulness of this polypeptide obtained by recombinant means was evaluated as vaccine antigen and compared with the effects of pP0Cr-KLH conjugate. 120 salmons with an average weight of 80 g were divided into 6 groups of 20 fish each. The experimental groups were:
Groups 1 and 2 were injected i.p. with the pP0Cr-KLH conjugate at a dose of 10 μg/g body weight (equivalent to 5 μg pP0Cr/g).
Groups 3 and 4 were injected i.p. with KLH at a dose of 5 μg/g weight.
Groups 5 and 6 were injected i.p with the TT-MVF-pP0Cr. chimera protein at a dose of 5 μg/g weight.
In all cases, the immunogen was formulated in Montanide 888 oil adjuvant. The experimental procedure was similar to Example 10, except that in this case as C. rogercresseyi sea lice has a shorter life cycle, on day 24 (after complete two life cycles of the parasite), fishes were sacrificed with an overdose of anesthesia, and the evaluation of the results proceeded by parasites counting. The following table shows a significant decrease in the number of parasites per fish in the groups vaccinated with pP0Cr-KLH and TT-MVF-pP0Cr, compared to negative controls immunized with KLH alone. The best protection, assessed as number of parasites/fish was observed in the group TT-MVF-pP0Cr.
TABLE 4
Parasite count results at the end of the challenging experiment.
Parameters
Group 1
Group 2
Group 3
Group 4
Group 5
Group 6
# parasites/
21 ± 7 a
19 ± 6 a
48 ± 10 b
47 ± 8 b
14 ± 3 c
13 ± 2 c
fish
% fish
90
85
95
85
95
90
survival
% infestation
55
60
—
—
70
72
inhibition
Different letters indicate significant differences. Dunn multiple comparison test was applied (p<0.001).
Example 12
Immunogenicity Determination of the pP0Cr Fused to My32 Polypeptide
A my32-pP0Cr chimera peptide using the same procedure described in the above examples for all fusion proteins was generated to evaluate the immunogenicity of the pP0Cr antigen fused to my32, previously known. In this case, the plasmid that was used to transform the P. pastoris MP36 strain contained a copy of pP0Cr fused by its N-terminus to a copy of my32 protein, under the control of the AOX 1 promoter, preceded by the ssSUC2 secretion signal. The my32-pP0Cr chimera peptide was detected in the culture supernatant at a concentration of approximately 135 mg/L of culture.
To evaluate the usefulness of this polypeptide obtained by recombinant via as vaccine antigen, 160 salmons with an average weight of 80 g were divided into groups of 20 fish each. The experimental groups were:
Groups 1 and 2 were injected with the pP0Cr-KLH conjugate at a dose of 10 μg/g body weight (equivalent to 5 μg pP0Cr/g).
Groups 3 and 4 were injected with KLH at a dose of 5 μg/g body weight.
Groups 5 and 6 were injected with pP0Cr-my32 chimera protein at a dose of 5 μg/g body weight.
Groups 7 and 8 were injected with the my32 protein obtained by recombinant means, at a dose of 5 μg/g body weight.
All animals received the immunogen by the ip route adjuvanted in Montanide 888. The experimental procedure followed was similar to that of Example 11. Table 5 shows the results of sampling at day 24 post-challenge, which evidenced a significant decrease in the number of parasites per fish in the groups vaccinated with pP0Cr-KLH, my32-pP0Cr, and my32 compared with animals inoculated only with KLH. The best protection, assessed as number of parasites/fish was observed in group pP0Cr-my32.
TABLE 5
Parasite count results at the end of the challenging experiment.
Parameter
Group 1
Group 2
Group 3
Group 4
Group 5
Group 6
Group 7
Group 8
# parasites/fish
17 ± 7 a
15 ± 6 a
30 ± 9 b
31 ± 8 b
3 ± 1 c
4 ± 2 c
15 ± 3 a
14 ± 6 a
% fish survival
85
95
95
85
90
95
95
85
% infestation
43
50
—
—
90
87
50
53
inhibition
Different letters indicate significant differences. We applied a Dunn multiple comparison test (p<0.001).
INCORPORATION OF SEQUENCE LISTING
Incorporated herein by reference in its entirety is the Sequence Listing for the application. The Sequence Listing is disclosed on a computer-readable ASCII text file titled, “sequence_listing.txt”, created on Apr. 28, 2014. The sequence_listing.txt file is 15.4 kb in size. | The present invention relates to the use of a peptide of P0 ribosomal protein in the manufacture of a vaccine composition to control of ectoparasite infestations and therefore the transmission of their associated pathogens. This peptide is located between 267 and 301 amino acids of the P0 protein, and can be obtained by recombinant means or by chemical synthesis. This peptide can be fused to a carrier protein or peptide, or an immuno-carrier and be included in an oily formulation. The formulations comprising the peptide vaccine confer protection against ticks and ectoparasites known as “sea lice” without generating autoimmunity in the host organism. Among these ticks may be mentioned species as Rhipicephalus microplus, Rhipicephalus sanguineus and Ixodes scapularis , and between sea lice are those of the Caligus and Lepeophtheirus genera. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to Italian Patent Application Serial No. TO2009A000146, which was filed Feb. 27, 2009, and is incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] Various embodiments relate to the techniques for dimming light sources. The description has been prepared with particular attention to the potential application in light sources that use light-emitting diodes (LED), for example high-current LEDs.
BACKGROUND
[0003] The block diagram in FIG. 1 refers to a “three wire” dimming solution. In the block diagram in FIG. 1 , the reference S indicates a light source fed via a driver D connected to three wires, specifically:
a pair of wires 10 that supply power (taking it, for example, from a continuous voltage source), and a third wire 12 carrying a pulse width modulated (PWM) control signal that commands the dimming function.
[0006] The power supplied via the pair of wires 10 is in fact a continuous power supply and the driver D transfers the power to the source S as a function of the PWM signal on the wire 12 , in particular as a function of its duty cycle: the luminosity of the source S is in fact a function of the average intensity of the current flowing through the source S, an intensity that in turn depends on the duty cycle of the control signal.
[0007] The block diagram in FIG. 2 refers instead to a system in which the dimming function is realized with a “two wire” system interposing on at least one of the wires of the pair 10 a switch T (for example an electronic switch such as a MOSFET) that is opened and closed using a PWM control signal.
[0008] In this case, the power supply of the driver D is no longer continuous but intermittent as schematized in FIG. 3 , including two parts indicated respectively with a) and b). The two parts of FIG. 3 are two diagrams that illustrate as a function of a single time scale (x-axis scale, indicated with t), respectively:
the closed, i.e. conductive (“Ton”), or open, i.e. non-conductive (“Toff”), state of the switch T, and the ideal flow of the supply power to the driver D.
[0011] In the drawing in FIGS. 2 and 3 , the dimming function is therefore implemented by controlling, using PWM, the power supply line 10 interrupting in a controlled manner the electrical power to the driver D. By controlling the switching frequency of the switch T such that it is higher than the sensitivity range of the human eye (related to the persistence of the image on the retina), the overall effect achieved is to make the light source S, a function of the average intensity of the current flowing through the source S, dependent on the duty cycle of the PWM signal used to turn the switch T on and off.
[0012] Compared to the “three wire” drawing in FIG. 1 , the “two wire” drawing in FIG. 2 presents the advantage of doing without one of the wires, which makes the circuit simpler and cheaper. Furthermore, the use of the circuit in FIG. 2 must take into account the presence, at the input of the driver D, of the capacitance C observable as a whole downstream of the switch T, capacitance which may also include at least one capacitor included in the input stage of the driver D.
[0013] In operation of the circuit, when the switch T is open, i.e. not conductive, the capacitance C supplies power to the driver D, with the resulting reduction in the voltage present in that capacitance. When the switch T is made conductive again, a voltage step creating an inrush current is applied to the capacitance C. The peak value of this current is nominally limited only by the parasitic resistance of the power supply line including the switch T and the capacitance C and is a function of the width of the aforementioned voltage step, this being the difference between the input voltage from the power source (or the source powering the line 10 ) and the residual voltage on the capacitance C when the switch T is closed again. This voltage step is therefore a function of the value of the capacitance C and the switching speed (frequency) of the switch T.
SUMMARY OF THE INVENTION
[0014] In various embodiments, a device for dimming a light source is provided. The device may include a two-wire power supply line having interposed therein a switch for controlling transfer of said power supply towards said light source; a capacitance located downstream of said switch being traversed by a charge current as said switch is switched on; and a pre-charge stage interposed between said switch and said capacitance; said pre-charge stage being configured to limit to a given value said charge current.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] In the drawings, like reference characters generally refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the following description, various embodiments are described, purely by way of a non-limiting example, with reference to the attached figures, in which:
[0016] FIGS. 1 to 3 have already been described above;
[0017] FIG. 4 is a block diagram of a device as described here,
[0018] FIG. 5 illustrates one embodiment of the drawing in FIG. 4 ,
[0019] FIG. 6 illustrates a detail of the embodiment in FIG. 5 ,
[0020] FIG. 7 , including four temporarily superposed diagrams, marked respectively a), b), c) and d), illustrates the temporary trend of certain signals present in the device in FIG. 4 ,
[0021] FIG. 8 illustrates one embodiment of the solution described here, and
[0022] FIG. 9 illustrates one embodiment of the solution described here.
DESCRIPTION
[0023] The description below illustrates various specific details to provide a more comprehensive understanding of the embodiments. The embodiments may be realized without one or more of the specific details, or with other methods, components, materials, etc. In other cases, known structures, materials or operations are not shown or described in detail so as not to obscure the different aspects of the embodiments.
[0024] Reference to “an embodiment” in this description indicates that a particular configuration, structure or characteristic described in relation to the embodiment is included in at least one embodiment. Therefore, phrases such as “in one embodiment”, which may appear in various places in this description, do not necessarily refer to the same embodiment. Furthermore, specific formations, structures or characteristics may be appropriately combined in one or more embodiments.
[0025] The references used herein are used solely for convenience and therefore do not define the field of protection or scope of the embodiments.
[0026] From FIG. 4 onwards, parts, elements or components identical or equivalent to parts, elements or components already described with reference to FIGS. 1 to 3 are marked with the same references, making it unnecessary to repeat the related descriptions.
[0027] It shall also be seen that, in some embodiments, the basic solution illustrated in FIG. 4 (interposing between the switch T and the capacitance C a pre-charge stage intended to limit—with an on/off function or with continuous adjustment—the inrush current on closure of the switch T) may advantageously use one or more components already present in the basic drawing in FIG. 2 .
[0028] In various embodiments, FIGS. 5 and 6 refer to an embodiment in which the pre-charge stage P is implemented around a “buck” converter 14 inserted in a negative-feedback drawing.
[0029] The drawing in FIG. 6 shows a possible embodiment of the buck converter 14 , containing a low-pass LC module comprising an inductor 16 and a capacitor 18 (in fact, arranged in parallel with the capacitance C and potentially included in said capacitance). The converter 14 may also include a diode 20 connected to the LC module 16 , 18 a π configuration with the cathode of the diode 20 connected to the inductor 16 .
[0030] The reference T B indicates a control switch that permits/prevents (respectively when closed, i.e. conductive, and when open, i.e. non-conductive) the transfer of power from the line 10 to the driver D. As a result, even though the switch T B is shown here as a separate component, in one embodiment its function may be incorporated into the function of the switch T.
[0031] The switch T B is commanded by a control module 22 that receives, via a difference node 24 , a signal representative of the difference between the intensity of the current Iout flowing from the stage P to the capacitance C (signal Isense−line 26 ) and a peak reference current value (Ipeak ref−line 28 ).
[0032] In diagram a) of FIG. 7 , Toff indicates the period of time for which the switch T is open, i.e. non-conductive; Ton however indicates the period of time for which the switch T is closed, i.e. conductive. The ratio Ton/(Ton+Toff) therefore indicates the duty cycle of the PWM control signal of the switch T used to command the dimming function of the source S.
[0033] In one embodiment, the control law implemented by the module 22 states that at the instant the switch T is closed (moving from Toff period to Ton period in diagram a) of FIG. 7 ) the switch T B is also closed thereby allowing the capacitance C (and the capacitor C B in FIG. 6 ) to be charged by the current Iout.
[0034] The sensing action performed via the line 26 makes it possible to adjust the intensity of the current Iout so that it does not exceed—at least in terms of the average value—the maximum peak value (Ipeak ref) set for the line 28 .
[0035] In one embodiment, the module 22 is configured such that when the intensity of the charge current Iout sensed as Isense on the line 26 reaches the peak value Ipeak ref set for the line 28 (which causes the output signal produced by the node 24 to drop to zero) the module 22 opens the switch T B interrupting the current flow across it.
[0036] This operating mode results in a sequence of opening and closing cycles of the switch T B (at a frequency greater than the frequency of the PWM signal driving the switch T) as shown in diagram d) of FIG. 7 .
[0037] The practical result is as shown in diagram b) of FIG. 7 , i.e. keeping the intensity of the current (average value) flowing out of the stage P (current Iout) within the reference value set Ipeak ref. All of which results in the charging of the capacitance C according to an at least approximately linear gradient, of the type shown in diagram c) of FIG. 7 .
[0038] The intervention of the control switch T B concludes when the capacitance C is fully charged, at the end of the gradient in diagram c) of FIG. 7 , for example once a continuous voltage corresponding to the voltage of the source applied to the pair of power supply wires 10 has been stabilized at the terminals of the capacitance C.
[0039] Under such conditions, the current Iout leaving the stage P is practically entirely absorbed as Idriver current by the driver D; the difference (Iref peak−Isense, with Isense=Idriver) generated by the difference node 24 is always at a high level, such as to ensure that the switch T B remains stably closed. Under such conditions the pre-charge state P is in fact “transparent” optimizing the power flow to the driver D.
[0040] When the switch T is opened again, the switch T B may remain at a high level thus reducing the losses in the successive Ton cycle.
[0041] FIG. 8 is a circuit diagram of a simplified, low-cost embodiment of the solution described with reference to FIGS. 5 and 6 .
[0042] In the drawing in FIG. 8 the reference 30 indicates a sensing resistor that detects the intensity of the current Iout generating a corresponding signal Isense on the line 26 .
[0043] The difference node 24 is implemented using a differential amplifier that receives:
on the inverting input, the signal present on the line 26 , on the non-inverting input, a reference voltage signal Vref indicative of the maximum threshold value of the current Ipeak ref.
[0046] The output of the comparator 24 can be used to directly drive the switch T B , which can be implemented using a MOSFET.
[0047] By way of example, when the MOSFET T B is closed, the output current in the stage P starts to increase (beginning of gradient in diagram c) of FIG. 7 ) with an angular coefficient defined by the value of the inductor 16 and the input and output voltages. When the voltage at the inverting input of the comparator 24 reaches the value Vref, the output of the comparator changes from “high” to “low”.
[0048] This often occurs with a typical delay of the comparator and, during this delay, the current continues to increase until the output of the comparator 24 changes causing the opening of the MOSFET T B , causing the output current to begin to drop.
[0049] As a result, the voltage at the inverting input of the comparator 24 also drops down again to the value present on the non-inverting input (voltage Vref) such as to cause, in all cases with the intrinsic delay of the comparator 24 , a new change of the output level, with the consequent switching of the MOSFET T B to a conductive state.
[0050] In other words, the comparator 24 is configured to detect the instant in which the intensity Isense of the charge current reaches (rising and falling, in the sample embodiment considered here) the value Ipeak ref and to command the switching of the control switch T B with a delay with respect to said instant.
[0051] Repeating this opening/closing mechanism of the switch represented by the MOSFET T B substantially determines the regulation of the current Iout with an average value linked to the voltage Vref and a ripple proportionate to the response delay of the comparator 24 (which induces an hysteresis mechanism in the switching having a stabilizing effect).
[0052] In full operation (capacitance C fully charged), with a current Idriver in the charge (driver D) below the maximum value admitted for the charge current, the MOSFET T B remains stably closed enabling the normal transfer of the power supply to the driver D (until the switch T is opened).
[0053] In the embodiments considered here, the switch T and the switch T B occupy different positions in the circuit as a whole. As stated above, in one embodiment, the function of the switch T B (for example MOSFET) may be in fact integrated into the function of the switch T, providing for the adjustment function of the charge current of the capacitance C represented by the rapid opening/closing sequence of the switch T B illustrated in diagram d) of FIG. 7 to be part of the drive function of the switch T as implemented in the section of the period Ton in which the PWM signal that drives the dimming function of the source S is such as to make the switch T conductive (“on” state).
[0054] In the embodiment shown in FIG. 9 (in which again parts, elements and components similar or equivalent to those already described are indicated using the same references) a control function similar to the one described above, instead of having a “digital” method of turning the switch represented by the MOSFET T B on and off, is actuated by using a MOSFET 33 as an analogue controller, i.e. as a current modulator.
[0055] In the embodiment shown in FIG. 9 , the resistor 30 that acts as the sensor to detect the intensity of the charge current Iout is again present. The MOSFET 33 acts as a current modulator interposed on the power supply line and driven by the sensor 30 to modulate the charge current Iout as a function of the intensity detected by the sensor 30 itself, limiting the charge current again as a function of a value Ipeak ref.
[0056] For this purpose, the MOSFET 33 (here an n channel type) is connected such that the current Iout flows through its source-drain line. The gate of the MOSFET 33 is connected to an electronic switch 32 , including, in the sample embodiment shown, an n-p-n bipolar transistor. The sensing resistor 30 (which detects the intensity of the current Iout) is here connected between the base and the emitter of the transistor 32 itself. A Zener diode 34 is then connected via its cathode and its anode, respectively, to the collector and the emitter of the transistor 32 .
[0057] The power flow to the driver D is as before controlled, using PWM, by the switch T that, in the same embodiment illustrated, is connected to the anode of the Zener diode 34 as well as to the emitter of the transistor 32 .
[0058] The MOSFET 33 has, as shown, its source-drain line crossed by the current Iout and is connected via its gate to the common connection point of the collector of the transistor 32 and of the cathode of the Zener diode 34 . This common connection point is then connected via a resistor 36 to the “high” wire of the power supply line 10 .
[0059] In the case of the embodiment in FIG. 9 , when the switch T is closed at the beginning of the period Ton, the gate voltage of the MOSFET 33 is at a high level and the MOSFET 33 is inhibited, with the gate voltage of the MOSFET 33 clamped to the Zener value of the diode 34 , chosen such as to maintain this voltage at a level below the maximum gate-source voltage permitted for operation of the 33 .
[0060] As soon as the switch T is closed, the current Iout begins to increase charging the capacitance C and causing a corresponding increase in the voltage detected at the terminals of the sensing resistor 30 . When this voltage reaches the base-emitter threshold voltage Vbe on of the bipolar transistor 32 , this transistor, initially inhibited, starts to conduct drawing current across its collector and causing (as a result of the increase of the voltage drop across the resistor 36 ) a reduction in the gate voltage of the MOSFET 33 . The MOSFET 33 is then operating in its linear operating region and acts as a controlled-voltage current modulator or regulator, limiting as before the charge current flowing through it.
[0061] The resistance value of the resistor 30 is chosen such as to make the switch 32 conductive and to trigger the regulation action of the MOSFET 33 such as to limit the peak value of the charge current of the capacitor C to a given maximum value. By way of example, increasing the resistance value of the resistor 30 results in a reduction of the value of the current Iout that triggers the modulation action of the MOSFET 33 , and therefore a consequent reduction of the maximum value reached by the charge current Iout.
[0062] Again, when the full-operation conditions are reached (capacitance C fully charged) the operation of the circuit stabilizes in a rated condition causing (with the maximum peak value admitted for the inrush current greater than the rated charge current Iout=Idriver of the charge in normal operation) the voltage at the terminals of the resistor 30 to be lower than the voltage Vbe on which causes the bipolar transistor 32 to become conductive. In the aforementioned full-operation conditions, the transistor 32 is inhibited, while the MOSFET 33 is entirely conductive.
[0063] Again in this case, once the transient of the inrush current has been contained at the desired value, the pre-charge stage P is transparent in terms of normal operation of the circuit.
[0064] It will be seen that the solution described here makes it possible to implement fully effective, low-cost two-wire dimming. It is also possible to use the pre-charge stage P for any power range and, potentially, also to drive additional D units.
[0065] The pre-charge stage described, intended to manipulate the conditions in which it is possible to determine an excessively high inrush current, is in all other respects entirely transparent in the other operating phases of the circuit.
[0066] In various embodiments, the inventors have determined that the above mentioned inrush current can reach quite high intensity values, with the risk of damaging the switch T and/or the input capacitor or capacitors of the unit D. Moreover, if the power supply connected to the lines 10 is provided with protection against overloads, such a current could trigger the protection and interrupt the power supply.
[0067] Various embodiments are intended to overcome these potential drawbacks.
[0068] According to various embodiments, this scope is achieved using a device having the features set out in the claims below.
[0069] Various embodiments also concern a corresponding method.
[0070] The claims are an integral part of the technical explanation provided herein in relation to various embodiments.
[0071] In one embodiment, the solution described here involves placing upstream of the driver a pre-charge stage capable of acting between the switch T and the capacitance C such as to limit the aforementioned current.
[0072] Notwithstanding the invention principle, the implementation details and the embodiments may therefore vary significantly from the descriptions given here purely by way of example, without thereby moving outside the scope of the invention, as defined in the attached claims.
[0073] While the invention has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is thus indicated by the appended claims and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced. | In various embodiments, a device for dimming a light source is provided. The device may include a two-wire power supply line having interposed therein a switch for controlling transfer of said power supply towards said light source; a capacitance located downstream of said switch being traversed by a charge current as said switch is switched on; and a pre-charge stage interposed between said switch and said capacitance; said pre-charge stage being configured to limit to a given value said charge current. | 3 |
BACKGROUND
[0001] 1. Field
[0002] The present invention relates to an iodine (I 2 ) or bromine (Br 2 ) adsorbent including a zeolite having a Si/Al ratio of 15 or greater; an I 2 or Br 2 carrier including the I 2 or Br 2 adsorbent; a column filled with the I 2 or Br 2 adsorbent; a article composed of the I 2 or Br 2 adsorbent or having the I 2 or Br 2 adsorbent attached thereto; a method for adsorbing or removing I 2 or Br 2 using the I 2 or Br 2 adsorbent; an iodine- or bromine-containing zeolite composite including a porous zeolite and iodine (I 2 ) or bromine (Br 2 ) confined in the pores of the zeolite; a semiconductor material including the iodine- or bromine-containing zeolite composite; and a method for preparing an iodine- or bromine-containing product using the iodine- or bromine-containing zeolite composite.
[0003] 2. Description of the Related Art
[0004] Iodine is a volatile (sublimating), corrosive solid at room temperature. Because of its volatility, it is difficult to accurately weigh the amount of iodine on a scale, and iodine vapor can corrode the scale being used. Likewise, bromine, being a highly volatile and corrosive liquid at room temperature, is difficult to accurately weigh on a scale, and bromine vapor can corrode the scale being used.
[0005] Of the 37 known isotopes of iodine, all are radioactive elements except the stable I-127. Whereas most of the radioactive isotopes have very short half-lives of 1 day or shorter, I-124, I-125, I-126, and I-131 have relatively long half-lives of 4-60 days. Among them, I-131 results in the greatest radioactive damage in the event of atomic reactor explosion. I-129 decays over a very long period of time with a half-life of Ser. No. 15/700,000 years. Due to its slow radioactive radiation, it is less dangerous than other radioactive isotopes and is classified as a potential radioactive material since a large amount of radioisotopes, despite slow radioactive radiation, can lead to high radiation doses. However, the capture of this isotope is an important part in the process of nuclear waste because about 0.55% of uranium decays into I-129. Since I-129 exists naturally at a certain level, it can be used as an index for chronometry. That is to say, the trace amount of the naturally existing I-129 captured enables accurate timekeeping.
[0006] In solutions, iodine usually exists as iodide ions (I) and iodine molecules (I 2 ). Theoretically, the iodide anions can be recovered using an anion exchanger. However, once the ions flow into seawater, it is impossible to recover the iodide ions using the anion exchanger because of the high chloride concentration in seawater. The neutral iodine molecules are oxidative and are easily converted into iodide ions via oxidation by various reducing materials present in seawater. Therefore, the neutral iodine molecules need to be recovered from the hydrosphere including the sea or air before they are converted into iodide ions. For this reason, a method allowing for effective capturing of iodine included in water or air may be useful for blocking the propagation of the radioactive iodine.
[0007] Until recently, activated carbon or zeolite has been used to recover neutral iodine molecules from water or air. However, these adsorbents tend to reduce a significant amount of the adsorbed neutral iodine to iodide ions. Due to this property, it is difficult to remove iodine, particularly that in water. Therefore, it is necessary to develop an iodine adsorbent or capturing agent capable of capturing neutral iodine well without converting the neutral iodine molecules to iodide ions.
SUMMARY
[0008] Activated carbon (AC) is known to adsorb I 2 well. However, a considerable amount of the adsorbed I 2 is reduced to I − by reducing materials present in the activated carbon. It is difficult to remove the thus generated I − , and the I 2 -adsorbing ability of the activated carbon containing I − is very low. Accordingly, when removing I 2 from waste fuel using AC filled into a fixed bed, the AC in the fixed bed should be replaced with fresh AC after several charge-discharge cycles. Accordingly, there is a need for a strong physical adsorbent enabling purely physical adsorption even after many charge-discharge cycles without the need for replacement.
[0009] The present inventors have examined various zeolites for their I 2 -adsorbing ability and formation of IT following I 2 adsorption. As a result, the inventors have found that a zeolite having a high Si/Al ratio adsorbs well not only iodine gas (I 2 ) in the air but also I 2 dissolved in water, and the adsorbed I 2 can be separated as I 2 because it is not reduced to I − . As a result, the zeolite adsorbent can be recycled many times with no decline in adsorbing ability. Also, the inventors have found that the zeolite can adsorb not only I 2 but also Br 2 as well. In addition, the inventors have found that the iodine (I 2 ) confined in the pores of the zeolite can be readily desorbed using an organic solvent and completely desorbed by heating.
[0010] Furthermore, the inventors have found that the iodine- or bromine-containing zeolite composite exhibits semiconductor properties and, accordingly, zeolites in which iodine molecules or bromine molecules are included can be used for various applications.
[0011] The present invention is based on these findings.
[0012] In an aspect, the present invention provides an I 2 or Br 2 adsorbent containing a zeolite having a Si/Al ratio of 15 or greater.
[0013] Specifically, the zeolite may have a Sanderson partial negative charge on oxygen (−δ 0 ) of 0.2 or lower.
[0014] Non-limiting examples of the zeolite may include SL-1F, Si-BEA, SL-1, ZSM-5, MTW, silica MTW, silica DDR, high-silica DDR (ZSM-58, Si/Al=190), silica SSZ-73, an all-silica clathrasil DD3R, a silica ferrierite, silica TON, silica LTA, silica ITQ-1, silica ITQ-2, silica ITQ-3, silica ITQ-4, silica ITQ-7, silica ITQ-29, silica ITQ-32, a silica zeolite having CHA, STT, ITW or SVR topology, silica FAU, silica AST, a silica zeolite YNU-2 having MSE topology, silica RUB-41, silica ZSM-22, silica MEL, or a zeolite analogue having a Si/Al ratio of 15 or greater. Preferred examples of the zeolite may include silicalite-1 (SL-1), fluoride (F − )-added silicalite-1 (SL-1F) synthesized by adding a fluoride (F − )-releasing reagent, a beta zeolite having a silica backbone (all-silica beta, Si-BEA), TON having a silica backbone (ZSM-22), a ferrierite having a silica backbone (ZSM-35), DDR having a silica backbone, ZSM-5, etc., or a mixture thereof. In the iodine (I 2 ) or Br 2 adsorbent according to the present invention, the zeolite may be in the form of powder, foam, or film or may be a blended mixture with a natural polymer, a synthetic polymer, or another zeolite not having superior iodine- or bromine-adsorbing ability.
[0015] In another aspect, the present invention provides an I 2 or Br 2 carrier including the I 2 or Br 2 adsorbent according to the present invention; a fixed-bed column filled with the I 2 or Br 2 adsorbent according to the present invention; and a article composed of the I 2 or Br 2 adsorbent according to the present invention or having the I 2 or Br 2 adsorbent attached thereto. The article may be clothing.
[0016] Non-limiting examples of methods for preparing a zeolite foam or attaching a zeolite onto a substrate are described in Korean Patent Nos. 0392408 and 0607013 owned by the inventors of the present invention, which are incorporated herein by reference.
[0017] In another aspect, the present invention provides a method for adsorbing I 2 or Br 2 , including adsorbing I 2 or Br 2 using the I 2 or Br 2 adsorbent according to the present invention, the fixed-bed column according to the present invention, or the article according to the present invention.
[0018] In another aspect, the present invention provides a method for removing I 2 or Br 2 , including: adsorbing I 2 or Br 2 using the I 2 or Br 2 adsorbent according to the present invention, the fixed-bed column according to the present invention, or the article according to the present invention; desorbing the adsorbed I 2 or Br 2 from the zeolite by bringing into contact with an organic solvent dissolving I 2 or Br 2 , by heating, or by blowing in heated air or nitrogen; and forming an insoluble silver iodide or silver bromide precipitate by reacting the desorbed I 2 or Br 2 with AgNO 3 .
[0019] In another aspect, the present invention provides an iodine- or bromine-containing zeolite composite including a porous zeolite and iodine (I 2 ) or bromine (Br 2 ) confined in the pores of the zeolite. A known content of iodine or bromine may be captured in the composite.
[0020] The iodine- or bromine-containing zeolite composite according to the present invention exhibits semiconductor properties and, thus, can be used as a semiconductor material.
[0021] In another aspect, the present invention provides a method for preparing an iodine- or bromine-containing product or a compound generated by an iodine or bromine catalyst, including forming an iodine- or bromine-containing product in an organic solvent dissolving I 2 or Br 2 via a chemical reaction between iodine or bromine desorbed from the iodine- or bromine-containing zeolite composite according to the present invention by the organic solvent and another compound, or forming the compound in an organic solvent dissolving I 2 or Br 2 via a catalytic action of the iodine or bromine, desorbed from the iodine- or bromine-containing zeolite composite according to the present invention by the organic solvent. This is based on the point that the iodine- or bromine-containing zeolite composite confines iodine (I 2 ) or bromine (Br 2 ) in pores thereof and the I 2 or Br 2 may be released by an organic solvent, heat, or contact with hot air or nitrogen.
[0022] A zeolite having a Si/Al ratio of 15 or greater can adsorb not only iodine (I 2 ) or bromine (Br 2 ) gas in the air but also I 2 or Br 2 dissolved in water. In particular, it can adsorb and capture not only the radioactive iodine gas in the air but also the radioactive I 2 or Br 2 dissolved in seawater or underground water. Furthermore, among the zeolites according to the present invention, a zeolite having a Sanderson partial charge on oxygen)(−δ 0 ) of 0.2 or lower convert neither the adsorbed I 2 to I − nor the adsorbed Br 2 to Br − , and can release I 2 or Br 2 perfectly without loss, by contact with an organic solvent or by heating and, thus, can be recycled indefinitely.
[0023] In addition, since the iodine- or bromine-containing zeolite composite according to the present invention, which includes a porous zeolite and iodine (I 2 ) or bromine (Br 2 ) confined in the pores of the zeolite, exhibits semiconductor properties, it may be used as a semiconductor material. Furthermore, since it captures iodine (I 2 ) or bromine (Br 2 ), it may be used for various applications, e.g., as an iodine or bromine carrier or an iodine- or bromine-releasing reagent which releases an exact amount of iodine or bromine.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 shows absorption of I 2 from its saturated aqueous solution onto activated carbon (AC) and various zeolites SL-1F, Si-BEA, SL-1, ZSM-5, AgMOR, SBA-15, NaY, MOR, NaX, NaA, and CaA as solid absorbents.
[0025] FIG. 2 shows the absorbed amount (wt %) of iodine (I 2 ) (the amount (g) of absorbed I 2 per 100 g of zeolite) with time for activated carbon (AC) and various zeolites in aqueous solutions.
[0026] FIG. 3 shows sublimation of I 2 from solid I 2 , and its absorption into silicalite foam (SL-1 form) and silicalite powder (SL-1 powder).
[0027] FIG. 4 compares the hydrophobicity of activated carbon (AC) and various zeolites through water vapor adsorption isotherms at 313 K (40° C.).
[0028] FIG. 5 shows an apparatus for desorbing I 2 by increasing temperature while injecting nitrogen gas.
[0029] FIG. 6 shows the degree of desorption of I 2 from solid absorbents according to temperature.
[0030] FIG. 7 shows XRD patterns of MFI-type zeolite powder (freshly calcined), MFI-type zeolite with 0.1%, 1.0%, 6.9%, 22.3%, or 34.4% I 2 adsorbed, and I 2 -adsorbed MFI-type zeolite which has been recalcined (recalcination).
[0031] FIG. 8 a and FIG. 8 b respectively show the amount (wt %) of iodide ion (I − ) formed inside a solid absorbent ( 8 a ) and in a solution ( 8 b ) by activated carbon (AC) and various zeolites with time. FIG. 8 a shows the amount (wt %) of iodide ion (I − ) formed inside the solid absorbent, FIG. 8 b shows the amount (wt %) of iodide ion (I − ) formed in an aqueous solution, and FIG. 8 c shows the total amount of the formed iodide ion (I − ).
[0032] FIG. 9 shows the relationship between the Sanderson partial charge on oxygen and the total amount (wt %) of iodide ion (I − ) formed inside a solid absorbent and in a solution for activated carbon (AC) and various zeolites.
[0033] FIG. 10A shows the absorbed amount (wt %) of I 2 by activated carbon (AC) and various zeolites from the I 2 -saturated aqueous iodide (I − ) solution with various concentrations of I − . FIG. 10B shows the absorbed amount (wt %) of I 2 by activated carbon (AC) and various zeolites from the I 2 -saturated seawater.
[0034] FIG. 11 shows scattering and reflection UV-Vis spectra of Br 2 -adsorbed Si-BEA, ZSM-5, and SL-1 DML. It can be seen that the zeolites effectively adsorb Br 2 .
DETAILED DESCRIPTION
[0035] The term zeolite collectively refers to crystalline aluminosilicates.
[0036] The zeolite backbone is composed of tetrahedral units formed by [SiO 4 ] 4− and [AlO 4 ] 5− , which are bridged by oxygen atoms. Since the Al of [AlO 4 ] 5− has a formal charge of +3, whereas the Si of [SiO 4 ] 4− has a formal charge of +4, each Al has one negative charge. Accordingly, cations are present for charge balancing. The cations are present not in the backbone but in the pores and the remaining space is usually occupied by water molecules.
[0037] Because the site occupied by aluminum in the aluminosilicate backbone is negatively charged, there are cations for charge balancing in the pores and the inside of the pores is strongly polarized.
[0038] Meanwhile, various analogues (zeotype molecular sieves), wherein the silicon (Si) and aluminum (Al) constituting the backbone structure of zeolite have been partially or entirely replaced by various other elements, are known. For example, a porous silicalite in which aluminum has been completely eliminated, an (AlPO 4 )-type zeolite analogue in which silicon has been replaced by phosphorus (P), and other zeolite analogues obtained by replacing the backbone metal atoms of a zeolite or a zeolite analogue with various metal elements such as Ti, Mn, Co, Fe, Zn, etc. are known. These analogues are also included in the scope of zeolite according to the present invention.
[0039] Examples of an MFI-type zeolite or an analogue thereof may include ZSM-5, silicalite-1, TS-1, AZ-1, Bor-C, boralite C, encilite, FZ-1, LZ-105, monoclinic H-ZSM-5, mutinaite, NU-4, NU-5, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, etc. ZSM-5 is an MFI-type zeolite formed of silicon and aluminum of a specific ratio, silicalite-1 is a zeolite consisting only of silica (SiO 2 ), and TS-1 is an MFI-type zeolite in which titanium (Ti) occupies some of the aluminum sites.
[0040] Both SL-1 and SL-1F are MFI-type. SL-1 is synthesized without adding NH 4 F at all, whereas SL-1F is synthesized by adding NH 4 F to significantly increase hydrophobicity.
[0041] The chemical composition and the Sanderson partial charge on oxygen of various zeolites are given in Table 1.
[0000]
TABLE 1
Chemical composition (formula)
−δ 0
SL-1
Si 96 O 192
0.1501
Ag-MOR
H 4.0 Ag 1.2 Al 5.2 Si 42.8 O 96
0.1596
MOR
H 4.0 Na 1.2 Al 5.2 Si 42.8 O 96
0.1613
ZSM-5
H 0.2 Na 0.75 K 2.75 Al 3.7 Si 94.3 O 192
0.1684
CaA
H 15 Ca 22.5 Na 34.5 Al 94.5 Si 97.5 O 384
0.2615
NaY
Na 52.3 Al 52.3 Si 139.7 O 384
0.2640
NaA
H 6 Na 88.5 Al 94.5 Si 97.5 O 384
0.3251
NaX
H 3 Na 92.7 Al 95.75 Si 96.25 O 384
0.3367
[0042] When I − is generated in an I 2 adsorbent, the I 2 adsorbent can no longer adsorb I 2 and the I − is difficult to remove therefrom. When the I − exists in a solution, it can be removed using an anion exchange resin or a silver solution. However, when the I − exists inside the adsorbent, it cannot be removed even with the anion exchange resin or silver solution. The inventors of the present invention have examined various zeolites for their I 2 -adsorbing ability and formation of I − following I 2 adsorption. As a result, the inventors have found that there are some zeolites which do not generate or hardly generate I − after I 2 adsorption, particularly in water.
[0043] A more detailed description is given herein below.
[0044] The I 2 concentration of a saturated I 2 aqueous solution is ˜1.5 mM. It was investigated whether activated carbon (AC) and various zeolites ZSM-5, SL-1 powder, SL-1 foam, Si-BEA, NaA, NaY, SBA-15, MOR, and AgMOR adsorb the I 2 saturated in water well ( FIG. 1 ). As seen from FIG. 1 , activated carbon, zeolite ZSM-5, SL-1 powder, SL-1 foam, and Si-BEA can adsorb I 2 in water.
[0045] Meanwhile, the adsorption amount (wt %) of iodine (I 2 ) with time for activated carbon (AC) and various zeolites SL-1F, Si-BEA (all-silica zeolite-β), SL-1, ZSM-5, AgMOR, SBA-15, NaY, MOR, NaX, NaA, and CaA was measured in aqueous solutions. As seen from FIG. 2 , activated carbon and zeolite SL-1F, BEA, SL-1, and ZSM-5 showed high iodine (I 2 ) adsorption amount of 15 wt % or greater, whereas AgMOR, SBA-15, NaY, MOR, NaX, NaA, and CaA hardly adsorbed iodine (I 2 ).
[0046] In addition, the adsorption of I 2 sublimating from solid I 2 was confirmed for both silicalite-1 foam (SL form) and silicalite-1 powder (SL powder) which are MFI-type zeolites ( FIG. 3 ). From FIG. 3 , it can be seen that the color of the silicalite-1 foam and silicalite-1 powder turns violet due to the adsorption of I 2 .
[0047] Meanwhile, the hydrophobicity of activated carbon (AC) and various zeolites SL-1F, Si-BEA, SL-1, ZSM-5, AgMOR, SBA-15, NaY, MOR, NaX, NaA, and CaA was investigated through water vapor adsorption isotherms at 313 K (40° C.). As seen from FIG. 4 , the zeolites SL-1F, Si-BEA, SL-1, and ZSM-5 with a larger iodine (I 2 ) adsorption amount exhibit higher hydrophobicity than other zeolites. That is to say, the iodine (I 2 ) adsorption amount increases with hydrophobicity, suggesting that the adsorption of iodine (I 2 ) in the zeolite is due to hydrophobic bonding. The hydrophobicity is in the order of ZSM-5<SL-1<Si-BEA<SL-1F. Since the hydrophobicity of the zeolite increases with the Si/Al ratio, the zeolite according to the present invention capable of adsorbing iodine (I 2 ) has a Si/Al ratio (molar ratio) of 15 or greater, specifically 20 or greater, more specifically 30 or greater. For SL-1, SL-1F, and Si-BEA, which are free from Al, the Si/Al ratio is infinite (∞).
[0048] Meanwhile, using an apparatus for desorbing I 2 by increasing temperature while injecting nitrogen gas as shown in FIG. 5 , the degree of iodine desorption depending on temperature was investigated for activated carbon (AC) and the various zeolites Si-BEA, SL-1F, and SL-1 ( FIG. 6 ). Although I 2 is highly volatile, it is not desorbed easily even at high temperatures once it is adsorbed to the zeolite. As seen from FIG. 6 , I 2 was desorbed at 175° C. for the zeolites Si-BEA, SL-1F, and SL-1, unlike activated carbon (AC). That is to say, I 2 is desorbed from all of these adsorbents when hot air or hot nitrogen above a certain temperature is injected. For activated carbon (AC), some of the adsorbed I 2 that turned to I − remained and iodine was not completely desorbed.
[0049] The XRD patterns of SL-1 powder (freshly calcined), SL-1 with 0.1%, 1.0%, 6.9%, 22.3% or 34.4% I 2 adsorbed, and I 2 -adsorbed SL-1 which has been recalcined (recalcination) were investigated. As seen from FIG. 7 , it was observed that the peaks related to porosity disappeared when the nanowire channel in SL-1 was completely filled with I 2 (34.4%). In addition, it can be seen from the XRD patterns shown in FIG. 7 that the porosity-related peaks appeared again for the I 2 -adsorbed SL-1 which had been recalcined (recalcination), as in the fresh SL-1. This confirms that the backbone structure is maintained regardless of the adsorption and desorption of I 2 .
[0050] Meanwhile, the amount (wt %) of iodide ion (I − ) formed inside the solid adsorbent and in a solution with time was measured for activated carbon (AC) and the various zeolites SL-1F, Si-BEA, SL-1, ZSM-5, AgMOR, SBA-15, NaY, MOR, NaX, NaA, and CaA. The results are shown in FIG. 8 a and FIG. 8 b , respectively. FIG. 8 a shows the amount (wt %) of iodide ion (I − ) formed inside the solid adsorbent, FIG. 8 b shows the amount (wt %) of iodide ion (I − ) formed in a solution, and FIG. 8 c shows the total amount of the formed iodide ion (I − ).
[0051] As seen from FIGS. 8 a - 8 c , the amount of iodide ion (I − ) formed inside the solid adsorbent was the highest for activated carbon (AC). The amount of iodide ion (I − ) formed in solutions was in the order of NaX>NaA>CaA>NaY. For MOR, AgM, ZSM-5, SL-1F, SL-1, Si-BEA, and SBA-15, iodide ion (I − ) was hardly formed either inside the solid adsorbent or in the solution.
[0052] FIG. 9 shows the relationship between the Sanderson partial charge on oxygen and the total amount (wt %) of iodide ion (I) formed inside the solid adsorbent and in the solution for activated carbon (AC) and the various zeolites SL-1F, Si-BEA, SL-1, ZSM-5, AgMOR, SBA-15, NaY, MOR, NaX, NaA and CaA.
[0053] From FIG. 9 , it can be seen that the formation amount (wt %) of iodide ion (I − ) is proportional to the Sanderson partial charge on oxygen for activated carbon (AC) and the various zeolites. Accordingly, the zeolite used as an iodine (I 2 ) adsorbent for preventing iodide ion (I − ) formation may have a Sanderson partial charge on oxygen)(−δ 0 ) of specifically 0.2 or lower, more specifically 0.1-0.2.
[0054] As seen from FIGS. 1-9 , the zeolites SL-1F, Si-BEA, SL-1, and ZSM-5 are advantageous in that they exhibit a high iodine (I 2 ) adsorption amount and hardly show iodide ion (I − ) formation inside the solid adsorbent and in the solution. The zeolites SL-1F, Si-BEA, SL-1, and ZSM-5 have stronger hydrophobicity and a lower Sanderson partial charge on oxygen as compared to other zeolites.
[0055] Accordingly, the present invention is characterized in that a zeolite having a Si/Al ratio of 15 or greater is used as a zeolite for adsorbing iodine (I 2 ) and, among such zeolites, a zeolite having a Sanderson partial charge on oxygen)(−δ 0 ) of 0.2 or lower is used to prevent formation of iodide ion (I − ) from the adsorbed I 2 .
[0056] FIG. 10A shows the I 2 -saturated adsorption amount (wt %) of activated carbon (AC) and the various zeolites Si-BEA, SL-1F, and SL-1 under different I − concentrations. It can be seen that the zeolite according to the present invention can adsorb I 2 even when it is dissolved in water as I − .
[0057] Additionally, FIG. 10B shows the I 2 -saturated adsorption amount (wt %) of activated carbon (AC) and the various zeolites Si-BEA, SL-1F, and SL-1 in artificial seawater (ASW). It can be seen that the zeolite according to the present invention can adsorb I 2 even when it is dissolved in seawater.
[0058] I 2 is more soluble in seawater because it forms a complex. The zeolite according to the present invention can readily remove I 2 , particularly radioactive I 2 , when it is dissolved in seawater, underground water, etc.
[0059] Meanwhile, the zeolites of the present invention can also adsorb Br 2 in water ( FIG. 11 ).
[0060] The zeolite according to the present invention can adsorb I 2 having not only stable I-127 but also all the isotopes of I described in Table 2.
[0000]
TABLE 2
Decay
Main γ-X-ray energy (keV)
Isotope
Half-life
mode
E max (keV)
(abundance)
123 I
13.27
h
EC + β +
1074.9
(97%, EC)
159 (83%)
124 I
4.18
d
EC + β +
2557 (25%, EC), 3160
602.7 (63%), 723 (10%),
(24%, EC), 1535 (12%, β + ),
1691 (11%)
2138 (11%, β + )
125 I
59.41
d
EC
150.6
(100%)
35.5 (6.68%), 27.2 (40%),
27.5 (76%)
126 I
13.11
d
EC + β + , β −
869.4 (32%, β − ), 1489 (29%,
338.6 (34%), 666.3 (33%)
EC), 2155 (23%, EC)
127 I
Stable
128 I
24.99
m
β − , EC + β +
2119
(80%, β − )
442.9 (17%)
129 I
1.57 × 10 7
y
β −
154.4
(100%)
39.6 (7.5%), 29.5 (20%),
29.8 (38%)
130 I
12.36
h
β −
587 (47%), 1005 (48%)
536 (99%), 668.5 (96%),
739.5 (82%)
131 I
8.02
d
β −
606
(90%)
364.5 (82%)
132 I
2.30
h
β −
738 (13%), 1182 (19%),
667.7 (99%), 772.6 (76%)
2136 (19%)
132m I
1.39
h
IT, β −
1483
(8.6%, β − )
600 (14%), 173.7 (8.8%)
133 I
20.8
h
β −
1240
(83%)
529.9 (87%)
134 I
52.5
m
β −
1307
(30%)
847 (95%), 884 (65%)
135 I
6.57
h
β −
970 (22%), 1388 (24%)
1260 (29%)
Half-lives of the isotopes are given as m: minutes; h: hours; d: days; and y: years.
The decay mode: EC for electron capture; β + for positron emission; β − for beta emission; IT for internal transfer. An isotope may decay by more than one mode.
[0061] Meanwhile, the solubility (wt %) of iodine (I 2 ) of SL-1F and BEA was compared in various organic solvents. The results are shown in Table 3. Electron donor solvents can dissolve a large amount of I 2 because they form electron donor-acceptor complexes. Even though silicalite-1 (SL-1F) is a weak electron donor, the solvent can dissolve a very large amount of I 2 .
[0000]
TABLE 3
Solubility of I 2 at
Solvent density
Solvent weight
Concentration
Solvent
25° C. (g/100 mL)
(g/mL)
(g)
(%)
wt %
Ethanol
21.43
0.79
79.0
21.34
27.12
Diethyl ether
25.20
0.71
71.0
26.19
35.49
AcOH
14.09
1.05
105.0
11.83
13.42
Benzene
14.09
0.88
88.0
13.80
16.01
CHCl 3
14.09
1.48
148.3
8.68
9.50
CCl 4
2.603 a
1.59
159.0
1.61
1.64
Carbon disulfide (CS 2 )
16.47
1.26
126.0
11.56
13.07
Water
0.029 b ,
1.00
100.0
0.029,
0.029,
0.078 c
0.078
0.078
Hexane (exp.
0.94
0.66
65.9
1.41
1.43
data)
Silicalite-1
63.72
1.80
180.0(100 mL)
26.14
35.40
(SL-1F)
BEA
56.96
1.61
161.0(100 mL)
26.25
35.60
AC
11.55
0.32
32.0(100 mL)
26.52
36.10
a at 35° C.,
b at 20° C.,
c at 50° C., density of I 2 = 4.93 g/mL.
[0062] As can be seen from Table 3, although the I 2 adsorbed to the zeolite according to the present invention cannot be removed in water, it can be removed using organic solvents exhibiting high solubility for I 2 . However, the I 2 adsorbed to activated carbon (AC) cannot be removed even when organic solvents exhibiting high solubility for I 2 are used. Since the zeolite according to the present invention is hydrophobic, it has a strong tendency to absorb the organic solvent and the absorbed organic solvent dissolves I 2 , thereby releasing I 2 from the zeolite.
[0063] The zeolite according to the present invention can be recycled indefinitely since the I 2 adsorbed thereto can be completely removed using organic solvents such as ethanol. In contrast, activated carbon (AC) must be discarded after 3-4 uses because the I 2 adsorbed thereto cannot be removed by water or organic solvents. Accordingly, whereas the zeolite according to the present invention can be used indefinitely when filled into a fixed-bed column since I 2 adsorbed thereto can be completely removed using organic solvents, the activated carbon (AC) being filled into a fixed-bed column as an I 2 adsorbent requires routine replacement.
[0064] Non-limiting examples of the organic solvent for dissolving I 2 from the zeolite may include ethanol, diethyl ether, AcOH, benzene, CHCl 3 , carbon disulfide or a mixture thereof.
[0065] Meanwhile, the I 2 recovered from the zeolite and remaining dissolved in the organic solvent may be converted to small-sized AgI or AgIO precipitates by reacting with a AgNO 3 aqueous solution for permanent burial.
[0066] The inventors of the present invention found that an iodine- or bromine-containing zeolite composite including a porous zeolite and iodine (I 2 ) or bromine (Br 2 ) confined in the pores of the zeolite exhibits semiconductor properties with a narrow band gap energy (E g ). For example, it may have a band gap energy E g <3.0 eV and an electrical conductivity of 0.1 siemens/m or greater.
[0067] Specifically, a result of measuring the electrical conductivity of iodine-containing silicalite-1 (I 2 @SL-1) by electron force microscopy was as follows:
[0000] σ a along a -axis=1.67×10 4 Sm −1
[0000] σ b along b -axis=1.99×10 4 Sm −1
[0068] In addition, since the iodine (I 2 ) captured in the iodine-containing zeolite composite according to the present invention is not evaporated at temperatures of 50° C. or lower, it allows accurate quantification of iodine. It can be applied for a variety of chemical reactions requiring iodine because an accurate known amount of iodine is released by an organic solvent if the iodine-containing zeolite composite which has been quantitated is added to a reactor.
[0069] Additionally, the iodine-containing zeolite composite according to the present invention may be used as a controlled-release system by slowly adding a solvent that enables release of iodine.
[0070] This application also holds true for the bromine-containing zeolite composite. | The present invention relates to an iodine (I 2 ) or bromine (Br 2 ) adsorbent including a zeolite having a Si/Al ratio of 15 or greater; an I 2 or Br 2 carrier including the I 2 or Br 2 adsorbent; a column filled with the I 2 or Br 2 adsorbent; a article composed of the I 2 or Br 2 adsorbent or having the I 2 or Br 2 adsorbent attached thereto; a method for adsorbing or removing I 2 or Br 2 using the I 2 or Br 2 adsorbent; an iodine- or bromine-containing zeolite composite including a porous zeolite and iodine (I 2 ) or bromine (Br 2 ) confined in the pores of the zeolite; a semiconductor material including the iodine- or bromine-containing zeolite composite; and a method for preparing an iodine- or bromine-containing product using the iodine- or bromine-containing zeolite composite. | 2 |
This is a divisional of U.S. application Ser. No. 08/306,346, filed on Sep. 15, 1994 and now U.S. Pat. No. 5,492,833 issued on Feb. 20. 1996, which is a continuation of U.S. application Ser. No. 08/062,857, filed on May 14, 1993 and now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to a particle analyzing apparatus and more particularly to a method and apparatus for achieving selective, discriminate, differential classification of individual blood cell types, primarily reticulocytes utilizing light scatter-technology without the utilization of fluorescent staining techniques or materials.
2. Description of the Prior Art
Reticulocytes are defined in the medical literature as immature erythrocytes (or cells from which the nucleus has been extruded) and such cells normally account for 0.7 to 2.2 percent of the erythrocyte total count. In confirming or helping to confirm the diagnosis of diseases such as, for example, various forms of anemia or acute internal hemorrhage, the determination of reticulocytes can be of critical importance.
Microscopic examination of human blood smears on a glass slide is the universal accepted method of reticulocyte determination. This method is not only time consuming but relies on the human eye for the actual reticulocyte count. This often results in an inaccurate reticulocyte count which could also result in misdiagnosis.
One such microscopic method of determining reticulocytes is disclosed by Bjorkman, "Method for Determining Absolute Reticulocyte Count," J. Clin. & Lab. Investigation, 435-436, 1958. Therein, the described method utilizes new methylene blue to stain capillary blood and then fixes the blood cell with a diluent. The diluent fluid consists of potassium thiocyanate in dilute sulfuric acid. The fixation process is attended by an escape of hemoglobin from the blood cells. The decrease in hemoglobin content enhances the definition of the reticulum when the cell is viewed under a microscope in a blood smear on a slide.
Automated reticulocyte counting apparatus is available, but in the known instrumentation reliance is universal on the employment of fluorescence as a basis for the reticulocyte determination. Apparatus utilizing fluorescent devices are expensive, complex and require relatively costly maintenance.
It is well known that reticulocytes can be discriminated and classified by utilization of flow cytometry instrumentation when coupled with fluorescent staining. One such method involves utilizing low angle light scatter in combination with 90° or high angle light scatter.
The prior art literature, scientific papers and reports, illustrate, describe, and discuss the utilization of light scatter techniques at a variety of angular positions relative to the axis of the light beam being utilized to illuminate and interrogate the sample. However, the majority of the literature material available rely on the utilization of fluorescence and fluorescent techniques and chemistry to detect reticulocytes.
Examples of such prior art teaching includes U.S. Pat. No. 4,985,174 to Kuroda et al. which describes a reagent containing a dye which intensifies the strength of reticulocyte fluorescence in a stained sample and at the same time reduces the background fluorescence of the sample, so as to raise the signal to noise ratio when fluorescence is measured. This is accomplished by a reagent containing auramine O.
U.S. Pat, No. 4,325,706 to Gershman et al. relates to a method of treating a whole blood sample with acridine orange wherein the sample is passed through an optical flow cytometry cell having a narrowed hydrodynamic focal region. Red fluorescent light and forward scattered light are detected. Based on threshold comparisons, a threshold level is developed to separate the red cells from the reticulocytes.
U.S. Pat. No. 4,883,867 to Lee et al. relates to a fluorescent composition. The utilization of thiazole orange has been found to be an effective dye for staining reticulocytes.
SUMMARY OF THE INVENTION
The present invention provides a new, useful, and heretofore unobvious biological cell counting, measuring, and differentiating method and apparatus providing automatic high speed, accurate analysis and separation of cell types from each other within biological cell samples.
Broadly, the present invention provides a structural combination in which a biological sample of ghosted red cells, in the form of a hydrodynamically focused stream of particles, is passed into and through a point focused beam of light such as electromagnetic radiated energy, laser light. Light detector structure suitably positioned with respect to the axis of the light beam, provides a light output pulse indicative of the passage of each cell.
Electrically conductive contacts within the fluid stream pathway can provide additional electrical pulse outputs as the result of interrogation of each cell. Suitably placed photo receptors, angularly disposed with respect to the light beam axis, provide output electrical pulses indicative of the reticulocytes within the moving sample. By utilization of suitable electronic circuitry, the light and electronic produced output pulses or signals can be combined to define and quantify reticulocytes as distinct from other known cell types.
The present invention has to do with apparatus and method for generating data representative of reticulocytes by utilization of light scattering techniques alone and in combination with technology of the Coulter type.
Still more specifically, novel apparatus and methodology is provided by the present invention for utilizing the information or data derived from a light responsive pulse generating assembly which is arranged in the output area of a masked laser beam at a range of angles relative to the laser axis.
In the practice of the present invention, erythrocytes, treated with a lysing or "ghosting" reagent are analyzed by light scatter in a flow system, illuminated by a low-power laser, to provide detection and enumeration of reticulocytes, as a separate sub-population of erythrocytes.
The effect is evident in a wide range of light scattering angles, from low forward angles, e.g., 10°, up to and including approximately 180°. The preferred angle of analysis is from about 20° to about 65°.
Low frequency aperture impedance, also known as Coulter volume or DC, can be sensed simultaneously to identify and count all red cells, to discriminate erythrocytes from other cell types, and in addition, to obtain a mean reticulocyte volume.
High frequency or radio-frequency aperture impedance can be sensed simultaneously to further discriminate erythrocytes from other cell types.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an idealized rendering of a cytometric flow cell and operably associated structure including a photodetector assembly;
FIG. 1A is a front view (not to scale) of a photodetector assembly utilized with the present invention, illustrating the signal reception areas;
FIG. 2 is a system block diagram of an apparatus and operational electronic circuit for implementing the present invention;
FIGS. 3A-C are flow diagrams illustrating three methods for differentiating and enumerating reticulocytes according to this invention;
FIGS. 4A-D are data plots which illustrate the effect of staining and ghosting on a blood specimen containing reticulocytes;
FIGS. 5A-D are data plots which illustrate the results obtained at various angles of light scattering of a blood specimen containing reticulocytes;
FIGS. 6A-C to 7A-G are data plots which illustrate reticulocyte analysis reports generated by automated population classification methods utilizing light or light and electronic sensing techniques;
FIGS. 8A-C, 9A-C, 10A-C and 11A-C are data plots which illustrate reticulocyte analysis reports for numerous clinical human blood samples in a broad range of reticulocytes from 0.0 percent to about 30 percent; and
FIG. 12 illustrates a plot of reticulocyte percent obtained with the present invention vs. reticulocyte percent obtained with the reference method.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Definitions
In numerous figures and throughout the text of this specification, certain names and abbreviations will be utilized to obtain and/or describe the results obtained with the present invention.
"Histogram" is defined to be a graph of frequency distribution for a single variable, displayed as a two dimensional line graph with the variable plotted on the X axis and the frequency, designated as "#", plotted on the Y axis. Histogram also is defined as the abstract numerical tabulation of such a graph as represented within a computer or some other form of electrical circuit.
"Matrix" is defined to be a graph of frequency distribution for two independent variables, displayed as a three dimensional contour graph with one variable plotted on the X axis, the second variable plotted on the Y axis, and frequency or count displayed as iso-count contours. For clarity, only one iso-count contour will be displayed to illustrate population outlines. Matrix also is defined as the abstract numerical tabulation of such a graph as represented within a computer or some other form of electrical circuit. When describing a matrix in this Specification, the X axis variable will be listed first, followed by the Y axis variable.
"Parameter" is synonymous with independent variable and, in this invention as set forth in the following Specification, refers to any of the simultaneous, independent measurements obtained from particles or cells being analyzed in a flow cytometer. The combination of two or more parameters, by some mathematical function, is defined as yielding another parameter.
"Gating" is defined as a filtering process utilized in constructing, from multi-parameter data, a histogram of one parameter, while interrogating one or more of the other parameters. For each event, which is the passage of a single blood cell through the flow cell and the generation of cell measurements by the parameter transducers, the value or measurement corresponding to each parameter that is to be utilized for gating is compared with one or two reference values, or thresholds, and "tested" for being below the threshold, above the threshold, or between the two thresholds. If this test yields a true result for all the gating parameters being considered, then the event is included in the histogram. Gating also can be utilized to construct a matrix. Thus, by utilizing gating, it is possible to simplify the analysis and graphic representation of multi-parameter data.
"Photodetector" refers to any kind of device, vacuum or solid-state, which collects light and generates an electrical current proportional to the amount of light received by the photodetector.
"Beam dump" is defined as an obstruction for removing unwanted laser light, which generally appears as a horizontal line across the light detector as a result of the interaction between the laser beam and the flow cell, which if not blocked, degrades the detected light scatter signal.
"Mask" is defined as a circular or elliptical obstruction that removes unwanted low angle light scatter information, and prevents reception of this information by the light detector.
"DC" and "RF" are electronic sensing parameters which refer to the Coulter Principle of aperture impedance cell sensing. "DC" is defined as the pulse peak information obtained from applying a direct or low-frequency current, such that the cell membrane is not penetrated and no current flows through the cell. The peak amplitude of the DC pulse is a function of cell volume.
"RF" is defined as the pulse peak information derived from the measurement obtained from applying a high-frequency current, such that the cell membrane is short-circuited and current flows through the cell. RF is a function of cell volume and internal conductivity.
"Opacity" is defined as the signal value or data obtained by the division of the RF signal data by the DC signal data, for every individual cell measurement or event, yielding a new cellular parameter which is independent of size, but is a function of internal conductivity.
"LMALS" is defined as Lower Median Angle Light Scatter, which is light received at the photodetector assembly 28 scattered in or throughout the range of 10°-20° from the axis of the light beam, for example, the axis 30 of the laser beam 22.
"UMALS" is defined as Upper Median Angle Light Scatter, which is light received at the photodetector assembly 28 scattered in or throughout the range of 20°-65° from the axis of the light beam, for example, the axis 30 of the laser beam 22.
"RALS" is defined as Reverse Angle Light Scatter, which is light received at a photodetector assembly located in a reverse direction relative to the light beam 22 in the approximate angular range of 160°-176°.
"SALS" is defined as Side Angle Light Scatter, which is light received at a photodetector assembly located in an approximate angular range of 90°-20° from the axis of the light beam.
"RLS" is defined as Rotated Light Scatter, which is the log of UMALS divided by DC.
"RETIC" and "RETIC%" are both indicative of the reticulocyte count expressed as a percent of total erythrocytes.
"REF RETIC" is the reference reticulocyte percent obtained by following the microscopy-based methodology described in NCCLS document H-16P.
"RBC" is indicative of the absolute Red Blood Count, or erythrocyte count, which is usually expressed as count ×10 6 /μL.
"RETIC-ABS" is indicative of the absolute reticulocyte count usually expressed as count ×10 6 /μL.
"MRV" is defined as Mean Reticulocyte Volume, obtained by measuring the mean DC value for the reticulocyte population.
"RMI" and "MI" are both indicative of Reticulocyte Maturity Index which is defined as the ratio of the count of higher intensity light scatter reticulocytes to the total reticulocyte count.
"LS" is indicative of Light Scatter in general without specifying any particular angle or angular range.
"LLS" is defined as log of "LS". The preferred angle or angular range for LLS is LOG UMALS.
"RLS" is LLS, preferably LOG UMALS, divided by DC, as described earlier.
"LSR" is defined as Low intensity Scatter Reticulocytes.
"HSR" is defined as High intensity Scatter Reticulocytes. A more complete description of LSR and HSR is provided in a following section of this specification.
In the following description, light scatter angles are defined as the angles of the light exiting the biological cell within an aperture or sensing zone, still to be described. The angles of the scattered light striking a photodetector assembly, described hereinafter, can differ from the true angles within the aperture due to differences in indices of refraction of sample, diluent, and/or hydrodynamic sheath flow fluid, air, and the flow cell material, and also due to the architecture of the flow cell, as predicted by Snell's Law.
FIG. 1 illustrates a portion of a type of particle analyzing apparatus employing the method and process of the present invention. The apparatus of FIG. 1 includes a cytometric flow cell 10 which is made of any optically transparent material, for example fused silica. In this example, the interior of the flow cell 10 is cylindrical throughout its length, except for a narrowed or necked-down aperture 12 through which a biological cell sample is passed or flowed as a hydrodynamically focused stream 14 by well known means, not illustrated in this figure. An exterior wall surface 16 of the flow cell 10 is cylindrical, except for one side portion 18 which is flat.
A laser 20 emits a coherent light beam 22 into a lens or lens system 24 which focuses the beam 22 down to a small spot in the aperture or sensing zone 12. The laser 20 can be of any kind or wavelength.
Further, the invention is not limited to utilizing a laser as the light source. Other light sources, such as an arc lamp can be utilized, as long as the light can be focused down to a spot of the order of magnitude required for flow cytometric analysis. In this example, the laser 20 is a helium-neon laser of relatively low power, 0.8 mW, which emits at 632.8 nm. The lens system 24 includes two cross cylindrical lenses which are designed to focus the laser light beam 22 down to an elongated spot, aligned horizontally, within the aperture 12 of the flow cell 10. This optical shaping of the laser beam 22 makes the system less sensitive to cell or particle position, as the cells or particles flow through the flow cell 10, resulting in more uniform illumination and thus more uniform light scatter levels for identical cells or particles.
As the biological cells flow through the hydrodynamically focused stream 14, they pass individually through the aperture 12 and through the focused light beam 22, emitting light scatter rays 26 which are illustrated as dashed lines. A photodetector assembly 28, acting as a light scatter radiation receptor and positioned in a plane orthogonal to the axis 30 of the laser radiated light and centered on the axis 30, collects the light scatter rays 26.
FIG. 1 illustrates the photodetector assembly 28 in an isometric view. FIG. 1A illustrates the same photodetector assembly 28 in a front plan view. The following discussion applies to both FIGS. 1 and 1A. The photodetector assembly 28 includes a photovoltaic detector 32 and a beam dump 34 and mask 36 combination which is placed in front of the detector 32 and horizontally aligned. The mask 36 is a circular or elliptical structure which is placed in the center of the beam dump 34. The mask 36 is oriented coaxial with the laser light beam axis 30.
The horizontal beam dump 34 can take the form of a bowtie, being larger or wider at the outer end thereof than at the center. The horizontal beam dump 34 is employed to accommodate the optics to the condition wherein the laser beam is shaped so as to be stretched or flattened in the horizontal direction to make the system less sensitive to cell or particle position, as the cells or particles flow through the flow cell 10. This optical shaping provides a more uniform light output signal for utilization in electronically utilizing the light scatter signal output.
In FIGS. 1 and 1A, the photodetector 32 is divided into two zones 38, 40 by a circular band 42. As a result of the dimensions of the photodetector 32, the dimensions of the zones 38 and 40, the dimensions of the mask 36, and as a result of the distance of the photodetector assembly 28 to the flow cell 10, the inner zone 38 receives LMALS light scattered in or throughout the range of approximately 10°-20°. The outer zone 40 receives LMALS light scattered in or throughout the range of 20°-65°.
For this description, blood cells are assumed to be passing, one by one, through the aperture 12 of the flow cell 10 illustrated in FIG. 1. A complete system description, which details how blood cells or other particles are introduced into the flow cell 10, and how multi-parameter data on the cells is obtained and processed in order to achieve classification, is provided in Assignee's U.S. Pat. No. 5,125,737.
FIG. 2 illustrates a block diagram of a particle analyzing apparatus, or flow cytometer, for implementing the present invention, which includes the components illustrated in FIG. 1 and FIG. 1A and previously described. The laser 20 emits a coherent beam 22 into a lens or lens system 24 which focuses the beam 22 down to a small spot in the aperture or sensing zone 12 of the cytometric flow cell 10. The beam 22 exits the flow cell 10 and strikes the mask 36 and beam dump 34 of the photodetector assembly 28. Blood cells in a dilution are introduced to the flow cell 10 through a line 44 and flowed through a sample introduction tube 46. A sheath fluid 48 hydrodynamically focuses the cells 50 to pass individually through the aperture 12. After the cells exit the aperture 12, a second sheath 52 directs them into a sample exit tube 54 and into a waste chamber 56. When a cell 50 is in the aperture 12 and is illuminated by the focused laser beam 22, it will scatter light in many directions. Certain light scatter rays 58, 60, 62 and 64 are illustrated as dashed lines.
The photodetector 32 of the photodetector assembly 28 includes the two zones 38, 40. The angular ranges of the two zones 38, 40 are determined by the dimensions of the photodetector 32, the distance and position of the photodetector 32 relative to the flow cell 10 and the diameter of the mask 36. The inner zone 38 collects the LMALS light rays 58 scattered in the approximate angular range of 10°-20°, producing a signal which is fed to a preamplifier 66 which outputs an LMALS pulse 68. The outer zone 40 collects the UMALS light rays 60 scattered in the approximate angular range of 20°-65°, producing a signal which is fed to a preamplifier 70 which outputs a UMALS pulse 72. A photodetector 74 is placed perpendicular to the axis 30 of the laser beam 22 (perpendicular to the plane of the figure) collecting the SALS light rays 62 scattered in the approximate angular range of 90°-20°, producing a signal which is fed to a preamplifier 76 which outputs a SALS pulse 78. A pair of photodetectors 80 are placed symmetrically about the laser beam 22 collecting the RALS light rays 64 scattered in a reverse direction relative to the laser beam 22, and in the approximate angular range of 160°-176°, producing a signal which is fed to a preamplifier 82 which outputs a RALS pulse 84.
An electrical source unit 86 provides electrical current source, detection, and amplification means for the RF and DC signals. Radio-frequency current from an oscillator-detector 88 and direct current from a DC source 90 are combined in a coupling circuit 92 and fed to a pair of electrodes 94, 96. The electrodes 94, 96 are located in the flow cell 10 on opposite sides of the aperture 12 in a known manner. The currents are combined via a line 98 establishing current flow through the aperture 12. The particle or cell 50 traversing the aperture 12 momentarily changes the impedance of the aperture 12, modulating the RF and DC components of the current through the aperture. The RF current modulation caused by this impedance change is filtered and fed through the coupling circuit 92, to the oscillator-detector 88, which provides a detected pulse to a RF preamplifier 100, which outputs an RF pulse 102.
Concurrently, the modulation to the direct current caused by the impedance change is filtered and fed through the coupling circuit 92, to a DC preamplifier 104, and which outputs a DC pulse 106. The above description of the electrical source unit 86 is a preferred form which is described fully in Assignee's U.S. Pat. No. 4,791,355 entitled "Particle Analyzer for Measuring the Resistance and Reactance of a Particle." The electrical source unit 86 can include any other design that is capable of yielding substantially the same results. Some embodiments of this invention utilize only DC and not RF currents; thus, in those cases, the electrical source unit 86 need contain only the DC source 90 and the DC preamplifier 104.
"Pulse processor" modules 108, 110, 112, 114, 116 and 118 each contain amplifier, low-pass and high-pass filters, and baseline restorers. "Peak detector" modules 120, 122, 124, 126, 128 and 130 each provide a "value" which is a steady voltage proportional to the pulse peak amplitude. Logarithmic amplifier modules (log amp) 132, 134, 136 and 138 are circuits that can be switched to provide as an output the logarithmic transform of the input or the unaltered, linear input. Analog-to-digital converters (ADC) 140, 142, 144, 146, 148, 150, 152 and 154 provide data to a computer 156 for further processing.
The DC pulse 106 is fed to pulse processor 110 and to peak detector 122 to produce a DC value on a line which is fed to ADC 144, which feeds the digitized pulse peak value to the computer 156. The RF pulse 102 is fed to pulse processor 108 and to peak detector 120 to produce an RF value on a line 160 which is fed to ADC 140, which feeds the digitized pulse peak value to the computer 156. A divider module 162 divides the RF value by the DC value and produces the opacity value on a line 164 which is fed to ADC 142, which feeds the digitized value to the computer 156.
The UMALS pulse 72 is fed to pulse processor 112, to peak detector 124 and through log amp 132 to produce a UMALS value on a line 166 which is fed to ADC 148, which feeds the digitized pulse peak value to the computer 156. A divider module 168 divides the log UMALS value by the DC value and produces the RLS value on a line 170 which is fed to ADC 146, which feeds the digitized value to the computer 156. The LMALS pulse 68 is fed to pulse processor 114, to peak detector 126 and through log amp 134 to produce an LMALS value on a line 172 which is fed to ADC 150, which feeds the digitized pulse peak value to the computer 156. The SALS pulse 78 is fed to pulse processor 116, to peak detector 128 and through log amp 136 to produce a SALS value on a line 174 which is fed to ADC 152, which feeds the digitized pulse peak value to the computer 156. The RALS pulse 84 is fed to pulse processor 118, to peak detector 130 and through log amp 138 to produce a RALS value on a line 176 which is fed to ADC 154, which feeds the digitized pulse peak value to the computer 156.
The reagent system utilized to enumerate the reticulocytes includes a red blood cell and reticulocyte ghosting solution comprising potassium thiocyanate and sulfuric acid. The function of the ghosting solution is to effectively swell the red blood cell to a spherical shape without bursting them and to permit hemoglobin to leak from the red blood cell. In addition, the ghosting solution has a fixative property so that the cell maintains the resulting spherical shape caused by the swelling.
The native reticulocyte has an irregular shape which produces unpredictable light scatter information in a flow cytometer when subjected to a light beam at angles from 0°-90°. The sphering of the red blood cell provides reproducible light scatter information which forms the basis for determining the reticulocytes in the sample.
The removal of hemoglobin from the swelled red blood cell is essential to this invention. The decrease in the hemoglobin content enhances the definition of the reticulum to permit flow cytometric determination of the reticulocytes.
It has been found that the ghosting process is effected by temperature. More specifically, it has been determined that temperatures below 55° F. appear to retard the ghosting process and longer time periods are necessary to permit the ghosting process to occur. As a result, it is preferred that the blood sample be mixed with the ghosting solution at a temperature of approximately 55° to approximately 106° F. for approximately 30 seconds. It has been determined that 106° F. (41° C.) provides the shortest time of ghosting.
The pH of the ghosting solution should be approximately 1.0 to 3.0, preferably 1.0 to 2.0. In addition, it appears that the acidic ghosting solution solubilizes the hemoglobin and facilitates its removal from the blood cell. It has been noted that when utilizing potassium thiocyanate, sulfuric acid is the preferred acid to be utilized in the combination. More specifically, other acids which did not work as well as sulfuric acid, include hydrochloric and nitric acids. The preferred concentration for the potassium thiocyanate is approximately from 1.0 to 6.0 grams per liter, and for the sulfuric acid is approximately from 0.7 to 3.0 grams per liter.
The osmotic pressure of the ghosting solution should be controlled so that there is a rapid, but controlled swelling of the blood cell. The osmotic pressure of the ghosting solution will range from 75 to 110 milliosmoles, and preferably 82 to 105 milliosmoles. The osmotic pressure causes the blood cell to swell and release the hemoglobin within thirty (30) seconds of mixing with the ghosting solution. If the osmotic pressure is less than 75 milliosmoles, then the blood cell will not retain an intact cell membrane and will lyse. More specifically, lower osmotic pressure results in red cells that are damaged so that reticulocyte enumeration is not reliable. If the osmotic pressure is not sufficient, the blood cells will retain hemoglobin which will obscure reticulocyte differentiation.
In a preferred embodiment of the present invention, a reticulocyte stain is employed before the ghosting procedure. The function of the reticulocyte stain is to further delineate the reticulocytes for light scatter enumeration in a flow cytometer. The reticulocyte stain is a non-fluorochrome dye that precipitates intracellular ribonucleic acid (RNA) of the reticulocyte. Examples of suitable stains include new methylene blue and brilliant cresyl blue. Utilizing a non-fluorescent dye to measure reticulocytes, allows the blood sample to be further analyzed for other constituents utilizing a fluorescent dye. More specifically, by utilizing a precipitating RNA dye for the enumeration of reticulocytes, a compatible fluorescent dye can be utilized in the same assay to investigate other components of the blood sample without interference from the fluorescence of the reticulocyte stain.
The preferred reticulocyte stain comprises an aqueous solution of new methylene blue. The aqueous new methylene blue solution has an alkaline pH and ranges from about 7.0 to 8.5 and preferably from 7.0 to 8.0. The aqueous new methylene blue solution has a stain concentration range from 0.2 to 2.0 grams per liter and preferably from 0.4 to 1.2 grams per liter. Moreover, the osmotic pressure of the stain solution ranges from approximately 120 to 160 milliosmoles, and preferably from 130 to 150 milliosmoles.
It has been found that the staining reaction time is shortened by higher temperatures, while at lower temperatures a longer reaction time is required. The preferred temperature range for the reaction is from 60° to 90° F. Utilizing this temperature range, the reaction time needed for the stain to sufficiently react with the blood cell is at least 5 minutes.
In the preferred method for analyzing a blood sample for reticulocytes, anticoagulated blood is employed. The anticoagulants used are EDTA salts, such as dipotassium, tripotassium and disodium salts.
It has been found that the staining of the cells is enhanced by increasing the alkalinity of the blood sample and stain mixture to range from pH 7.0 to 7.5. However, the staining is non specific and does not enhance the differentiation of the reticulocytes. Rather, the staining offsets the light scatter signal to a higher channel.
In addition, the reticulocyte stain should include antimicrobial agents as preservatives. Preferred antimicrobials are propylparaben, methylparaben and combinations thereof. More preferred antimicrobial agents are a combination of propylparaben at a concentration of 0.3 grams per liter and methylparaben at a concentration of 0.5 grams per liter.
The following specific examples of the staining and ghosting reagents are utilized in obtaining the results illustrated in FIGS. 4-12.
______________________________________Staining Reagent #1 K.sub.3 EDTA 10 g/LNew methylene blue 0.6 g/LNaCl 2 g/LGhosting Reagent #1 KSCN 3 g/L1N H.sub.2 SO.sub.4 30 mL/L______________________________________
FIGS. 3A-C represent various operations of an apparatus or methods of preparing and analyzing blood samples to obtain reticulocyte classification and enumeration.
FIG. 3A illustrates two methods or operations of an apparatus for classifying and enumerating reticulocytes in step or flow diagram format. In both operations, a whole blood sample or portion 180 is treated with a ghosting reagent 182. The ghosted blood mixture is incubated 184 and analyzed in a flow cytometer 186. In the first option, the data from the flow cytometer is classified 188 using at least LS to yield RETIC% and RMI. In the second option, the data from the flow cytometer is classified 190 using at least LS with DC to yield RETIC%, MRV and RMI. With both options, RETIC-ABS then is obtained 192, 194 by multiplying RETIC% by RBC.
FIG. 3B illustrates two other methods or operations of an apparatus for classifying and enumerating reticulocytes. In both operations, a whole blood sample or portion 200 is treated with a staining reagent 202. The stained blood mixture is gently mixed 204 and incubated 206. The stained blood mixture 208 then is treated with a ghosting reagent 210. The ghosted blood mixture is incubated 212 and analyzed in a flow cytometer 214. Again as a first option, the data from the flow cytometer is classified 216 using at least LS to yield RETIC% and RMI. In the second option, the data from the flow cytometer is classified 218 using at least LS with DC to yield RETIC%, MRV and RMI. With both options, RETIC-ABS is obtained 220, 222 by multiplying RETIC% by RBC.
FIG. 3C illustrates yet two other methods or operations of an apparatus for classifying and enumerating reticulocytes. In both cases, 50 μL of whole blood 230 is treated with 100 μL of Staining Reagent #1 232. The stained blood mixture is gently mixed 234 for 5 seconds and incubated 236 for 5 minutes. A 2 μL portion of the stained blood mixture 238 then is treated with 2 mL of Ghosting Reagent #1 240. The ghosted blood mixture is incubated 242 for 30 seconds and analyzed in a flow cytometer 244. In a first option 246, the data from the flow cytometer is classified using at least UMALS to yield RETIC% and RMI. In the second option 248, the data from the flow cytometer is classified using at least UMALS with DC to yield RETIC%, MRV and RMI. With both options, RETIC-ABS is obtained by multiplying RETIC% by RBC 250, 252.
FIGS. 4A-D illustrate the effect of staining and ghosting on reticulocytes, analyzed in a particle analyzer or flow cytometer such as illustrated in FIG. 2. Each of the four figures is a matrix, or two-dimensional dot plot, of LOG UMALS vs. DC (LOG UMALS on the x axis and DC on the y axis) of the same whole blood specimen prepared with different combinations of the staining and the ghosting reagents. Other light scatter angular measurements, such as LMALS, SALS and RALS can be utilized, but UMALS is preferred. FIG. 4A illustrates the data pattern obtained by diluting a whole blood sample in a balanced electrolyte solution commonly utilized as a diluent in hematology analyzers sold by the assignee of the present invention and without any other treatment including a staining reagent or a ghosting reagent. One such solution is sold under the name ISOTON® II, by the assignee of the present invention.
It is evident in FIG. 4A that there is a single population 260, identifiable by LOG UMALS, which consists of erythrocytes and reticulocytes data massed together. FIG. 4B displays the data pattern obtained by treating the whole blood sample with the staining reagent only and not utilizing the ghosting reagent. The pattern of FIG. 4B is very similar to that of FIG. 4A, illustrating a single population 262 of erythrocytes and reticulocytes together, as identified by LOG UMALS. FIG. 4C displays the data pattern obtained by treating the whole blood sample with the ghosting reagent only and not with the staining reagent, illustrating a population of reticulocytes 264 to the right or a higher level of LOG UMALS than the mature erythrocytes 266. FIG. 4D displays the data pattern obtained by treating the whole blood sample with both the staining reagent and the ghosting reagent, illustrating a population of reticulocytes 268 to the right or a higher level of LOG UMALS than the mature erythrocytes 270, and better separated than the reticulocyte population 264 of FIG. 4C.
From the data illustrated in FIGS. 4A-D and the description thereof, it can be concluded that the minimum requirement to identify and enumerate reticulocytes by utilizing light scatter without fluorescence is to treat the blood sample with a ghosting reagent. It can also be concluded that treating the blood sample with both a staining reagent and a ghosting reagent results in the optimum configuration for identifying and enumerating reticulocytes with light scatter and without utilizing fluorescence.
FIGS. 5A-D illustrate the results obtained by analyzing a whole blood sample treated with the staining reagent and with the ghosting reagent and analyzed with the particle analyzer or flow cytometer of FIG. 2. at various angles of light scatter. Each of the four figures display a data matrix of a light scatter measurement on the x axis vs. DC on the y axis with a reticulocyte population 280 to the right of the mature erythrocyte population 282. FIG. 5A displays a data matrix of LOG LMALS vs. DC. FIG. 5B displays a data matrix of LOG UMALS vs. DC. FIG. 5C displays a data matrix of LOG SALS vs. DC. FIG. 5D displays a data matrix of LOG RALS vs. DC. From the data presented in FIGS. 5A-D and the description thereof, it has been demonstrated that reticulocytes, treated with at least a ghosting reagent, can be identified and enumerated by analyzing with light scatter, and that the light scatter can be collected at any of a variety of different angles, without using fluorescence. UMALS is the preferred light scatter angle, and will be used exclusively throughout the remainder of this specification.
In the methods illustrated in FIGS. 3A-C and throughout this specification the step of obtaining RBC can be implemented in two different procedures. Referring to FIG. 2, the first procedure involves performing the absolute erythrocyte count on the same blood sample which is treated and analyzed for reticulocyte classification and enumeration, and performing the count at the same time the blood cells 50 traverse the aperture or sensing zone 12. Any of the simultaneously measured parameters, such as DC, RF, LMALS, UMALS, SALS and RALS, can be utilized to obtain the absolute erythrocyte count, RBC. DC is the preferred parameter for obtaining RBC. The second procedure for obtaining RBC is to use another apparatus, a particle or blood cell counter (for example, the COULTER® STKS sold by the assignee of the present invention), which can be physically attached to the reticulocyte analyzer of, for example, FIG. 2, or which can be part of another instrument. Using either the first or second procedure to obtain RBC, the RBC and RETIC% results are combined to compute RETIC-ABS.
FIGS. 6A-C and FIGS. 7A-G illustrate data classification methods applicable to data generated by any of the methods of FIGS. 3A-C. The methods of FIG. 3C, involving treating a blood sample with Staining Reagent #1 and Ghosting Reagent #1, and analyzing the treated sample with at least UMALS in a particle analyzer, for example such as illustrated in FIG. 2, provide the optimum configuration for practicing this invention, and provide the reticulocyte data illustrated in FIGS. 6A-C.
FIGS. 6A, 6B and 6C illustrate numerous data classification methods where the reticulocytes are classified and enumerated utilizing at least a combination of LLS and DC. With the classification method illustrated by FIG. 6A, a boundary 290 separates a thrombocyte population 292 from populations of erythrocytes 294, 296, 298 and leucocytes 300 utilizing DC. Utilizing LLS, a boundary 302 separates the mature erythrocytes 294 from the reticulocytes 296, 298. A boundary 304 separates the reticulocytes 296, 298 from the leucocytes 300. A boundary 306 separates LSR 296 from HSR 298. Thus, it can be concluded from FIG. 6A, that utilizing a combination of LLS and DC, and treating the blood sample with the staining and the ghosting reagents, a classification can be made of the thrombocytes 292, the leucocytes 300, the mature erythrocytes 294 and the reticulocytes 296, 298, and that the reticulocytes 296, 298 can be subclassified into LSR 296 and HSR 298.
Another method for achieving the just described classification is by analyzing one-dimensional histograms one at a time, applying the "gating" technique defined earlier.
1. Utilizing a DC histogram, FIG. 6C, find the boundary 290 or valley which separates the thrombocyte population 292 from a single peak 308 which contains the erythrocytes and leucocytes.
2. Gating on DC values greater than the boundary 290 of FIG. 6C, which effectively removes the thrombocytes 292 from subsequent analysis, generate LLS histogram, FIG. 6B, and utilizing that histogram perform the following steps:
a) Find the boundary 302 which separates mature erythrocytes 294 from the reticulocytes 296, 298; count the mature erythrocytes 294 from the origin (leftmost extreme) of the histogram to the boundary 302;
b) Find the boundary 304 which separates the reticulocytes 296, 298 from the leucocytes 300; count the reticulocytes 296, 298 from the boundary 302 to the boundary 304;
c) Find the boundary 306 which separates LSR 296 from HSR 298; count LSR 296 from the boundary 302 to the boundary 306; count HSR 298 from the boundary 306 to the boundary 304.
3. Gating on DC values greater than the boundary 290 of FIG. 6C, and gating on LLS values greater than the boundary 302 and LLS value less than the boundary 304 of FIG. 6B, generate a DC histogram (not shown) of reticulocytes only and perform statistical analysis of those reticulocytes to yield DC mean.
4. Compute the following results:
a) Compute total erythrocytes=mature erythrocytes+reticulocytes;
b) Compute RETIC%=(reticulocytes/total erythrocytes )*100;
c) Compute MRV=DC mean*calibration factor;
d) Compute RMI=HSR/reticulocytes.
5. Obtain RBC as previously described and compute RETIC-ABS=RETIC%*RBC.
Another method for reticulocyte classification and enumeration involves utilizing only LLS.
1. Generate a LLS histogram, such as shown in FIG. 6B, and utilizing that histogram perform the following steps:
a) Find the boundary 302 which separates the mature erythrocytes 294 from the reticulocytes 296, 298; count the mature erythrocytes 294 from the origin (leftmost extreme) of the histogram to the boundary
b) Find the boundary 304 which separates the reticulocytes 296, 298 from the leucocytes 300; count the reticulocytes 296, 298 from the boundary 302 to the boundary 304;
c) Find the boundary 306 which separates LSR 296 from HSR 298; count LSR 296 from the boundary 302 to the boundary 306; count HSR 298 from the boundary 306 to the boundary 304.
2. Compute the following results:
a) Compute RETIC%=(reticulocytes/total erythrocytes)*100;
b) Compute RMI=HSR/reticulocytes.
3. Obtain RBC as previously described and compute RETIC-ABS=RETIC%*RBC.
A drawback of the just described method is that thrombocytes are not excluded from the analysis and can distort the RETIC% and other results. The preferred method requires a DC or some other equivalent measurement of cell volume, taken with the light scatter measurement for each blood cell, which can be utilized to discriminate and to eliminate thrombocytes from the reticulocyte analysis.
FIGS. 7A-G illustrate numerous data classification methods where reticulocytes are classified and enumerated utilizing at least a combination of LLS and DC, preferably the combination of LLS, DC, RLS and "OP", which is an abbreviation for opacity. Where applicable, the same numerals are utilized as utilized in FIGS. 6A-C.
With the classification method of FIG. 7A, the boundary 290 separates the thrombocytes 292 from the erythrocyte population 294 and 310 and the leucocytes 300 utilizing DC. Utilizing LLS, a slanted boundary 312 separates the mature erythrocytes 294 from the reticulocytes 310. The boundary 304 separates the reticulocytes 310 from the leucocytes 300. Thus, it can be concluded from FIG. 7A, that utilizing a combination of LLS and DC, and treating the blood sample with the staining and ghosting reagents, a classification and enumeration can be made of the thrombocytes 292, the leucocytes 300, the mature erythrocytes 294 and the reticulocytes 310. In addition, the following results can be reported: RETIC%, MRV and, by obtaining RBC, RETIC-ABS.
The classification method illustrated by FIG. 7B is combined with the just described method illustrated by FIG. 7A to expand and refine the results obtained. The data pattern shown in FIG. 7B is equivalent to the pattern of FIG. 7A with the exception that RLS is displayed on the x axis, resulting in a rotation of the data, and that the leucocytes 300 on FIG. 7A are gated-out or excluded from the analysis. In FIG. 7B, the boundary 290 separates the thrombocytes 292 from the erythrocytes 314, 316, 318; a boundary 320 separates the mature erythrocytes 314 from the reticulocytes 316, 318; a boundary 322 separates LSR 316 from HSR 318. The advantage of working with the RLS parameter is that the boundaries 320, 322 can be found that are completely orthogonal to the x and y axes. The boundary 320 of FIG. 7B, when projected onto FIG. 7A shows up as the sloping line 312. Thus, the rotated parameter RLS, utilized in conjunction with LLS and DC, and utilized to analyze a blood sample treated with the staining and the ghosting reagents, provides a preferred method of classifying and enumerating the reticulocytes, yielding the following results: RETIC%, MRV, RMI and, by obtaining RBC, RETIC-ABS.
The classification method illustrated by FIG. 7C is combined with the Just described methods illustrated by FIGS. 7A-B to further refine the results obtained. FIG. 7C illustrates a matrix of OP vs. DC. The boundary 290 separates the thrombocytes 292 from all other cell populations being analyzed 324, 326 by DC. A boundary 328 separates the cluster 324 including the erythrocytes and leucocytes from the thrombocyte or platelet clumps 326. The platelet clumps 326 are easily identified and gated-out or removed from further analysis utilizing opacity, as illustrated in FIG. 7C. Referring to FIG. 7A, the platelet clumps, if not identified and gated-out by opacity, may overlap with the mature erythrocytes 294 and the reticulocytes 310, distorting the RETIC% and other results. Platelet clumps occur infrequently, but should not interfere with the analysis of reticulocytes. Thus the OP parameter, utilized in conjunction with DC, LLS and RLS, and utilized to analyze a blood sample treated with the staining and ghosting reagents, provides a preferred method of classifying and enumerating the reticulocytes, yielding the following results: RETIC%, MRV, RMI and, by obtaining RBC, RETIC-ABS.
Another way of achieving the just described classification, illustrated by FIGS. 7A-C, is by analyzing one-dimensional histograms FIGS. 7D-G one at a time, applying the "gating" technique defined earlier.
1. Utilizing a DC histogram, FIG. 7E, find the boundary 290 which separates the thrombocytes 292 from a single peak 330 which contains the erythrocytes, leucocytes and platelet clumps.
2. Gating on DC values greater than the boundary 290 of FIG. 7E, which effectively removes the thrombocytes 292 from the subsequent analysis, generate a OP histogram, FIG. 7G, and utilizing that histogram, find the boundary 328 which separates the erythrocytes and leucocytes 324 from the platelet clumps 326.
3. Gating on DC values greater than the boundary 290 of FIG. 7E, which effectively removes the thrombocytes 292 from the subsequent analysis, and also gating on values less than the boundary 328 of FIG. 7G, which effectively removes the platelet clumps 326 from the subsequent analysis, generate a LLS histogram, FIG. 7D, and utilizing that histogram, find the boundary 304 which separates the erythrocytes 294, 310 from the leucocytes 300.
4. Gating on DC values less than the boundary 290 of FIG. 7E, which effectively removes the thrombocytes 292 from the subsequent analysis, also gating on OP values less than the boundary 328 on FIG. 7G, which effectively removes the platelet clumps 326 from the subsequent analysis, and also gating on LLS values less than the boundary 304 of FIG. 7D, which effectively removes the leucocytes 300 from the subsequent analysis, generate a RLS histogram, FIG. 7F, and utilizing that histogram, perform the following steps:
a) Find the peak of the mature erythrocyte population 314;
b) Fit a normal probability function curve on the mature erythrocytes peak 314;
c) Find the boundary 320 which separates the mature erythrocytes 314 from the reticulocytes 316, 318 by computing the channel at which the fitted curve and the remaining data overlap at equal probabilities; count the mature erythrocytes 314 from the origin (leftmost extreme) of the histogram to the boundary 320;
d) Find the boundary 322 which separates LSR 316 from HSR 318; count LSR 316 from the boundary 320 to the boundary 328; count HSR 318 from the boundary 322 to the maximum (rightmost extreme) of the histogram.
5. Gating on DC values greater than the boundary 292 of FIG. 7E, gating on OP values less than the boundary 328 on FIG. 7G, gating on LLS values less than the boundary 304 of FIG. 7D, and gating on RLS values greater than the boundary 320 of FIG. 7F, generate a DC histogram (not shown) of the reticulocytes only and perform statistical analysis of those reticulocytes to yield DC mean.
6. Compute the following results:
a) Compute total erythrocytes=mature erythrocytes+reticulocytes;
b) Compute RETIC%=(reticulocytes/total erythrocytes)*100;
c) Compute MRV=DC mean*calibration factor;
d) Compute RMI=HSR/reticulocytes.
7. Obtain RBC as previously described and compute RETIC-ABS=RETIC%*RBC.
FIGS. 8A-C, 9A-C, 10A-C and 11A-C show examples of human blood specimens prepared with the reticulocyte treatment method of FIG. 3C, analyzed with at least UMALS and DC in an apparatus as illustrated in FIG. 2 and classified by the methods illustrated by FIGS. 7A-G. The plots in each of the FIGS. 8-11 are depicted the same as in FIG. 7A, but without boundary and population numerals. The actual reticulocyte classifications are illustrated for each of FIGS. 6-11.
FIG. 12 shows a correlation study of human blood specimens with the "REFERENCE%" plotted on the x axis and "RETIC% on the y axis. "REFERENCE%" is the reticulocyte percentage obtained by the reference method outlined in the proposed NCCLS standard, H16-P. The "RETIC%" is the result generated by the preferred methods and apparatus as described earlier. A dotted 45° line 332 represents a perfect data fit or a correlation coefficient of 1.0. The actual data fit is illustrated by a solid line 334. The difference between the two lines represents a correlation coefficient of 0.95. | A reticulocyte analyzing method and apparatus in which a biological sample stream of ghosted red cells is passed into and through a point focused beam of light, such as laser light. A light detector structure is positioned with respect to the axis of the light beam to provide a light output pulse indicative of the passage of each cell. Electrically conductive contacts within the fluid stream can provide additional electrical pulse outputs of each cell. A staining reagent can be utilized with a ghosting reagent to further differentiate the reticulocytes. The light and the light and electronic produced output pulses or signals can be combined to define and quantify reticulocytes as distinct from other known cell types. | 6 |
RELATED APPLICATIONS
[0001] The present Application claims priority of U.S. Provisional Patent Application No. 61/593,400, entitled “Improved Vitis vinifera Variety,” and filed on Feb. 1, 2012, and which is incorporated herein by reference in its entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable.
BACKGROUND OF THE INVENTION
[0003] The present invention relates to a new and distinct variety of grapevine, Vitis vinifera , which is hereinafter denominated by the variety name “Green Emerald,” and also referred to hereinafter as JPD-001. More specifically, the invention relates to a grapevine that produces fruit maturing for commercial harvesting and shipment around August 20, in the San Joaquin Valley of Central California. The fruit is naturally large and responsive to berry size augmentation treatments. There is no lignified seed trace, and the berries exhibit excellent crispness and a skin not prone to cracking.
[0004] The grapevine of the present invention originated from the white, seedless variety, Sheehan-Genetics 10-418 (unpatented). In the spring of 2002, Sheehan-Genetics 10-418 was grafted onto 2-A Thompson Seedless in a variety plot owned by Jakov P. Dulcich and Sons, near McFarland, Calif. The plant that resulted from this grafting was grown from 2002 until 2006, at which time asexual one-bud cuttings of plants resulting from the Sheehan-Genetics 10-418/2-A Thompson Seedless graft were selected from this vineyard and grafted upon a variety known as Crimson at another Jakov P. Dulcich and Sons varietal plot near Delano, Calif. In January, 2010, select samples from this plot exhibiting characteristics desired for what would become JPD-001 were propagated by one-bud asexual cuttings and grafted onto Red Globe (U.S. Plant Pat. No. 4,787) in a variety plot near McFarland, Calif. Resulting plants harvested in 2011 were stable, unique, and distinguishable from the parent plant material. The stability of the resulting plants was demonstrated again in 2012, with additional production of the new variety. These resulting plants are the subject of this plant patent application.
SUMMARY OF THE INVENTION
[0005] A new grape vine, denominated “Green Emerald,” also referred to as JPD-001, is of Vinis vinifera parentage. JPD-001 is a large berry-size, white, seedless grape maturing for harvest in approximately the third week of August in the San Joaquin Valley of Central California. JPD-001 is distinguished from its parent cultivar, Sheehan-Genetics 10-418, in that it has a much larger natural berry size, crisper texture, and lacks a noticeable seed trace. The lack of a noticeable seed trace is due to the fact that the aborted seed does not lignify, and is aborted much earlier in development and maturity as compared to the parent variety. The present variety also exhibits a heightened response to berry size augmentation treatments.
BRIEF DESCRIPTION OF THE ILLUSTRATIONS
[0006] The illustrations of the grapevine of the present invention are color photographs showing the following:
[0007] FIG. 1 shows the new variety growing on a trellis in the field.
[0008] FIG. 2 shows growing tips, leaves, and a berry cluster of the new variety.
[0009] FIG. 3 shows a berry cluster of the new variety, as well as cross-sections of the berries thereof. A measurement of berry size is also provided.
[0010] FIG. 4 shows a berry cluster of the new variety and provides a measurement of berry size.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The following is a detailed description of plants in the new variety, JPD-001, grown outdoors near McFarland, Calif., on their own rootstock. The color-terminology used herein is in accordance with the Royal Horticultural Society Color Code.
[0012] JPD-001 is a large berry-size, white, seedless grape maturing for harvest in approximately the third week of August in the San Joaquin Valley of Central California.
Botanical description:
Vineyard .—The vineyard is trained to a quadrilateral cordon on a wood trellis. The approximate height of the trellis is 114 cm with cordons resting at approximately 112 cm. The width between the cordons is approximately 56 cm. Vigor .—Moderately vigorous. Growing season .—April 1 through December 1. Productive capacity .—Good.
Trunk characteristics:
Size .—Circumference of 16.5 cm and length of 76 cm from graft union to the cordons. Surface texture .—Rough and shaggy. Color of bark .—(One year or older wood) Gry/G 197-B. Cane length.— 1.65 meters. Mature/lignified cane color .—Gry/B N199-D. Mature/lignified cane texture .—Smooth. Internode length.— 8 to 10.5 cm.
Branch characteristics:
Size.— 102 cm in length and 11 cm in circumference. Surface texture .—Slightly tough and shaggy. Color .—(One year old wood) Gry/G 197-B. Lenticels.— 0.
Leaves/shoots:
Size.— 12 to 17 cm. Density .—Moderately dense. Form .—Pentagonal. Leaf base .—Sagittate. Texture .—Upper: Smooth. Lower: Glabrous. Color .—Upper: G 141-B. Lower: G 138-A. Leaf vein .—Color: Y/G 144-B. Thickness: 1.5 to 2 mm. Presence of anthocyanin: Absent. Leaf margin .—Serrated/toothed; slightly undulating. Glands .—Absent. Petiole .—Length: 9 to 11 cm. Thickness: 2 to 4 cm. Erect Hairs on Petiole: Absent. Color: Y/G 144A but with streaks of Gry/R 180-A on side exposed to sun. Petiole sinus .—General shape: Open (ovate). Stem glands .—Absent. Stipules .—Absent. Lobes.— 5. Teeth .—Serration length: 0.33 to 1.5 mm; width 0.5 to 1.0 mm. Ratio of length/width: about 1:1. Size .—Large; approximately 18 cm in length at full bloom. Shape .—Long, conical. Number borne per shoot .—One or two. Number borne per vine.— 45 to 55.
Flowers:
General .—Flower sex: Perfect. Flower buds .—Size: 5 to 7 mm in width and 7 to 8 mm in length. Shape: Triangular. Fruitfulness: Good. Flowers .—Pedicle length: 3 mm. Calyptra color: G 134-A. Ovary: length 2mm; width 1.5 mm; color G 135-B. Pistil: length 1.5 mm. Anthers: length 0.5 mm; color Y 6-C. Filament: length 1.0 mm; color G 142-C. Date of visible berries .—Approximately May 14.
Fruit:
Maturity .—Ripening approximately August 27. Solids.— 17.5 to 18.0 brix at desired maturity. Acids.— 5.0 to 7.5 TA. Sugar/acid ratio.— 2.5:1 to 3.5:1. Seeds ( number, characteristics ).—Two aborted, non-lignified seeds due to embryo abortion. Capstem .—Normal size; color Y/G 145-A. Berry weight .—Average weight; large natural berry size, around 6 g to 7 g; with size augmentation, berry weight increases to around 9 g to 15 g. Juice color .—Y/G 145-B. Cluster .—Large, loose, conical cluster with an average weight of 2 to 3 lbs. Stem size ( general characteristics ).—Strong stem; not prone to breaking, with average thickness. Berry size ( number/bunch ).—Large natural berry size of around 19 mm; with size augmentation treatments, berry size increases to 23 mm to 28 mm. Skin .—Berry skin is of average thickness, and not prone to cracking. Seed trace .—Slight trace of non-lignified seed due to embryo abortion. Flesh color .—Y/G 149-D; very nice eating quality and crunchy texture. Flavor and aroma similar to Thompson Seedless, but with much crisper texture. Use .—Table.
[0072] Although the new variety of grapevine described herein possesses the described characteristics noted above as a result of the growing conditions prevailing in or around McFarland, in the Central San Joaquin Valley of California, United States of America, it is to be understood that variations of the usual magnitude and characteristics incident to changes in growing conditions, training, irrigation, fertilization, pruning, pest control, climatic variation, and the like, are to be expected. | A new and distinct variety of grapevine denominated “Green Emerald,” which is characterized by its large natural berry size, increased responsiveness to berry size augmentation, and lack of a noticeable seed trace. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This case is the U.S. national phase of International Application No. PCT/EP2005/001973 filed Feb. 25, 2005 which claims priority of European Application No. 04405133.2 filed Mar. 5, 2004.
BACKGROUND OF THE INVENTION
[0002] The invention concerns a method for the continuous production of fibre-reinforced plastics plates with a thermoplastics matrix, and particularly a method for continuous production of a planar thermoplastic plate material reinforced with flat fibre structures, characterised in that a first web-like fibre structure is supplied to a fibre laying device, by means of in-line fibre feed units one or more further web-like fibre structures are arranged over the first fibre structure, by means of one or more matrix feed units connected before or after the fibre feed units a matrix starting material is supplied to exposed layers of fibre structures, and the multilayer fibre web emerging from the fibre laying device and coated one or more times with intermediate layers of matrix starting material is supplied to a continuous press in which the matrix starting material is transformed under the effect of heat and/or pressure into a low viscosity fluid and the multilayer fibre web under impregnation of the fibre structure is pressed into a plate-like plastics material.
[0003] Previously, it was difficult to produce thermoplastics plastics matrix systems in a continuous method for the production of fibre-reinforced plastic plates. The difficulty in processing thermoplastic plastics matrix systems lies amongst others in the provision of a suitable reactive starting material which is not only chemically stable but can also be transformed into a low viscosity state for further processing. In addition, no suitable method is known for continuous production of plate material with a thermoplastic plastics matrix system.
[0004] Thus previously the production of fibre-reinforced plate material with thermoplastic plastics matrix has been restricted to discontinuous and correspondingly costly processes.
[0005] The object of the present invention is to propose a continuous method for the production of plate material reinforced with fibre structures and with a thermoplastic plastics matrix.
SUMMARY OF THE INVENTION
[0006] According to the invention the object is achieved by a method for continuous production of a planar thermoplastic plate material reinforced with flat fibre structures, characterised in that a first web-like fibre structure is supplied to a fibre laying device, by means of in-line fibre feed units one or more further web-like fibre structures are arranged over the first fibre structure, by means of one or more matrix feed units connected before or after the fibre feed units a matrix starting material is supplied to exposed layers of fibre structures, and the multilayer fibre web emerging from the fibre laying device and coated one or more times with intermediate layers of matrix starting material is supplied to a continuous press in which the matrix starting material is transformed under the effect of heat and/or pressure into a low viscosity fluid and the multilayer fibre web under impregnation of the fibre structure is pressed into a plate-like plastics material.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The invention is explained in more detail below with reference to the enclosed drawing as an example. This shows:
[0008] FIG. 1 a, b : a device for performance of the method according to the invention;
[0009] FIG. 2 an exemplary arrangement of a fibre structure according to the method in the invention;
[0010] FIG. 3 an exemplary arrangement of the powder scatterer within the device;
[0011] FIG. 4 a cross-section through A-A according to FIG. 3 with exemplary arrangement of the fibre structure.
DETAILED DESCRIPTION
[0012] The definitions of the terms below are valid for the present text:
[0013] Reactive starting material in the definition comprises amongst others cyclic or macrocyclic oligomers of polyester, in particular PBT (known as CPBT) which are mixed with a polymerisation catalyst. Furthermore, the reactive starting material also comprises blends (alloys) containing the above substances which for example after completion of the polymerisation lead to a PBT blend (PBT plastic alloy). Reactive starting materials of the said type for production of polyester or PBT plastics are described in more detail in U.S. Pat. No. 6,369,157, the content of which is hereby part of the disclosure. A particularly suitable reactive starting material with cyclic oligomers is sold under the name CBT™ (Cyclic Butylene Terephthalate) by the company Cyclics or Dow Chemical Company.
[0014] The polymerisation catalyst can for example be a zinc catalyst or other suitable catalyst. The reactive starting material in the definition is characterised in particular in that for processing, it can be transformed into a low viscosity melt which thoroughly impregnates the fibre structure.
[0015] Polyesters according to the definition comprise amongst others plastics such as PET (polyethylene terephthalate) and associated plastics alloys and in particular PBT (polybutylene terephthalate) or PBT blends also known as PBT plastics alloys.
[0016] Fibre structures according to the invention are planar structures and comprise amongst others textile structures e.g. fleeces, non-wovens, non-mesh forming systems such as weaves, uni- or bidirectional lays, braids or mats etc. or for example mesh-forming systems such as knitted fabrics and knitted structures.
[0017] The fibres of the fibre structure contain by definition long fibres with fibre length of e.g. 3-150 mm, or endless fibres. They are processed for example in the form of rovings into fibre structures.
[0018] The fibres can be glass fibres, aramid fibres, carbon fibres, plastic fibres, natural fibres or mixtures thereof. Plastics fibres can in particular be polyester fibres e.g. PET, PBT or PBT blends. With regard to inorganic fibres, glass fibres are used for preference as these, in contrast to aramid or carbon fibres, can be separated relatively cheaply from the plastics matrix on recycling of the fibre-reinforced plastics article, and furthermore glass fibres are relatively cheap.
[0019] PBT fibres are characterised in that due to the production process these have a crystalline alignment in the fibre direction while the matrix between the fibres largely has no crystalline alignment i.e. is amorphous or of partly crystalline nature.
[0020] A plate according to the definition means a planar body with a certain bending stiffness and a thickness which in comparison with the length and width is substantially smaller. The plates which are produced according to the method of the invention continuously, i.e. endlessly, have for example a thickness of 1 mm or greater, preferably 3 mm or greater and in particular 5 mm or greater, and of 50 mm or smaller, preferably 20 mm or smaller and in particular 10 mm or smaller.
[0021] For execution of the method, a first web-like and preferably unfolded fibre structure is fed to a fibre laying device in the advance direction. By means of fibre feed units, in line one or more further web-like fibre structures are arranged over the first fibre structure. Before or after at least one, and preferably several, fibre feed units are provided matrix feed units by means of which a matrix starting material is supplied to exposed layers of fibre structures.
[0022] The multilayer fibre web which is guided through the fibre laying device and continuously coated with further fibre layers and/or matrix starting material, after conclusion of the coatings i.e. after emergence from the fibre-laying device, is supplied to a continuous press in which the matrix starting material is transformed under the effect of heat and/or pressure into a low viscosity fluid, and the multilayer fibre web under impregnation of the fibre structure is pressed into a plate-like material.
[0023] The fibre laying device and the continuous press are here arranged in-line. In-line means arranged in a (single) production line.
[0024] The fibre structures can be supplied dry or already pre-impregnated, in particular pre-impregnated with a binding agent. The composition of the pre-impregnation corresponds preferably to the matrix starting material supplied.
[0025] The matrix starting material is preferably by definition a reactive starting material. The reactive starting material contains in particular cyclic oligomers of PBT (CPBT) mixed with a polymerisation catalyst or comprising this.
[0026] The matrix starting material is applied e.g. in liquid form, as a foil or film and preferably in powder form onto the fibre lay(s). If the matrix starting material is applied in liquid form, this can be done by spraying, coating, casting, rolling or scraping. The matrix feed units are equipped accordingly. Furthermore, the matrix starting material can also be applied by impregnation of the fibre structures in a continuous immersion bath.
[0027] By heating of the fibre structure or fibre lay coated with the matrix starting material, in particular with powder or a film or foil, in the fibre laying device, due to the adhesive properties of the softened or melted starting material, the fibre structure or its fibres are glued together, wherein the polymerisation process need not necessarily be triggered but in a special embodiment of the invention can already begin.
[0028] The low viscosity properties of the matrix starting material which is used guarantee optimum saturation or impregnation of the fibres, which is of great importance in particular in plastics articles with a high fibre content in the form of dense fibre structures. The fibre content of the fibre-reinforced plastics panels which are produced with the method according to the invention is preferably more than 30 vol. % (volume percent), in particular more than 40 vol. % and preferably less than 80 vol. %, in particular less than 70 vol. % and advantageously less than 60 vol. %.
[0029] Polymerisation of the reactive matrix starting material into a thermoplastic plastics matrix, in particular a PBT plastics matrix, takes place fully or at least mainly in the continuous press.
[0030] According to a first specific embodiment of the invention, the matrix starting material in powder form is scattered by means of a powder scattering device onto the fibre structure.
[0031] According to a second specific embodiment of the invention the matrix starting material is applied to the fibre structure in the form of a foil or film.
[0032] The fibre laying device preferably contains one or more pressing stations arranged in-line, in particular impression cylinders, by means of which the multilayer fibre web can be pre-pressed in-line.
[0033] The said impression cylinders comprise a contact roller and an impression roller arranged in pairs, between which the multilayer fibre web is guided under pressure.
[0034] In a refinement of the invention the pressing station or impression cylinder is part of the fibre feed unit, where the contact roller serves simultaneously as transport roller by way of which a web-like fibre structure is supplied or deflected in the advance direction and applied to the fibre lay. The pressing station is preferably arranged in a fibre feed unit supplying the fibre structure unfolded in the advance direction.
[0035] In the refinement of the invention at least one fibre feed unit is designed as a cross layer by means of which a web-like flat structure, supplied obliquely or diagonally to the advance direction of the multilayer fibre web, by regular folding thereof along side edges, forming laying edges of the multilayer fibre web, is applied as multiple layers i.e. in particular as two layers with simultaneous advance on the fibre web. The fibre structure which is applied is preferably supplied at an angle of around 45° to the advance direction of the fibre lay and in each case laid at an angle of around 45° to the advance direction of the fibre lay. The web width of the obliquely supplied fibre structure here corresponds to the length of the edge line running obliquely over the fibre web from one laying edge to the opposite laying edge. Furthermore, the web width of the obliquely supplied fibre structure corresponds to the product b×√2 (square root of 2) where b is the width of the (multilayer) fibre web.
[0036] However, other feed and laying angles and other web widths can be selected. The fibre feed unit with cross layer here allows adjustment of the feed and laying angle.
[0037] The fibre structure is applied crossing by means of deflections in the cross layer in an alternating sideways movement i.e. a reciprocating movement in relation to the advance direction. Furthermore, the fibre structure can be applied crossing by means of deflection in the cross layer in a coil-like rotary movement. The multilayer fibre structures which are applied crossing can in some cases be fixed to each other or to other fibre structures in secondary stations by means of aids such as fibres, needles or threads.
[0038] If the fibre structures for example contain aligned fibres, in particular fibres aligned in one or two directions as is normal with woven structures, due the sectional laying of the fibre structures the fibre direction in the fibre web changes continuously, whereby the mechanical values are reinforced in several directions.
[0039] In a refinement of the invention, a web-like unfolded fibre structure is supplied in the advance direction of the fibre lay and alternately a secondary web-like fibre structure, folded crossways, is supplied obliquely or diagonally to the advance direction of the fibre lay. The fibre structure forming the first final fibre cover layer of the multilayer fibre web and the fibre structure forming the second final fibre cover layer of the multilayer fibre web are preferably unfolded and supplied in the advance direction of the multilayer fibre web. The two fibre structures are supplied accordingly with the first and last fibre feed unit of the fibre laying device.
[0040] For the purpose of supplying the matrix starting material, preferably at least after each fibre feed unit with cross layer is arranged a matrix feed unit, in particular a powder scatterer. However, each fibre feed unit can also be followed by a matrix feed unit, in particular a powder scatterer. In the preferred embodiment of the invention, in particular between the last fibre feed unit and the continuous press, is arranged a last matrix feed unit, in particular a powder scatterer.
[0041] The number of fibre layers and the quantity of the matrix starting material which are used determines the achievable thickness of the multilayer fibre web and hence the plate material to be produced and its fibre content. The individually applied fibre structures can have structures which deviate from each other. Thus for example alternate layers of fibre fleece and fibre weave can be provided.
[0042] The multilayer fibre web in a preferred embodiment of the invention is coated, after the supply of all fibre structures and all matrix starting material and before entering the continuous press, on one or both sides with a cover layer in the form of a plastic film or extruded plastic film by means of a film feed device. In the secondary continuous press, the cover layer thus connects with the polymerising plastics matrix of the multilayer fibre web. The cover layer is then an integral part of the fibre-reinforced plate material to be produced.
[0043] The cover layer is preferably made of polymerised thermoplastic plastics, preferably a (polymerised) polyester such as PET, in particular a PBT or PBT plastic alloy. The cover layers and plastics matrix of the multilayer fibre web in the polymerised state can comprise the same plastics or similar plastics alloys.
[0044] The cover layer which is applied to the fibre web can also be a fibre-reinforced web-like plastics material with an outer, exposed, fibre-free (polymerised) plastics layer of the composition given above.
[0045] The said cover layer for example has a thickness of more than 50 μm, in particular more than 100 μm and less than 2000 μm, in particular less than 1000 μm.
[0046] Thanks to the sticky properties of the reactive starting material, the plastics film preferably remains glued to the impregnated or coated multilayer fibre web.
[0047] The melt or decomposition point of the cover layers is here higher than the polymerisation temperature of the reactive starting material. Thus the cover layer is not harmed during the polymerisation process of the plastics matrix.
[0048] Since the melt point of the PBT cover layer which is already polymerised (approx 220° C.) is higher than the polymerisation temperature of the reactive starting material which is used (approx 180° C.-190° C.), the cover layer of PBT is not disadvantageously harmed by the effect of heat on polymerisation of the plastics matrix.
[0049] The integral application of the said cover layers has the advantage that a high surface quality of the plate material is achieved as the cover layers contain no fibres. Furthermore, the cover layers at the same time serve as release layers (separating layers) which prevent the impregnated multilayer fibre web from adhering to the device parts which are in contact therewith, such as rollers or pressing plates, and hence their soiling.
[0050] In one embodiment of the invention the cover layers can be dyed and thus already give the plate material its external colour appearance. The dyeing can be such that the fibre-reinforced layers which are arranged below the cover layers are no longer visible. As a result, where applicable a subsequent paint application layer can be omitted.
[0051] The multilayer fibre web which is present in the form of a material laminate is formed in the continuous press under the supply of heat and/or pressure with polymerisation of the plastics matrix into a polyester, in particular into a PBT internally, and preferably pore-free into a plate-like material.
[0052] The multilayer fibre web in the continuous press is preferably guided through several separately adjustable pressing zones and tempering zones, where the contact pressures are generated by floating, hydraulically activated lower pressing plates which work against an upper, rigid press construction. The pressure in the continuous press is created in particular by way of segmented pressing plates with adjustable gap intervals from each other. Floating of the fibre web is prevented by the gap openings between adjacent pressing segments.
[0053] In a preferred embodiment, after a particular number of segmented pressing plates is arranged an additional pressing station, in particular an impression cylinder, which exerts a linear pressure on the impregnated fibre lay. By exerting a linear pressure any bubbles and pinholes present in the plastics matrix are expelled. The continuous press can have one or more pressing stations, in particular impression cylinders, arranged after the pressing plates so that the fibre web undergoes a complete and bubble-free impregnation of the fibre structure with the melt-fluid plastics matrix.
[0054] The fibre lay or plate material in the continuous press is advanced preferably by means of a double belt system.
[0055] The finished plate material after leaving the continuous press can be supplied on a roller conveyor to a cutting or sawing device and cut or trimmed longitudinally and/or transversely to the throughput direction or advance direction into individual plates or strips and stacked in batches.
[0056] The device for performance of the method according to the invention, as already stated, contains a fibre laying device and following this in-line a continuous press. The fibre laying device contains several fibre feed units for in-line supply of web-like fibre structures and one or more matrix feed units connected between or after the fibre feed units to supply a matrix starting material onto exposed layers of fibre structures.
[0057] The matrix feed unit is for example a powder scatterer by means of which the matrix starting material which is present in powder form is scattered, in each case on a layer of an exposed fibre structure. The matrix feed unit can also be a film supply device by means of which a film-like matrix starting material is applied to an exposed layer of a fibre structure.
[0058] The fibre laying device preferably contains one or more pressing stations, in particular impression cylinders, by means of which the multilayer web-like fibre lay can be pre-pressed in-line. The pressing station preferably contains a contact roller and an impression roller arranged in pairs, between which the web-like fibre lay is guided. The pressing station is preferably part of a fibre feed unit, in particular to feed the fibre structure in the advance direction, the contact roller serving simultaneously as a transport roller to supply the web-like fibre structure.
[0059] At least one fibre feed unit of the fibre lay device is designed as a cross layer. In a preferred embodiment of the invention the fibre laying device alternately comprises a fibre feed unit for the supply of web-like fibre structures in the advance direction of the fibre lay and a subsequent fibre feed unit with cross layer.
[0060] Preferably, at least following a fibre feed unit with cross layer are arranged matrix feed units. The matrix feed units can also be arranged after any fibre feed unit.
[0061] The continuous press preferably contains several separately adjustable pressing and tempering zones, where the pressing zones, to exert the pressure, contain floating hydraulically activated lower pressing plates which work against an upper rigid press construction. The pressing zones have in particular a multiplicity of segmented pressing plates with adjustable gap spacing to each other. The gap openings form for example an air gap of 1 to 10 mm, in particular 3 to 5 mm.
[0062] In a refinement of the invention, after a certain number of segmented pressing plates is arranged a pressing station, preferably a design of an impression cylinder to generate a linear pressure. The continuous press can contain one or more such pressing stations.
[0063] The continuous press is preferably operated by means of a double belt system. The associated belts can be PTFE (polytetrafluoroethylene) belts or steel belts. This construction depending on the length of the heating section allows medium to high throughputs.
[0064] The method according to the invention allows the continuous production of fibre-reinforced endless plate material with thermoplastic plastics matrix, which allows a fully automated production operation from the supply of the fibre structure and matrix starting material through to the trimming of the finished plate material after emergence from the continuous press.
[0065] The fibre-reinforced plate material according to the invention is used as flat panel or strip goods. Furthermore, the plate material can be processed further into thermally formed three-dimensional articles e.g. by means of thermal deep drawing. Furthermore, the said plate material can be processed further in the form of flat panels into multilayer laminates i.e. containing several further layers, in particular for sandwich constructions, where the further layers can comprise foams, metal foil or metal plates.
[0066] The said plate material or composite plates formed from this or thermoformed articles are used in the transport industry such as road vehicle construction (cars, buses, trucks, vans etc), rail vehicle construction (rail vehicles, trams, high speed trains, maglev trains), aviation (aircraft construction, space travel), ship or boat construction or in cable cars. Furthermore, the said plate material can be used in construction and civil engineering, interior construction and in particular in building technology and in the production of sports equipment.
[0067] From the plate material according to the invention for example can be made body trim panels, underfloor trays, structure profiles, trim strips etc., trim elements, panels etc.
[0068] FIG. 1 shows a device 1 a , 1 b for continuous production of a fibre-reinforced plate material. A first web-like fibre structure 2 is supplied unfolded in the feed direction to the device 1 a . Over the fibre structure 2 is applied, by means of a cross layer 3 a , a further fibre structure 7 a obliquely/diagonally, transversely from laying edge to laying edge. By means of powder scatterer 5 a , in-line and continuously, powdery matrix starting material is applied evenly onto the exposed surface of the fibre web 6 . Over the fibre web 6 which is coated with the matrix starting material, by way of a fibre feed unit 4 a in the advance direction, is supplied a further unfolded web-like fibre structure 9 a and laid over the transversely arranged fibre structure 7 a . The web-like fibre structure 9 a is pressed by means of an impression cylinder onto the multilayer fibre web 6 and connects to the powder-coated fibre structure 7 a below. By way of a further cross layer 3 b a further web-like fibre structure 7 b is applied obliquely/diagonally onto the multilayer fibre web 6 transversely from laying edge to laying edge, and by means of powder scatterer 5 b again coated with powdery matrix starting material. Over the fibre structure 7 b which is coated with the matrix starting material, by way of a fibre feed unit 4 b in the advance direction, is supplied a further unfolded web-like fibre structure 9 b which is laid over the transversely arranged fibre structure 7 b . The web-like fibre structure 9 b is again pressed onto the multilayer fibre web 6 by an impression cylinder and connects to the powder-coated fibre structure 7 b below.
[0069] By way of a further cross layer 3 c a web-like fibre structure 7 c is again applied onto the multilayer fibre web 6 obliquely/diagonally, folded cross-ways from laying edge to laying edge, and by means of powder scatterer 5 c again coated with powdery matrix starting material. Over the fibre structure 7 c which is coated with the matrix starting material, by way of a fibre feed unit 4 c in the advance direction, is supplied a final unfolded web-like fibre structure 9 c which is laid over the cross-ways arranged fibre structure 7 c . The web-like fibre structure 9 c is here pressed by an impression cylinder onto the fibre structure 6 and connects to the powder-coated fibre structure 7 c below. Before entering the continuous press a final powder scatterer 5 d is provided which coats the exposed surface of the multilayer fibre web 6 with powdery matrix starting material.
[0070] The fibre structure 6 which is coated with the matrix starting material is supplied in-line (see continuation arrow A) to a continuous press 1 b in which the continuously supplied multilayer fibre web is pressed into a plate material in several pressing zones with segmented pressing plates. Between the pressing plates are arranged impression cylinders 8 a, b, c to generate a linear pressure.
[0071] The advance of the fibre lay in the continuous press is here guaranteed by a double belt conveyor unit 12 . On emergence of the plate material from the continuous press this is trimmed into individual plates 10 by means of cutting or sawing device 13 .
[0072] FIG. 2 shows a possible structure of a plate material which is produced according to the method of the invention. Arrow B shows the advance direction of the multilayer fibre web in the device.
[0073] The fibre lay contains a first fibre structure 21 which was supplied first, unfolded, in the advance direction of the device. The second fibre structure 22 is laid onto the first fibre structure 21 cross-ways by means of cross layer at an angle of 45° obliquely/diagonally to the advance direction and folded into an upper fibre layer 22 b and a lower fibre layer 22 a . Over the folded applied fibre lay 22 is in turn laid an unfolded fibre structure 23 which is supplied unfolded in the advance direction.
[0074] The next layer is again a fibre structure 24 applied obliquely/diagonally crossed by means of a cross layer at a 45° angle to the advance direction, with an upper fibre layer 24 b and below this a fibre layer 24 a . Over these fibre layers, similar to the above-mentioned laying pattern, are applied fibre structures 25 and 26 and finally an unfolded fibre layer 27 which is also supplied in the advance direction.
[0075] FIG. 3 shows an extract from a multilayer fibre web 30 with a lower and an upper unfolded fibre structure 25 , 27 and arranged between these two fibre structures a fibre structure 26 which is applied by means of cross layer. A powder scatterer 31 is applied over the cross-ways laid fibre structure 26 and coats this with powdery matrix starting material. Then the next unfolded fibre layer 27 is applied.
[0076] FIG. 4 shows a diagrammatic cross-section A-A through a fibre lay according to FIG. 3 with alternate layers of fibre structures 42 , 44 folded cross-ways and accordingly in two layers, and between these the unfolded fibre structures 41 , 43 , 45 which are applied in the advance direction. | A method for the continuous production of a thermoplastic plate material which is reinforced with a flat-shaped fibrous structure. The method is characterized in that a first web-shaped fibrous structure is guided to a fibre laying device, and one or several additional web-shaped fibrous structures are arranged inline over the first fibrous structure by means of fibre guiding units. One or several matrix guiding units, which are mounted upstream of or downstream from the fibre guiding units, are used to guide a matrix starting material to free layers of the fibrous structure, in particular, a reactive starting material such as cyclic oligomers of PBT, and the multi-layered fibrous web, which is covered one or several times with intermediate layers of matrix starting material, exiting from the fibre laying device, is guided to a through press wherein the matrix starting material is transformed into a low-viscous liquid under the effects of heat and/or pressure. The multi-layered fibrous web is pressed into a plate-shaped plastic material made of PBT (polybutylene terephthalate) by impregnating fibrous structures. | 1 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This patent application claims the benefit of U.S. Provisional Patent Application No. 60/742,008, filed Dec. 2, 2005, the teachings and disclosure of which are hereby incorporated in their entireties by reference thereto.
FIELD OF THE INVENTION
[0002] This invention generally relates to consumer and commercial appliances, and more particularly to a consumer or commercial clothes dryer.
BACKGROUND OF THE INVENTION
[0003] Accidental Carbon Monoxide (CO) poisoning is a growing issue. Every year hundreds of people are sickened and many deaths occur due to Carbon Monoxide poisoning, principally from improperly vented or maintained appliances. Ten states now require the installation of CO alarms in residential new construction and several metropolitan areas, including Chicago and New York City, require CO alarms in all residential dwellings.
[0004] Gas-fired clothes dryers are a significant source of Carbon Monoxide and improperly vented dryers have resulted in several confirmed deaths in the past few years. Additionally, blockages that may result from lint build-up even in properly vented dryers can result in poor exhausting and a build up of CO.
[0005] There exists, therefore, a need in the art for a consumer and commercial clothes dryer that is able to detect such a condition and reduce the impact thereof.
[0006] The invention provides such a clothes dryer. These and other advantages of the invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.
BRIEF SUMMARY OF THE INVENTION
[0007] In view of the above, an embodiment of the present invention provides a new and improved clothes dryer. More particularly, an embodiment of the present invention provides a new and improved clothes dryer that can sense the production and/or build up of carbon monoxide thereby and act to reduce the generation and/or effect of such condition.
[0008] In one embodiment of the present invention, a Carbon Monoxide (CO) sensor is incorporated into residential clothes dryers to monitor CO gas levels in the vicinity of the dryer. The presence of elevated CO levels in the vicinity of a gas-fired dryer, beyond that associated with normal operating conditions, could be indicative of venting issues (blocked, damaged or an improperly installed vent) that could result in potentially dangerous levels of CO entering the home.
[0009] In one embodiment of the present invention, once the elevated level of CO is detected, the clothes dryer alerts the user to the condition. The alert may be audible and/or visual. In another embodiment, the clothes dryer disables operation of the burner to minimize the further production of carbon monoxide.
[0010] Other aspects, objectives and advantages of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention and, together with the description, serve to explain the principles of the invention. In the drawings:
[0012] FIG. 1 is an isometric illustration of a clothes dryer constructed in accordance with the present invention.
[0013] While the invention will be described in connection with certain preferred embodiments, there is no intent to limit it to those embodiments. On the contrary, the intent is to cover all alternatives, modifications and equivalents as included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Referring to FIG. 1 , a typical dwelling 20 is illustrated having a basement in which is installed a clothes dryer 10 constructed in accordance with the teachings of the present invention. This clothes dryer 10 includes a carbon monoxide sensor 12 positioned so that it can sense the level of carbon monoxide in the ambient air of the room in which the dryer 10 is located. In the illustrated embodiment, the CO sensor 12 is positioned on the control panel of the dryer 10 so that it can easily sense the ambient environment around the dryer 10 for the presence of CO. However, those skilled in the art will recognize that the CO sensor 12 may also be positioned elsewhere on or in the dryer 10 in locations that allow sensing of the ambient environment, including in the air intake for the dryer 10 for models that draw air from the ambient environment of the room in which the dryer 10 is located. Indeed, those skilled in the art will also recognize that on the control panel also includes mounting of the CO sensor 12 behind the control panel with appropriate vents being provided to allow sensing of the ambient environment outside of the dryer housing.
[0015] In one embodiment, the CO sensor 12 is an electrochemical CO sensor. This CO sensor 12 is incorporated into the clothes dryer 10 and continuously monitors the level of CO in the vicinity of the dryer 10 . In an alternate embodiment, the CO sensor 12 monitors the level of CO in the vicinity of the dryer 10 only during operation of the dryer. According to the Consumer Products Safety Commission (CPSC), the health effects of CO depend on the level of CO and length of exposure, as well as each individual's health condition. The concentration of CO is measured in parts per million (ppm). Health effects from exposure to CO levels of approximately 1 to 70 ppm are uncertain, but most people will not experience any symptoms. Some heart patients might experience an increase in chest pain. As CO levels increase and remain above 70 ppm, symptoms may become more noticeable (headache, fatigue, nausea). As CO levels increase above 150 to 200 ppm, disorientation, unconsciousness, and death are possible.
[0016] In the event unusual levels of CO are detected that may indicate a problem condition, the sensor 12 may interrupt operation of the dryer 10 , directly or via the dryer controller or other circuitry, to stop further production of CO. Indeed, as used herein for ease of understanding, interruption of the dryer 10 operation by the CO sensor 12 shall include interruption via the dryer controller or other circuitry based on the detection of CO by the CO sensor 12 . This interruption may include disabling the burner of the dryer 10 to stop further production of CO. In an embodiment of the present invention, the dryer 10 may also stop the blower of the dryer 10 in addition to the burner. However, in another embodiment, the blower is allowed to continue to operate, or may be started so as to aid in venting the detected CO in the vicinity of the dryer 10 .
[0017] The CO levels that trigger this interruption of the dryer 10 may be similar as those currently used to activate a CO alarm in standard CO detectors installed today (UL 2034), e.g. an inverse relationship between the level of CO concentration and the time duration of exposure. Alternatively, the threshold may be lower than the levels that would trigger a CO detector to sound its alarm, e.g. less than 30 ppm. Indeed, embodiments of the present invention disable the dryer 10 based on the detection of CO or the detection of CO above a certain level.
[0018] In an embodiment of the present invention, the clothes dryer 10 may sound a continuous or discontinuous audible warning to alert the homeowner to a potential problem. The alarm must be manually silenced in one embodiment. In a further embodiment, a visual alarm indicator 16 (i.e. LED) is enabled to help the homeowner understand the nature of the alarm.
[0019] If the home is equipped with RF enabled carbon monoxide alarms 18 , a signal is sent from the dryer 10 causing the alarms 18 to activate. If the home is equipped with a smart or connected home system, such as the Samsung Homevita system, a text message alerting the homeowner to the condition may also be sent over the gateway.
[0020] The dryer 10 preferably would incorporate a long-life CO sensor 12 , such as a sensor that utilizes the Invensys Monox™ self-test technology, and would preferably be field serviceable. In the event the sensor 12 is not functioning, a visual and/or audible signal would alert the homeowner to replace the sensor. The dryer would continue to function normally in this condition in one embodiment, and would be disabled in an alternate embodiment.
[0021] All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
[0022] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
[0023] Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. | A gas clothes dryer having a carbon monoxide sensor incorporated therewith to detect the possibility and/or presence of a carbon monoxide that may be indicative of blockage in the exhaust vent or an improperly maintained appliance is provided. The dryer of the present invention incorporates carbon monoxide sensing to determine when an elevated level of carbon monoxide is present, and provides a warning to the consumer of the impending or existing hazardous condition. The warning may be audible, visual, and may include an interface to installed hazardous condition alarms within the dwelling. Additional interface to connected home systems providing text messaging may also be provided. | 3 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. provisional application No. 61/810,855 filed on Apr. 11, 2013.
BACKGROUND OF THE INVENTION
[0002] This invention concerns torque limiters which are well known devices which act to produce an overload release in a rotary drive train when the torque transmitted exceeds a predetermined level, in order to prevent damage to components in the drive train.
[0003] Resettable torque limiters are also well known in which drive balls are installed in detent pockets and held therein by a plunger urged against the drive ball by spring pressure. When a predetermined maximum torque is reached, the drive ball can force the plunger away and allow the drive ball to climb out of the pocket allowing relative rotation of two interfit parts to interrupt the driving connection therebetween.
[0004] In conventional practice, grease is applied to the wearing components by injection into a passage drilled through the plunger to the drive ball engaged with the plunger end, and passages radially out past a bushing to reach various wear components.
[0005] However, in prior designs grease does not flow past the drive ball to the detent pocket without release of the torque limiter since the drive ball normally blocks the grease flow until the torque limiter releases. Grease flow past the bushing is limited due to the limited clearance.
[0006] For high torque release settings, it is difficult to manually trip the limiter for routine maintenance purposes.
[0007] In such torque limiters there are sometimes also heavily preloaded bearings supporting one interfit part on the other. Normally these parts do not relatively rotate, but both parts rotate together since connected together by the torque limiter drive ball, and these bearings become dry as the grease migrates out overtime due to centrifugal force generated by rotation together of the interfit parts. Due to their location, these bearings are not able to be greased, except when the torque limiter is released.
[0008] It is an object of the present invention to provide improved lubrication for a resettable torque limiter of the type described above by providing enhanced distribution of grease to the wear in components.
SUMMARY OF THE INVENTION
[0009] The above object and other objects which will become apparent upon a reading of the following specification and claims are achieved by forming lubricant passages in the plunger and bushing that allow free flow of lubricant to points which will adequately lubricate the moving components in a drive device such as a torque limiter. This includes a central passage extending lengthwise down the plunger which terminates short of the end in contact with the drive ball which central passage is connected to a cross passages extending radially short offset longitudinal passages then distribute lubricant to an open annular space extending around the drive ball, as well as laterally to a clearance between the plunger and the ID of a bore in a bushing in which the plunger is slidably fit. Lubricant from the open spaces further enters cross passages in the bushing which extends to the bushing bore ID as well as lengthwise passages through the bushing to reach the lower regions and the detent pocket.
[0010] In addition, a disconnect nut threadably engages the upper end of a plunger shroud secured to the plunger upper end and when rotated with a wrench causes raising of the plunger to manually elevate the plunger sufficiently to release the torque limiter by driving the locking balls radially outward.
[0011] The torque limiter release enables the lubrication of bearings supporting the interfit drive parts which are included in the torque limiter, which normally cannot be greased when the torque limiter is not in a released condition. Improved lubrication of the torque limiter running parts is also facilitated.
DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a sectional view of a prior art torque limiter of a type with which the present invention is concerned showing a conventional grease passage pattern.
[0013] FIG. 2 is a view of prior art driving and driven interfit parts combined with a conventional torque limiter to create a driving connection therebetween.
[0014] FIG. 3 is an external pictorial view of a torque limiter according to the present invention.
[0015] FIG. 4 is an enlarged sectional view of the torque limiter according to the present invention shown in FIG. 3 .
[0016] FIG. 5 is an enlarged sectional view of a plunger included in the torque limiter shown in FIGS. 3 and 4 .
[0017] FIG. 6 is an enlarged sectional view of a bushing included in a torque limiter according to the invention shown in FIGS. 3 and 4 .
DETAILED DESCRIPTION
[0018] In the following detailed description, certain specific terminology will be employed for the sake of clarity and a particular embodiment described in accordance with the requirements of 35 USC 112, but it is to be understood that the same is not intended to be limiting and should not be so construed inasmuch as the invention is capable of taking many forms and variations within the scope of the appended claims.
[0019] Referring to FIGS. 1 and 2 , a prior art torque limiter 10 of the type which the present invention is concerned is shown. One or more of such torque limiters may be installed circumferentially spaced about the axis of a pair of interfit rotary parts 12 and 14 other arrangements of such torque limiters are well known.
[0020] One interfit rotary part 12 is secured to a drive (or driven) member 16 and the other rotary part 14 is secured to a driven (or drive) member 18 .
[0021] A drive ball 20 is normally seated within a detent pocket 22 fixed in rotary member 14 and a bushing 24 fixed within a housing 26 is secured to rotary member 12 . The drive ball 20 creates a rotational connection so that the rotary members 12 and 14 normally rotate together.
[0022] Upon the development of a transmitted torque of a predetermined level, the drive ball 20 begins to ride up the sloping sides of the detent pocket 22 and to thereby push up a plunger 28 which has radiused pocket 21 ( FIG. 5 ) at its lower end in contact with the drive ball 20 . The plunger 28 is urged downwardly by the effect of a stiff spring 36 .
[0023] The spring 36 exerts pressure on a set of small locking balls 30 engaged by a rounded shoulder surface 29 on the upper end of the plunger 28 tending to force the balls 30 radially out.
[0024] Any axial movement of the plunger 28 is resisted by the constraining effect exerted by an outer thrust race 32 and an inner thrust race 34 urged together by the preloaded spring 36 applying an axial force to inner thrust race 34 . An adjusting nut 37 allows setting of the spring preload.
[0025] If the transmitted torque level reaches a predetermined release value, the spring force described is overcome to move the outer race 34 down and allow the locking balls 30 to move out radially sufficiently to move onto the outer diameter 36 on the plunger 28 .
[0026] At this point, the drive ball 20 has moved up into the interior bore of the bushing. A snap ring 38 then holds the ball 20 up and out of engagement with the detent pocket 22 , allowing interfit parts 12 , 14 to freely rotate, relative each other, supported by rotary bearings 40 .
[0027] The torque limiter 10 can be reset by striking the upper end 42 of the plunger with sufficient force in the well know manner.
[0028] In order to keep grease on the torque limiter rotating wear parts, a grease fitting 44 is normally provided which allows injection of grease into an axial central passage 46 in the plunger 28 which passes down to the top of the drive ball 20 which normally prevents any further grease flow.
[0029] Two (or more) pairs of cross passages 48 and 50 branch off from the central plunger passage 48 . The upper pair of passages lubricate the races 32 , 34 and locking balls 30 . The lower pair of feed cross passages 52 reach the bottom of the bushing and theoretically reach the detent pocket 22 and drive ball 20 via a clearance and small grooves. However, little or no grease will reach the lower components as a practical matter due to the slight clearances.
[0030] Grease will only exit the lower end of the passage 46 when the torque limiter 10 has been released by movement of the plunger 28 .
[0031] Additionally, the bearings 40 can only effectively be greased during routine maintenance when the torque limiter is tripped. This is almost impossible to do manually due to very high torque limit settings often used in some applications. Since the bearings 40 are typically heavily preloaded and do not rotate while the torque limiter remains locked, heavy wear can result as the grease over time tends to migrate out due to rotation of the assembly and consequently the bearings 40 become dry.
[0032] Referring to FIGS. 3 and 4 , a torque limiter 54 according to the invention is shown. This includes a housing 56 which has a threaded extension 58 which receives a disconnect nut 60 which engages a plunger shroud 66 threaded to the upper end 64 of the plunger 28 .
[0033] A recess 68 in the plunger shroud 66 receives a grease fitting 70 .
[0034] An axial central lengthwise grease passage 72 is provided in the plunger 28 , which terminates short of the drive ball 74 . Instead, there are two cross passages 76 which connect with two pairs of offset longitudinal passages 78 that extend to an annular clearance space 80 adjacent the drive ball 74 .
[0035] The bushing 82 has two cross passages 84 , each receiving grease from the annular space 80 and direct into the same out through down passages 86 through the bushing 82 so that grease can reach the detent pocket 88 .
[0036] The cross passages 76 extend to the inside diameter of the bushing 82 to provide additional grease.
[0037] Thus, the set of grease passages described are able to effectively direct grease to the wearing components without releasing the torque limiter.
[0038] A second aspect of the invention does involve the disconnect nut 60 and plunger shroud 66 . The disconnect nut 60 has a series of wrenching flats 90 thereon so that a wrench can be used to turn the same and advance the disconnect nut 60 up as viewed in FIG. 4 on the external threads on the housing extension 58 .
[0039] The upper recessed face of the disconnect nut 60 will engage an underside of flange 92 on the plunger shroud 66 so as to pull up the plunger 62 as the shroud 66 is elevated.
[0040] The powerful mechanical advantage exerted by of the threaded engagement of the disconnect nut 60 enables the balls 96 to be forced out until the torque limiter 54 becomes disconnected, even if the torque release level is set to be very high.
[0041] Once released, the bearings 40 can be rotated and greased as a part of a regular maintenance regime. In addition, flow of grease to the torque limiter wear components as described above is enhanced. | A torque limiter in which grease passages are provided to enable better lubrication of the wearing components. A disconnect nut is also provided to readily enable release of the torque limiter even for very high release sellings to afford greasing as a part of a maintenance regimen. | 5 |
FIELD OF THE INVENTION
This invention relates to an advertising device and method for printed matter, and in particular, to an advertising device and method that includes a pop-up insert that through various aspects attracts the attention of consumers.
BACKGROUND OF THE INVENTION
The consuming public is inundated with print advertisement, such as mail, newspaper ads and magazine ads. This places advertisers in competition with each other to gain the attention of consumers. Prior attempts to gain the attention of consumers have included catchy slogans, startling artwork, novelty items, contests, prizes, redeemable coupons and in some cases even the inclusion of token sums of money. Though these traditional attempts at gaining the attention of consumers have been somewhat successful, a continuous need exists for a structure that gains the attention of consumers, to gain more sales per advertising dollar.
Additionally, attempts to gain the attention of consumers must be capable of reaching numerous consumers in an efficient manner. Thus, the most efficient attention grabbing advertisement should be easily mass manufactured and otherwise cost effective.
SUMMARY OF THE INVENTION
Accordingly, one aspect of the present invention provides an advertising device and method with novel structural features for gaining the attention of consumers.
In accordance with another aspect of the present invention, an advertising device and method are provided that may be manufactured using commercially available printing press and in-line finishing equipment.
In accordance with the principles of the present invention, an advertising device or vehicle, which may be in the form of a mailing device, a magazine insert or a stand-alone circular, is provided. The advertising device may be mass manufactured using available graphic arts web press equipment. The advertising device includes a novel insert device that pops up from the advertising device, attracting the attention of the person opening the device.
In one aspect of the present invention, an advertising device in the form of a mailing device is formed from a first sheet having a cover panel, a front panel and a spring panel. The cover panel adjoins the front panel at a first fold and the front panel adjoins the spring panel at a second fold. The cover, front and spring panels each have an inner surface and an outer surface. The front panel serves as the front of the mailing device wherein the address is displayed. The spring panel and cover panel jointly form the back of the mailing device, the intersection of the two providing a means for accessing the interior of the mailing device. A pop-up insert is retained within the mailing device. The pop-up insert has an attaching panel and a free panel. The attaching and free panels are adjoined at a third fold and have an inner surface and an outer surface. The outer surface of the attaching panel is attached to a portion of the inner surface of the cover panel. The free panel is oriented by the third fold such that its inner surface is adjacent the inner surface of the free panel. In a closed configuration, a free end of the spring panel opposite the first fold overlies the attaching panel near the third fold. A portion of the inner surface of the cover panel is adhesively attached near the free end of the cover panel to the outer surface of the spring panel near the free end of the spring panel.
In normal operation, the receiver of the mailing device will hold it near the second fold with his thumb and finger securing the spring panel in place. The cover panel is then lifted. Initially, the spring panel retains the insert within the mailing device, resisting the movement of the cover panel to which it is attached. Eventually, the person opening the mailing device will overcome the force retaining the insert, allowing the insert to escape the confines of the spring panel and "pop-up" to gain the attention of the person opening the device.
In another aspect of the present invention, the pop-up insert, in addition to the attaching panel, may have a plurality of free panels, adjacent ones of which are adjoined by a fold. Most preferably, the folds will vary in vertical relation to each other to provide multiple pop-ups in steps upon opening the mailing device.
In yet another aspect of the present invention, an enclosure is confined within the mailing device. The enclosure will preferably contain useful information and will most preferably include a return envelope and a response card or order form or pledge card for a donation. The enclosure may be adhesively attached to either the inner surface of the front panel or the inner surface of the cover panel. Where attached to the cover panel, the enclosure may add to and vary the pop-up effect.
In another aspect of the present invention, an advertising device in the form of a magazine insert is provided. The magazine insert is formed from a single sheet folded into two panels. At least one of the panels has an opening through which a pop-up insert is accessible. The insert is partially covered by the panels and the panels are adhesively joined in an area near the insert. A person may gain access to the insert through the opening in the panel. The insert is partially restrained initially by the portion of the panel that partially covers the insert. However, this restraint is easily overcome by additional force from the person lifting the insert. Once the initial restraint is overcome by lifting the insert, the insert will be quickly released, popping up and gaining the attention of the person lifting the insert. The insert may include a specialty item, such as an encapsulated fragrance area that is broken when the insert is opened to release a scent. Alternatively, the specialty item may be a scratch and sniff fragrance sample, a scratch-off coating hiding a message, prize or other information, or other specialty items.
In another aspect, the present invention provides a method for producing a mailing device. The method may be performed by using conventional web printing press equipment. First, a first web or ribbon of paper is conveyed along a first path while a second web or ribbon of paper is conveyed along a second path. Most preferably, the first web and the second web are ribbons formed from portions cut from a single web. The first web is folded to form an attaching panel and a free panel. Then the folded first web is aligned adjacent an inner surface of the second web. With the first web in place, the second web is first folded to form a spring panel that overlies the folded portion of the first web. A first adhesive is applied along at least a portion of the outer surface of the spring panel and a second adhesive is applied along at least a portion of the outer surface of the attaching panel that is not covered by the spring panel. Finally, the second web is folded again at an end opposite the spring panel to produce a cover panel. The cover panel overlies the portion of the attaching panel not covered by the spring panel and also covers a portion of the spring panel including the portion with the first adhesive. Thus, the cover panel is attached to the attaching panel of the first web by the second adhesive and attached to the spring panel by the first adhesive. Preferably, a third adhesive may be applied to the inner surface of the second web to secure a portion of the spring panel to a portion of the second web.
In another aspect of the above-described method, an enclosure to be included in the mailing device is formed from a third web or ribbon that is conveyed along a third path and folded a desired number of times to produce the desired enclosure. The enclosure is aligned along the inner surface of the second web and the folded first web is aligned with the enclosure such that the free panel of the first web is adjacent the enclosure. Once the enclosure and first web are aligned along the second web, the second web is folded to form the spring panel and adhesives are applied to the outer surface of the spring panel and the attaching panel prior to the cover panel being folded and attached thereto.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an advertising device in accordance with the present invention in the form of a mailing device;
FIG. 2 is a back view of the mailing device shown in FIG. 1 in an open configuration;
FIG. 3 is a side view of the mailing device shown in FIG. 2;
FIG. 4 is a front view of the mailing device shown in FIG. 2;
FIG. 5 is a front view of the mailing device shown in FIG. 2 with the pop-up insert in accordance with the present invention fully articulated;
FIG. 6 is a side view of a mailing device in accordance with the present invention shown in a closed configuration;
FIG. 7 is a side view of an alternative embodiment of a mailing device in accordance with the present invention;
FIG. 8 is a side view of a mailing device in accordance with the present invention in a partially open configuration;
FIG. 9 is a side view of a mailing device in accordance with the present invention in an open configuration;
FIG. 10 is an embodiment of a mailing device in accordance with the present invention including an enclosure;
FIG. 11 is a front view of the enclosure shown in FIG. 10;
FIG. 12 is a side view of the enclosure shown in FIG. 10;
FIG. 13 is a back view of the enclosure shown in FIG. 10;
FIG. 14 is a back view of the enclosure shown in FIG. 10 with a slight modification to the enclosure;
FIG. 15 is a front view of an advertising device in accordance with the present invention in the form of a magazine insert;
FIG. 16 is a cross sectional view of the magazine insert shown in FIG. 15 taken along line 16--16; and
FIGS. 17A-I are perspective views illustrating a method of producing an advertising device in accordance with the principles of the present invention.
DETAILED DESCRIPTION
Referring to the Figures generally where like numerals refer to like parts or steps, and in particular, to FIG. 1, there is illustrated an advertising device in accordance with the present invention in the form of a stand-alone mailing device 20. Mailing device 20 is one sheet formed into three panels. Front panel 22 is the address side of mailing device 20. A first fold 24 runs horizontally across the top of mailing device 20 defining a point of intersection between front panel 22 and adjoining cover panel 26. A second fold 28 runs horizontally across the bottom of mailing device 20 being substantially parallel to first fold 24. Second fold 28 separates and defines a point of intersection between front panel 22 and adjoining adjacent spring panel 30. Cover panel 26 overlays spring panel 30 forming the back of mailing device 20. As is traditional with mailing devices, mailing device 20 has sendee address portion 32 centrally located within front panel 22. In accordance with the teachings of the present invention a pop-up insert 40 is retained within mailing device 20.
FIG. 2 shows the back of mailing device 20 with cover panel 26 articulated to be substantially parallel and coplanar to front panel 22. Cover panel 26 has a free end 42 opposite first fold 24 and spring panel 30 has a free end 44, shown partially in phantom, opposite second fold 28. A portion of pop-up insert 40 is visible beyond free end 42 of cover panel 26. The sendee address portion 32 is shown in the form of a die-cut opening or window for exposing a card or enclosure (not shown) containing the sendee's address. If no card or enclosure is required, the sendee's address may be applied directly to front panel 22 in sendee address portion 32, eliminating the need for a window. Through sendee address portion 32 a portion of spring panel 30 may be seen.
FIG. 3 is a side view of mailing device 20 with cover panel 26 articulated or unfolded. Pop-up insert 40 is adhesively attached to an inner surface 48 of cover panel 26. This attachment is preferably made by permanent glue 50. Spring panel 30 is preferably attached at its inner surface 52 to inner surface 54 of front panel 22 by permanent glue 56. The preferred permanent glue is water-based envelope or spine glue. One such envelope glue is sold under the designation WA2907PK by Elekromek Co., Inc.
FIG. 4 is a front view of mailing device 20 with cover panel 26 articulated as in FIGS. 2 and 3. A portion of outer surface 60 of pop-up insert 40 is visible and contains advertisement to catch the attention of the consumer opening mailing device 20. As shown in FIG. 5, pop-up insert 40 may be articulated around fold 46 to reveal inner surface 62 which contains additional eye catching advertisement for the consumer.
FIG. 6 shows a side view of mailing device 20 in a closed configuration for mailing. In the closed configuration, a portion of inner surface 52 of spring panel 30 overlays and restrains pop-up insert 40. Fold 46 divides pop-up insert 40 into a free panel 64 and an attaching panel 66. The outer surface 60 of attaching panel 66 lays adjacent to inner surface 52 of spring panel 30. Outer surface 60 of free panel 64 is adjacent to inner surface 54 of front panel 22. Fugitive glue 70 is used to releasably secure cover panel 26 to outer surface 72 of spring panel 30. Fugitive glue 70 sufficiently secures cover panel 26 to spring panel 30 to prevent inadvertent opening during transit or mailing, but allows cover 26 to be released from spring panel 30 with a small amount of force from a consumer without tearing or otherwise damaging device 20. Fugitive glue 70 is applied near free end 44 of spring panel 30. The preferred fugitive glue is water-based fugitive glue. One such fugitive glue is sold under the designation Craigbond #3991 PLV by Craig Adhesives & Coatings Co.
FIG. 7 is an alternative preferred embodiment of an advertising device in accordance with the principles of the present invention in the form of a mailing device 120, shown in a side view. Mailing device 120 has three panels formed from a single sheet. Front panel 122 serves as the address side of mailing device 120. Fold 124 extends horizontally along the top of device 120 where front panel 122 adjoins cover panel 126. A second fold 128 extends horizontally along the bottom of device 120 substantially parallel to fold 124 between front panel 122 and adjoining spring panel 130. Preferably, spring panel 130 is adhesively secured to front panel 122 by permanent glue 156 near fold 128. In the closed configuration, as shown in FIG. 7, cover panel 126 is releasably secured to an outer surface of cover panel 130 by fugitive glue 170. A pop-up insert 140 is retained within mailing device 120. Pop-up insert 140 has a plurality of panels defined by folds 146A-C. Attaching panel 166 is attached to the inner surface of cover 126 by permanent glue 150. The remaining panels 164A-C of pop-up insert 140 are not attached to device 120. Notably, similar to the embodiment shown in FIG. 6, spring panel 130 overlays an outer surface of attaching panel 166 to retain pop-up insert 140 within mailing device 120 even when cover panel 126 is first articulated. The inner surface of cover 126 is releasably secured to the outer surface of spring panel 130 near a free end of spring panel 130 and a free end of cover panel 126. Preferably, fold 146C extends deeper into device 120 than fold 146A, which is adjacent fold 146C and closer to cover panel 126.
The operation of mailing device 20 is best described with reference to FIGS. 6, 8 and 9 which are side views that show progressively the mailing device 20 going from the closed configuration to an open configuration. As previously described, FIG. 6 shows mailing device 20 in a closed configuration with cover panel 26 releasably secured to spring panel 30 and pop-up insert 40 retained by spring panel 30. In normal operation, a consumer receiving mailing device 20 will secure the bottom portion of mailing device 20 near fold 28 in his hand by placing his thumb over a bottom portion of spring panel 30. In accordance with the normal procedures for opening an envelope and preferably, also in accordance with written instructions on cover panel 26, the consumer will lift cover panel 26 at the free end to release the fugitive glue bond between the inner surface of cover panel 26 and the outer surface of spring panel 30. After releasing cover panel 26 from spring panel 30 by moving panel 26 generally in the direction of arrow A, the mailing device 20 will attain a configuration similar to that shown in FIG. 8. Notably, pop-up insert 40 is retained within mailing device 20 by spring panel 30. Additionally, the consumer's thumb may also help to retain insert 40 within device 20. The force of moving cover panel 26 will cause energy to be stored in the spring mechanism comprising spring panel 30 and insert 40. When the consumer supplies sufficient force to overcome the restraint provided by spring panel 30, pop-up insert 40 will accelerate briskly from within the confines of device 20 drawing the attention of the consumer and also producing a rustling sound due to the brisk movement of the paper. This will cause mailing device 20 to attain a configuration substantially as shown in FIG. 9. The device 20 may then be articulated as shown in FIGS. 4 and 5. The pop-up effect may be adjusted by varying the weight of the paper, the amount of overlap between the insert and the spring panel and the application of glue between the spring panel and front panel.
Mailing device 120 operates in a manner similar to mailing device 20 with variations in effect caused by the plurality of free panels 164A-C. Most preferably, where fold 146C extends deeper into device 120 than fold 146A, which is adjacent cover panel 126, the pop-up effect will be repeated when fold 146C is released from within device 120. Additional folds in pop-up insert 140, each fold extending deeper than the adjacent fold, may be added to multiply the pop-up effect.
In a preferred embodiment, an advertisement device in accordance with the principles of the present invention in the form of a mailing device will also include an enclosure as illustrated in FIGS. 10 through 14. The enclosure may carry valuable information for a consumer and preferably may include a business reply envelope and an order form.
FIG. 10 shows a side view of mailing device 20 with an enclosure 200 retained within the device. Enclosure 200 is preferably one contiguous form or sheet with a plurality of panels, one or more of which may be formed into an envelope. Enclosure 200 may simply rest within mailing device 20 between pop-up insert 40 and the inner surface of front panel 22. Preferably, enclosure 200 is releasably secured within mailing device 20 by fugitive glue in area 202A or optionally in area 202B. Generally, enclosure 200 will be secured either to cover panel 26 in area 202A or front panel 22 in area 202B but not to both. Notably, securing enclosure 200 to cover panel 26 will vary the pop-up effect of the mailing device since in addition to pop-up insert 40, enclosure 200 may also be released when cover panel 26 is fully articulated.
FIGS. 11, 12 and 13 show respectively, a front view, a side view and a back view of enclosure 200 with its plurality of panels fully articulated to be parallel to each other. When fully articulated or unfolded, the front of enclosure 200 reveals a top panel 204, a middle panel 208 and a bottom panel 212. Top panel 204 and middle panel 208 are adjoined and adjacent, being separated by fold 206. Middle panel 208 and bottom panel 212 are adjacent and adjoined and separated by fold 210 which is also perforated. Top panel 204 preferably includes the greeting to the consumer and is followed by valuable printed matter contiguously to the end of bottom panel 212. As best seen in FIG. 12, panel 212 is the back of an envelope 214. The front address portion of envelope 214 is formed by panel 216. Panel 212 and panel 216 are adhesively secured together around two of their edges by permanent glue 220, leaving an opening 218 for accessing the content of envelope 214. Preferably panel 222 is an order form for the consumer to return a reply to the advertiser. Most preferably, panel 222 is easily detached from enclosure 200 by perforations along fold 224. As best seen in FIG. 13, panel 222 has an addressee portion 228, which preferably aligns with die-cut window 32 in mailing device 20, as shown in FIGS. 1-5. A distinct advantage of the present invention is the alignment of the addressee portion 228 with die-cut window 32, allowing imaging of the address information. Additionally, since the sendee's address is imaged on the order form, the consumer need not rewrite it when ordering. The reuse of the sendee's address reduces the possibility of mistake or omission because only one address is used for both sending and a subsequent reply. Panels 230 and 232, which are the backs of panels 204 and 208, respectively, may continue the message to the consumer preferably ending at panel 232. FIG. 14 is a back view of enclosure 200 similar to FIG. 13, except that the order form, panel 222, has been removed, revealing the front of envelope 214. Envelope 214 may preferably be detached from enclosure 200 by the perforations along fold 210. A flap 234 for closing envelope 214 is found intermediate panel 216 and the perforations along fold 224. Preferably flap 234 has a water-based remoistenable adhesive that may be activated by the consumer by applying moisture, such as the type of adhesive commonly used on conventional envelopes. One such water-based remoistenable adhesive is sold under the designation Craigbond #3198A by Craig Adhesives & Coatings Co.
Where no order form is necessary, enclosure 200 may be formed without panel 222, as is reflected in FIG. 14. In this alternative embodiment, enclosure 200 is preferably placed within mailing device 20 such that panel 204 is adjacent front panel 22 and die-cut window 32 is aligned with the sendee's address as printed on panel 204.
FIG. 15 shows an advertising device in accordance with the principles of the present invention in the form of a magazine insert 300. Magazine insert 300 appears as a normal page in a magazine bound along side 304. An opening or thumb notch 306 is formed within the page. The opening 306 may be used by the consumer to gain access to pop-up insert 310. The consumer's attention may be directed to opening 306 by conspicuous words on the page such as "sample." Retained below window 306 is pop-up insert 310 in accordance with the principles of the present invention. Preferably, magazine insert 300 may also include a zip strip 312 that may be removed by the consumer. Zip strip 312 is formed by two parallel lines of perforations 314, 316. Magazine insert 300 may have perforations (not shown) adjacent side 304 for removing insert 300.
FIG. 16 is a cross sectional view of magazine insert 300 taken along lines 16--16 in FIG. 15. Bottom panel 322 of insert 300 is adjoined to panel 302 by fold 320 and also adhesively through a center portion of panels 302, 322 by permanent glue 324. Bottom panel 322 has an opening or thumb notch (not shown), similar to panel 302. Glue 324 effectively divides insert 300 into two compartments, a first compartment 326 containing pop-up insert 310 and a second compartment 328. Compartment 328 is accessible by removing zip strip 312 and articulating the portions of panel 302 as shown by arrows B and C. Preferably compartment 328 may hold items of interest to the consumer, such as coupons or game/sweepstakes tickets that may be unique per insert. Pop-up insert 310 is retained in compartment 326 by glue 324, glue 330 and the spring action from panel 302. A line of perforations 332 are provided so that pop-up insert 310 may be removed from compartment 326 and retained by a consumer. Most preferably, a specialty item 336 is maintained within pop-up insert 310. Specialty item 336 may be a fragrance sample or other specialty item that is made available when the top panel 334 of pop-up insert 310 is pulled from opening 306.
In operation, a consumer is directed by the insert to pull top flap 334 of pop-up insert 310 to gain access to a sample. Initially insert 310 is retained within insert 300 by panel 302. However, the consumer may eventually supply enough force to overcome the retaining means and will force pop-up insert 310 to escape from between panels 302 and 322 gaining the attention of the consumer and also freeing access to the specialty item 336. Where specialty item 336 is a fragrance sample, the force applied by the consumer in removing pop-up insert 310 will break the coating on the encapsulated sample allowing the essential oil to emit its scent. Additional force on pop-up insert 310 will facilitate its removal from within insert 300 by detaching portion 340 of page 322 at perforations 332. Insert 310 may be retained by the consumer for additional uses, such as the use of additional fragrance samples that may be contained within the insert but not released by its removal. Additionally, the consumer may pull zip strip 312 to gain access to compartment 328 which may contain other specialty items, such as coupons or sweepstakes tickets which may be unique for a particular insert 300.
Mailing devices 20, 120, shown in FIGS. 1-10, may be adapted to be magazine inserts. For example, folds 28, 128, may be bound into a magazine spine. A line of perforations running adjacent and parallel to folds 28, 128 on spring panels 30, 130 and front panels 22, 122 may be provided to make devices 20, 120 detachable.
FIGS. 17A-I illustrate a method by which an advertising device in the form of a mailing device or magazine insert may be constructed in accordance with the principles of the present invention. In particular, FIGS. 17A-I illustrate a method by which device 20, including insert 200, as shown in FIG. 10, may be constructed. While a wide variety of finishing equipment may be used to produce the advertising devices, the preferred equipment consists of an appropriate number of plowfolding stations, multiple glue application systems, die cutter, a rotary cutter and a delivery system.
FIG. 17A shows three separate ribbons, top ribbon 400, middle ribbon 402 and bottom ribbon 404, vertically aligned with each other. Preferably, top ribbon 400, middle ribbon 402 and bottom ribbon 404 are initially a part of a single web of paper that is cut to form the three ribbons prior to the ribbons being vertically aligned. However, ribbons 400, 402 and 404 may be considered separate webs. The ribbons are printed and contain any necessary perforations or remoistenable adhesives, such as the remoistenable adhesive for a reply envelope. Top ribbon 400 will eventually form pop-up insert 40. Middle ribbon 402 will be formed into enclosure 200. Bottom ribbon 404 will wrap around top ribbon 400 and middle ribbon 402 forming the cover panel 26, front panel 22 and spring panel 30 of mailing device 20.
Preferably, enclosure 200 is first formed by manipulating middle ribbon 402 as shown in FIGS. 17B-E. As shown in FIGS. 17A&B, adhesive or glue 220 is applied along the desired points of middle ribbon 402 for sealing the sides of envelope 214. This adhesive is preferably a water-based envelope or spine glue. The fold formed in FIG. 17B serves as the bottom of envelope 214. Middle ribbon 402 is then folded in an opposite direction as shown in FIG. 17C. The fold produced corresponds to fold 210, which is perforated. Fold 206 and fold 224 are formed in FIGS. 17D and 17E, respectively, completing the formation of enclosure 200.
FIG. 17F illustrates how top ribbon 400 is folded to form pop-up insert 40. Fold 46 divides the portion of top ribbon 400 that will become attaching panel 66 from the portion of top ribbon 400 that becomes free panel 64. Before bottom ribbon 404 is folded, folded top ribbon 400 and folded middle ribbon 402 are aligned to overlay each other and bottom ribbon 404, as shown in FIG. 17G. Adhesive 56 is applied along bottom ribbon 404 as shown in FIG. 17G in an area that will be folded as shown in FIG. 17H. Fold 28 is then formed by wrapping a free end 44 around middle ribbon 402 and top ribbon 400 as shown in FIG. 17H. Then adhesive 50 and adhesive 70 are applied, respectively, to the attaching panel 66 of pop-up insert portion 40 and a portion of spring panel 30. Finally, fold 24 is produced by wrapping the end of bottom ribbon 404 around enclosure 200 and pop-up insert 40 onto spring panel 30. Cover panel 26 is adhesively secured by adhesive 50 and adhesive 70. Alternatively, adhesive 50 and adhesive 70 may be applied to cover panel 26 in the areas to be attached to pop-up insert 40 and spring panel 30 prior to folding. The webs may then be cut to size as illustrated in FIG. 17I.
In a preferred embodiment of mailing device 20, mailing device 20 in a closed configuration is approximately 5 inches (")×7"; ribbons 400, 402, 404 are respectively, approximately 51/2", 181/2" and 111/8" wide; cover panel 26, front panel 22, and spring panel 30 are respectively, approximately, 33/8"×7", 5"×7", and 23/4"×7"; attaching panel 66 and free panel 64 are approximately 23/4"×7"; panels 216 and 204 of enclosure 200 are approximately 4"×7"; and panels 222, 212 and 208 of enclosure 200 are approximately 31/2"×7".
Alternative embodiments of the above-described method may be produced by altering or eliminating enclosure 200. Mailing device 20, as shown in FIG. 6 without enclosure 200 may be produced by completing the folding and adhesion steps in FIGS. 17F-I, of course without enclosure 200.
Whereas the present invention has been described with respect to specific embodiments thereof, it will be understood that various changes and modifications will be suggested to one skilled in the art and it is intended that the invention encompass such changes and modifications as fall within the scope of the appended claims. | A printed advertising device is formed by folding a sheet to enclose a pop-up insert. The pop-up insert is a folded sheet that is initially retained within the advertising device by a novel arrangement, but "pops-up" when the advertising device is accessed to gain the attention of the person opening the device. The advertising device is created by several manipulations of a web, such as folding and applying adhesive using web printing equipment. The advertising device may be a mailing device, a magazine insert or a stand-alone circular. | 8 |
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