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indicated at 1 , 2 in the drawings are two sidepieces of the belt sander frame which are interconnected by a base 3 . directly above the base 3 , centrally and on the sidepieces 1 , 2 , there is rotatably supported a shaft 4 driven from a gear motor 5 mounted to the outside of the sidepiece 1 . keyed to the shaft 4 , close to the inward faces of the sidepieces 1 , 2 , are two sprocket wheels 6 ( in the drawings , only the one adjacent the sidepiece 2 being shown ) wherearound two respective chains 7 are trained with runs extending vertically upwards . the chains 7 form closed loops around sprocket idlers 8 mounted on the tops of the sidepieces 1 , 2 cantilever - fashion . attached to those runs of the chains 7 which confront the sander front side , and at the same level , are two respective shoes 9 which are guided in their vertical movement by guides 10 attached to the inward faces of the sidepieces . pivotally connected to the shoes , as by coaxial trunnions 11 , is the table or working deck 12 which may be rotated from the horizontal position shown in full lines to the upright position shown in dash lines in fig1 - 3 . carried rotatably beneath the table is a longitudinal rod 13 , the ends whereof extend outwards from the opposite ends of the table and carry two radial arms 14 secured thereto . the arms 14 are provided at the free ends thereof with fingers 15 which form extensions of the arms 14 and have notches 16 therein which are adapted to be engaged by trunnions 17 projecting from the shoes 9 and lying below the trunnions 11 . the rod 13 is provided , at the middle thereof , with a manually operated handle 18 which enables the rod , and hence the arms 14 , to be turned when the table 12 is to be shifted between the horizontal and vertical positions . expediently , the trunnions 17 would include angularly adjustable cams to permit the lay of the working deck 12 to be adjusted . fixedly mounted to the sidepieces 1 , 2 , close to the rear edges thereof , are pairs of vertically aligned bushings 19 , 20 which carry rods 21 , 22 rotatably journalled therein adapted to axially support guides 23 , 24 . each guide 23 , 24 comprises a bracket 25 having a cylindrical rail 26 attached to the top edge thereof . the guides 23 , 24 may be shifted , by rotation in the bushings 19 , 20 , from an operative position wherein they extend parallel to each other , ( as shown in fig1 ) to an inoperative position wherein they are in alignment with each other and parallel to the longitudinal direction of the sander . along the guides 23 , 24 , in the operative position thereof , a carriage 27 is movable which comprises a beam 28 , the opposite ends whereof carry outwardly bent angle pieces 29 , 30 , positionable on the tops of the sidepieces 1 , 2 , when the carriage 27 is inoperative . journalled to the angle pieces 29 , 30 , cantilever - fashion in an inward direction , are pairs of peripherally grooved wheels 31 , 32 adapted to roll along the rails 26 of the guides 23 , 24 . the wheels 31 of each pair are interconnected by an axle 33 to ensure a proper movement of the carriage , i . e . to cause it to move in a constantly perpendicular attitude to the guides 23 , 24 . carried at the opposite ends of the carriage 27 , about parallel and horizontal axes , are training pulleys 34 , 35 for a sand belt 36 . the pulley 34 is driven by a motor 37 supported on the carriage 27 . the pulleys 34 , 35 have the same diameter , thereby the two sand belt runs will extend parallel to each other . the upper run moves over the beam 28 , and the lower run under the bottom edges of the guides 23 , 24 . the distance separating the beam 28 from the lower belt run is selected to allow the guides 23 , 24 therebetween . in order to prevent the lower run of the sand belt from interfering , as the carriage 27 is moved along the guides 23 , 24 , with the sidepieces 1 , 2 , forwardly open slots 38 , 39 are provided in the latter . engagement of the wheels 31 , 32 with the rails 26 is controlled by devices operative to control the raising of the guides 23 , 24 . each device comprises a lever 40 having a pivot pin 41 journalled in the sidepiece 1 , 2 . radially attached to the pin 41 is a short arm 42 biased by a spring 43 and carrying , at its free end , a roller 44 and a plate 45 in the shape of a semicircle adjacent the roller . by acting on the lever 40 , the arm 42 may be swung from a tilted position into a substantially vertical position . in the latter position of the arm , the rollers 44 will engage with the bottoms of the brackets 25 , thereby raising the latter and bringing the rails 26 to tangentially contact the rollers 31 , 32 of the carriage . the upward movement length is calculated to also elevate the angle pieces 29 , 30 off the tops of the sidepieces 1 , 2 whereon they rest when the carriage 27 is inoperative . in this position , any rotation of the guides 23 , 24 is inhibited , in the outward direction by abutment on the sidepieces 1 , 2 , and in the inward direction by the plates 45 acting as stops . on the arms 42 being turned into the tilted position shown in phantom lines in fig5 the carriage 27 is brought , by means of the angle pieces 29 , 30 , to bear on the tops of the sidepieces 1 , 2 , whilst the guides 23 , 24 are moved further down until the rails 26 are separated from the wheels 31 , 32 to a sufficient extent to permit the guides to be turned inwards . at the end of the downward movement of the guides 23 , 24 , as determined by detents 46 on the rods 22 abutting the bushings 20 , the plates 45 have assumed an orientation which permits the guides to be turned inwardly . in order to hold the abrasive surface of the lower run of the sand belt 36 in contact with the workpiece , a pressure member generally indicated at 47 mounted slidably on the carriage 27 , is arranged to act on the back side of the belt . more specifically , and as shown best in fig4 the pressure member includes a carriage 48 in the form of a u - like element having two plane parallel vertical walls 49 interconnected by a portion or bottom 50 . cantilevered to the outside of the walls 49 are pairs of rollers 51 , 52 mounted idly . each pair of rollers 51 , 52 are adapted to engage from above and below opposed wings 53 of the sectional member forming the beam 28 . within the carriage 48 and between the walls 49 , there extend upwards small posts 54 which are placed side - by - side in pairs and carry at the top respective rollers 55 , 56 . in between each pair of rollers 55 , 56 , there is inserted a rib 57 which is located inwards of the beam 28 and extends longitudinally in the centerplane thereof . thus , the pairs of rollers 51 , 52 will guide the carriage 48 in the horizontal plane , the pairs of rollers 55 , 56 guiding it in the vertical plane . formed at the middle of the portion 50 of the carrage 48 is a hole opening into an underlying tube 58 made vertically fast with it . the tube 58 accommodates slidably therein a spigot 59 the upper portion whereof extends between the walls 49 of the carriage . attached to the top of the spigot 59 is a washer 60 acting as a detent for a spring 61 fitted over the spigot 59 and disposed between the washer 60 and bottom 50 . rigidly fast with the bottom end of the spigot 59 is a rectangular plate 62 which supports a pad 63 elastically ( in a manner known per se and , accordingly , not detailedly described herein ). to prevent the plate 62 from turning relatively to the carriage 48 , a rod 64 is rigidly attached to the plate which extends parallel to the spigot 58 and extends upwards , slidably through a hole formed in the bottom 50 of the carriage 48 . the pad 63 is held pressed against the sand belt by means of a handle 65 having two bent arms 66 , 67 interconnected at one end by a handgrip 68 . the opposite ends of the arms 66 , 67 are journalled to a projection 69 of a sleeve 70 surrounding the tube 58 . the sleeve 70 is locked on the tube 58 by means of a screw extending through the sleeve 70 and having an operating knob 71 at its outward end . the bends of the arms 66 , 67 carry two idler rollers 72 which are held in tangential contact with the plate 62 by the weight of the handle 65 . in the operating condition , the sander is as shown in fig1 where the table 12 is held in a horizontal position by the arms 14 , while the guides 23 , 24 , being raised by the action of the arms 42 raise , in turn , the carriage 27 off the tops of the sidepieces 1 , 2 allowing it to be moved along the rails 26 . at this stage , one provides for holding the workpiece on the table 12 . the holding of the workpiece on the table may be achieved by means of clamps or one or more adjustable stops 12a ( which may substantially have a double ` t `- like cross - section ), which are moveable ( and can be locked in position ) in grooves 12b ( having a corresponding inverted ` t `- like cross - section ) extending longitudinally and laterally on the table 12 , as known per se , and as such , discussed no further herein . by operation of the gear motor 5 , the table 12 is brought to a desired elevation whereat the surface to sanded directly underlies the lower run of the sand belt . then , after energizing the motor 37 and by acting on the handle 65 , the carriage 27 is shifted along the guides 23 , 24 in a transverse direction to the direction of movement of the sand belt . simultaneously , by lowering the handle 65 , the sand belt 36 is brought into contact with the workpiece and the sanding passes are effected by sliding the carriage 48 along the beam 28 . of course , the operations may be performed by the operator in a different order from that described , and sanding can be controlled by applying a higher or lower pressure to the pad 63 through the handle 65 . it should be noted that the pad 63 is always held parallel to the working table 12 in the operative position thereof to ensure true sanding at all times . when the sander is not in use and its overall dimensions are to be reduced , the table 12 is first tilted into a vertical position . to this end , the table is first brought to a preset elevation to permit tilting without interfering with the sand belt 36 or base 3 . then , the table is raised at the front edge to disengage the cam trunnions 17 from the notches 16 of the arms 14 . thereafter , by operating the handle 18 , the arms 14 are turned downwards and the table is turned about the trunnions 11 as indicated by the arrow a into a position between the sidepieces 1 , 2 to eventually take the vertical attitude shown in phantom lines in fig1 - 3 . it should be noted that during this step the cam trunnions 17 are held peripherally in engagement with the upper edges of the arms 14 . thus , the knob 71 is exposed which , once loosened , enables the handle 65 to be turned into a position lying longitudinally beneath the beam 28 thereby avoiding that the same may protrude frontally out ( see arrow b ). at this point , the overall dimensions of the guides 23 , 24 are reduced . the carriage 27 is pushed toward the rear of the sander where specially provided detents , not shown in the drawings but easily appreciated , lock it at a position where the angle pieces 29 , 30 are located above the tops of the sidepieces 1 , 2 . now , by raising the handles 40 into the position indicated in phantom lines in fig5 the guides 23 , 24 are lowered . during this downward movement ( arrow c in fig1 ), the carriage 28 is first brought to bear onto the tops of the sidepieces 1 , 2 , and immediately afterwards , the rails 26 are separated from the wheels 31 , 32 of the carriage . the downward movement of the guides 23 , 24 is halted by the stops 46 abutting the bushings 20 . it now becomes possible , by swinging as indicated by the arrow d the guides 23 , 24 , to bring the latter into a position of mutual alignment beneath the beam 28 , thereby the transverse dimension of the sander practically becomes that established by the sidepieces 1 , 2 . a peculiar feature of the sander according to the invention is that the sander may be operated with the table 12 lying on a vertical plane . this enables sanding of the board edges , which would be otherwise impossible with conventional machines or would involve unusual engineering . with the table laid vertically , it is also possible to sand workpieces of a large size since the useful clearance under the sand belt , with the carriage shifted out of the frame , that is at the lower extremity of the guides 23 , 24 , is unaffected by the presence of the underlying table . the invention may be variously modified and altered without departing from the purview of the inventive concept . in particular , reduction of the guides 23 , 24 to within the overall dimensions of the frame may be implemented in various ways . fig6 shows an embodiment wherein the rails are attached with their portion 73 directly to the upper edges of the sidepieces 1 , 2 , and for the remainder 74 are attached to brackets 75 journalled at 76 about vertical axes to the front edges of the sidepieces . in the inoperative condition , the brackets 75 are turned into a horizontal plane from a cantilevered position , wherein the portions 73 , 74 of the rails are aligned together , to a position wherein the brackets 75 are close to the inward faces of the sidepieces 1 , 2 . the brackets 75 , instead of turning in a horizontal plane , may be journalled to the sidepieces along the horizontal pivot axis 77 , as shown in fig7 . in this case , the brackets 75 , with the sander inoperative , would be brought to bear on the front edges of the sidepieces . compared to the embodiment of fig1 - 5 , the embodiments of fig6 and 7 are simpler construction - wise because they require no lifting devices for the brackets and carriage , and on account of the bracket articulation also being made simpler . however , the need for breaking the rails results in a junction which may adversely affect the smooth movement of the carriage 27 . in a further embodiment , the guides 23 , 24 are provided with a telescopic construction , reducable over the edges of the sidepieces 1 , 2 . | 1 |
fig1 b - 1c show a shaping part 10 in accordance with a first exemplary embodiment of the present invention , and fig1 a shows a u - shaped rigid - resilient plastic part 11 , for example , with circular or rectangular cross section , which is integrated as a bend impression element in the shaping part 10 . the shaping part 10 is produced by overmolding the u - shaped plastic part 11 with a soft silicone in a suitable injection mold . during the overmolding , the end portions 10 b with widened inner diameter and also the central lumen 10 a are produced at the same time . inner and outer lateral layers of the shaping part 10 are thus produced in one injection molding process . fig2 c shows , as further exemplary embodiment , a second shaping part 20 , and fig2 b shows , as associated preliminary product or semi - finished product , an extruded silicone tube 20 ′ having a central first lumen 20 a and a second lumen 20 b , which is arranged in the wall and has a much smaller diameter . fig2 a shows a rigid - resilient plastic rod 21 with circular or rectangular cross section , which is introduced into the second lumen 20 b of the silicone tube 20 ′ of circular or semi - circular cross section and provides this , as bend impression element , on the whole with a u - shape . as can be seen in fig2 c , the shaping part 20 is lengthened at the ends by overmolding of the extruded plastic tube , wherein widened end portions 20 c of the central lumen 20 a are again formed . in its outer form , the shaping part 20 according to fig2 c is , fundamentally , no different from the shaping part 10 according to fig1 b - 1c ; the main difference lies in that fact that , in the case of the second shaping part 20 , the bend impression element is introduced into a second lumen of the original silicone tube , said lumen being continuous lengthwise , whereas the first shaping part 10 is placed in the injection mold and is only embedded in the wall of the part during the subsequent overmolding . the shaping pat 30 according to a third exemplary embodiment shown in fig3 d - 3e is also structured similarly in essence , the preliminary product 30 ′ of said shaping part stretched in a straight line being illustrated in fig3 a - 3c . here too , a silicone tube with a central lumen 30 a of large diameter and a second lumen 30 b , which is arranged in the wall and has a much smaller diameter , is used as preliminary product . as shown in fig3 b - 3c , a plastic strip 31 , that in its initial form is also stretched in a straight line , is introduced into the second lumen 30 b and is anchored once tensioned . here , a semi - circular lumen with a plastic strip ( rectangular cross section ) can also be used . during a subsequent annealing of the silicone tube , the plastic strip 31 fixed at both ends of the preliminary product 30 ′ contracts in such a way that it entrains the entire tube into a u - shape . in this state , the silicone tube is then provided with ends with widening portions 30 c of the central lumen 30 a , again by injection molding . as mentioned with the aforementioned embodiments , an additional silicone casing layer can also be placed over the entire tube . this is merely optional , however , and the ends can also contact the extruded tube bluntly . fig4 a - 4d each show preliminary stages 40 ′ of a further shaping part , which is not illustrated in the end state , but of which the end form corresponds essentially to the form of the first to third shaping part . here , however , the shaping part is not an extruded silicone tube , as in some of the aforementioned exemplary embodiments , but is a silicone injection molded part with end portions having widened central lumen 40 b , said end portions being integrally formed from the outset . a plastic strip 41 is inserted , as a bend impression element or a force - intensifying element , via corresponding access points 40 c on one side of the wall into a recess ( groove ) 40 d intended for this purpose and running lengthwise . this bend impression element 41 is largely plastically deformable and can be transferred from the stretched state shown in fig4 d into a u - shape of the central portion , wherein it impresses this shape on the entire shaping part . at the same time , it has sufficient resilience in the deformed state to meet the general requirements placed on the shaping part according to the invention , as explained in greater detail above . fig5 a - 5b show two configurations of electrode line arrangements that can be provided with shaping parts of the above - described type . fig5 a shows an electrode line arrangement 50 with an electrode line ( electrode ) 50 . 1 , which has a tip electrode 50 . 2 and a ring electrode 50 . 3 as electrode poles and is deformed so as to be v - shaped in the end portion by a shaping part 50 . 4 shrunk - fit on the line between the two electrode poles 50 . 2 , 50 . 3 . the electrode line arrangement 50 thus tenses between the opposite walls of a vessel , which in turn leads in a desirable manner to the fact that the electrode poles 50 . 2 and 50 . 3 have reliable wall contact and can thus reliably performed their stimulation and / or sensing task in a durable manner . fig5 b shows , as modification of this configuration , a further electrode line arrangement 50 ′, which comprises a three - pole electrode line 50 . 1 ′ with the electrode poles 50 . 2 ′, 50 . 3 ′ and 50 . 4 ′ and two shaping parts 50 . 5 ′, 50 . 6 ′. both shaping parts are each placed between the three electrode poles around the corresponding portions of the electrode 50 . 1 ′ and are tightly glued there to the electrode . it can be seen that the electrode line in this embodiment has assumed a form that is undulating on the whole in the end portion , wherein this form in turn has the desired result that all electrode poles 50 . 2 ′, 50 . 3 ′ and 50 . 4 ′ have reliable wall contact . the shaping parts are shrunk - fit on the electrode in a manner known per se . shaping parts made of silicone are swollen ( for example , with heptane ) prior to assembly , such that the parts can be slid over the coil into the desired position — heptane escapes little by little and the silicone contracts together again and is thus shrunk fit onto the coil . if plastic reinforcement parts are integrated in this silicone part , this method can be used only to a limited extent , since plastic does not swell and the two materials may detach from one another . a further possibility is the short - term widening of the inner diameter of the shaping part by compressed air . the ends are sealed , compressed air is filled in , and the part can be mounted and placed on or over larger diameters . in a further variant the part is mechanically widened , for example , by a number of wires of half - shells arranged internally . the part can thus also be mounted and placed here on or over larger diameters . in addition , the present invention can also be embodied in a multitude of modifications of the examples shown here and aspects of the present invention highlighted above . it will be apparent to those skilled in the art that numerous modifications and variations of the described examples and embodiments are possible in light of the above teachings of the disclosure . the disclosed examples and embodiments are presented for purposes of illustration only . other alternate embodiments may include some or all of the features disclosed herein . therefore , it is the intent to cover all such modifications and alternate embodiments as may come within the true scope of this invention , which is to be given the full breadth thereof . additionally , the disclosure of a range of values is a disclosure of every numerical value within that range . | 0 |
a first step in this invention is acquiring the full analog value of the memory state ( e . g . the actual cell current , which in turn reflects the actual stored floating gate voltage vfg ). the following describes two alternative embodiments for rapidly sensing and converting , to digital form , data stored in a large number of physical cells ( e . g . a chunk of 256 cells ) simultaneously , each cell capable of storing a large number of multi - states ( e . g . four states or more ), and sensing capable of spanning a wide dynamic range . the basis underlying both of these embodiments is the analog property of the memory cell , wherein its current drive capability is in proportion to its stored floating gate charge ( voltage ). consequently , each memory state is characterized by its current drive capability ( in actuality a narrow range of current drives , including margin capability ). therefore sensing and discriminating the various states comes down to differentiating between the various drive level ranges . two exemplary embodiments are now described for achieving this differentiation . a first embodiment is described with reference to fig1 a and 1 b , and involves dynamic - type sensing , wherein the bit lines ( such as bit line 101 ) of the selected memory cells ( such as cell 102 ) are precharged ( e . g . to 2 . 5v ), and then the row ( e . g . word line 103 ) of the selected cells is turned on , preferably using a controlled ramp ( e . g . 5 usec rise time ) or a stepped staircase ( for example over 5 usec ), allowing the respective bit lines to discharge through the selected memory cells at rates proportional to their current driving capability . when the bit lines discharge to a predetermined voltage ( e . g . 1v ), they flip a corresponding sense amplifier ( e . g . sense amplifier 104 ), indicating sense achieved . the time taken to flip the sense amplifier from the start of sensing is an analog measure of the cell drive : the longer the time , the lower the drive ( i . e . cell is more programmed , having more negative charge on the floating gate as depicted in fig1 b ). table 1 is an example of sense amplifier trip time to cell current drive capability based on simulation using floating gate cell i - v data . in the example of table 1 , bit line 101 is precharged to 5v and tripped at 2 . 5v , load capacitance is 1 . 25 pf and control gate rate of increase is 1 . 25 v / usec , ramped to 7v in a staircase fashion . because of disturbs , it is undesirable to expose the memory cell drain to more than 2v . therefore the 5v precharge is , in one embodiment , applied to sense capacitor 105 isolated from the memory cell drain , and the drain is only allowed to charge to a lower voltage ( e . g . 1 . 5v ). with column segmentation this drain voltage lowering is , in one embodiment , done locally , using a segment select transistor to limit the voltage transferred from a global bit line to the local bit line , such as is described in copending u . s . pat . no . 5 , 315 , 541 assigned to sandisk corporation . in one embodiment , the trip times are converted en masse to a binary code using an a / d approach , as shown in fig2 . time is metered using clock 205 which increments master counter 204 which in the example shown here is an 8 bit counter . counter 204 drives lines 209 ( 8 lines in this example ) which feed into registers 201 - 1 through 201 - n via transfer gates 202 - 1 through 202 - n , respectively , with one register for each cell being sensed ( e . g . 256 , 8 - bit registers for a 256 bit memory chunk size ). at the start of sensing , counter 204 is initialized to zero , and then starts counting up , with the registers reflecting the count . at the point of a cell sensing ( i . e . at the sense amplifier trip time ), the corresponding sense amplifier flips , which isolates the corresponding register from counter 204 , thereby freezing the time ( and its associated binary code ) in that register . in this way , each register contains a binary representation of the analog storage level of the memory cell to the resolution of the a / d ( e . g . with 8 bits this gives resolution of approximately 1 part in 256 or about 0 . 4 %). to insure both adequate resolution and dynamic range , the clock frequency ( i . e . sampling rate ) must be properly chosen . if too fast it will not span the full range of times needed for a sense amplifier to flip for all possible stored memory cell data values before hitting the maximum count , while if too slow the result will be poor resolution and the risk of inability to discriminate between neighboring states . in order to provide some relationship with the memory cells &# 39 ; drive characteristics , in one embodiment the frequency of clock 205 is governed by a memory cell ( or group of memory cells ) set at an appropriate drive level . in this way , clock 205 tracks process variation and operating conditions ( e . g . voltage and temperature ), setting up the optimum clocking rate to span the cell &# 39 ; s dynamic range and associated memory states . although this embodiment is relatively simple and effective , it does have limitations by nature of its being dynamic . time constants associated with word line and / or bit line delays and their variations contribute both relative and absolute error . for example , if word line rc time constants are long relative to ramp ( or step interval ) times , then there can be significant differences in the times in which cells along the word or steering line ( or a single line serving as both the word line for selection and steering line for capacitive coupling ) experience a given word line steering drive voltage . the consequence of this is that cells at different positions along such lines will respond at different times . also , conversion from cell current drive to comparator trip time is not exactly linear , because the discharge rates and characteristics depend on the drive levels of the cell which will vary with the bit line bias level ( with conduction tending to decrease as bit line voltage levels drop , stretching out bit line discharge time ). also , the bit line capacitance can have a significant voltage dependence arising from junction cv characteristics . this nonlinearity in comparator trip time results in nonlinearity in time in the separation of states and margins in going from the lowest to the highest charged memory states ( whereas it is desirable to space the memory states evenly , charge - wise , to get maximum fit of states within the dynamic range and to have uniform margins ). a second exemplary embodiment removes these limitations by using a static sensing approach utilizing current comparators , as shown in the exemplary embodiment of fig3 . the fixed reference voltage , vref , of the embodiment of fig2 is replaced with a staircase reference current ( iref ) source 310 , which starts off at a minimum level , imin , and increments by _i with each count of clock 305 ( i . e . after n clock pulses iref = imin + n * _i ). for a given memory cell , when the reference current just exceeds the cell current , the associated one of current comparator sense amplifiers 104 - 1 through 104 - n will flip , freezing the corresponding count of counter 304 ( which increments in sync with staircase current generator 310 ) into the corresponding one of registers . in one embodiment , the scale factor for staircase current source 310 ( e . g . its maximum current ) is established using one or a population of floating gate memory cells ( e . g . erased strongly ) in order to provide optimum dynamic range with tracking of process and operating conditions ; i . e . the regulation of current source includes monitoring the characteristics of one or more floating gate cells dedicated for use in connection with this current source regulation . this second embodiment , while a bit more complex , offers better control , linearity and minimizes or eliminates sensitivity to dynamic effects . this includes eliminating the need for repetitive , controlled ramping of word lines in the case of dynamic sensing , simplifying many of the timing and associated control operations . once sensing is completed and data is frozen into all registers 301 - 1 through 301 - n , it is shifted out , for example , serially . a simple way to do this is to have the registers 301 - 1 through 301 - n tied together in shift register fashion . in the above example , the data stored in each register each comprises eight bits , requiring an eight line wide bus to shift the full data out of the memory chip ( for example to a memory controller , such as is described in u . s . pat . no . 5 , 430 , 859 assigned to sandisk corporation , for sending to requesting devices ) in one controller clock cycle , and thus requires eight output pads / pins . if data rate to the controller is less critical while keeping the number of pads / pins down is important , then the eight bits could be broken down , e . g . shifting out the four msb bits first followed by the four lsb bits through four pads in two controller clock cycles , or shifting out groups of two bits four times through two output pads in four controller clock cycles , etc . as previously stated , one goal of the present invention is to provide self - consistent , adaptive and tracking capability for sensing , capable of establishing both the data and the “ quality ” of the data ( i . e . the margins ). in accordance with certain embodiments of this invention , tracking cells are included within each of the sectors such as those described in u . s . pat . no . 5 , 172 , 338 assigned to sandisk corporation . these tracking cells are set at known states to reliably establish the optimum discrimination points for each of the various states . in certain embodiments , this is accomplished using as few as one cell per state . however , if better statistics are vital to establishing the optimum discrimination point , a small population of cells sufficient to establish such optimum points statistically is used . for example in one embodiment ten physical cells are used for each state , in which case for 4 - state encoding a total of 40 physical cells are used , as part of the overhead portion of the sector . as will be described below , data from these tracking cells will be the first information from the sector to be read into the controller , in order to establish the optimum discrimination points for the remainder of the sector data . however , in order to make these cells track the rest of the sectors in terms of data history and wear , they are not repeatedly erased and written into the same , fixed , pre - assigned states . this is because the amount of wear will be peculiar to that state and may not reflect the wear / history of the remainder of the sector . in one embodiment , managing wear , both in terms of insuring uniformity ( i . e . intra - sector wear leveling ) and in keeping such wear to a minimum , is handled by some method of continuous or periodic re - assignment of each of the logical states ( e . g . logical states l0 , l1 , l2 and l3 ) to a corresponding physical state ( e . g . physical states p 0 , p 1 , p 2 , and p 3 ), an example of which is shown in table 2 . these physical states p 0 to p 3 correspond to specific conduction levels of each memory cell ; e . g . p 0 is the highest conducting state , p 1 is the next highest conducting state , p 2 the next highest , and p 3 the least conductive state . a description of this concept applied to two state encoding and termed “ program / inverse program ” is disclosed in u . s . pat . no . 5 , 270 , 979 assigned to sandisk corporation . re - assignment of states with subsequent writes ( in one embodiment with each subsequent write , and in alternative embodiments after a specific number of writes ) is done , for example , by rotation or on a random number basis . this guarantees that , on the average , over many cycles , only about half of the full possible charge is transported to the cells , and that the wear of each cell is virtually identical to all others within its sector . the embodiment utilizing a random number assignment between logical and physical states has the advantage that it eliminates the possibility of synchronization between the logical to physical data re - assignment algorithm and variable user data , which would defeat such wear leveling . all tracking cells for each given logical state are re - assigned to the same physical state , e . g . all ten cells of one tracking group assigned with the role of storing logical state l1 , are set to either p 0 , p 1 , p 2 or p 3 , for a particular write cycle , dictated by the scrambling algorithm . given that the tracking cells go through the same scrambling operation as the remainder of the sector , they not only reflect the wear of that sector , but also provide the translation means to convert back from physical to logical state . since each tracking group is given a constant pre - assigned logical state responsibility , when the controller deciphers the various tracking cells groups ( e . g . the four groups of ten cells each ) it will concurrently establish the translation for the sector . more resolution requires more time to sense ( more steps in the a / d ), more die area associated with the larger registers , more cost associated with shipping data out to the controller ( more parallelism dictates more pads and thus an area penalty or , with same number of pads , takes longer to shift out all the data , and thus a performance penalty ), and more cost associated with processing the data in the controller . inadequate resolution results in limited visibility in common mode population margin shifts ( e . g . due to trapping / detrapping effects ), resulting in larger error in establishing comparator points . this larger error must be included in the multi - state budget , forcing larger separation between states , and consequently fewer states , i . e . lower multi - state scalability . a reasonable resolution target is a / d resolutions equal to approximately 3 % of the state - to - state separation . this provides visibility into sufficiently small cell current shifts within a population to allow meaningful correction ( i . e . avoiding margin failure from tail bits within a population due to poorer resolution ), and does not impose such a high resolution that it becomes meaningless vis a vis the various noise and error terms associated with setting and measuring states . specific examples for state ranges and counter / a / d resolution are shown in fig4 a and 5 b for 4 - level and 8 - level multi - state encoding , respectively . the cell current / floating gate voltage relationship used in fig5 a and 5 b for read are representative of cell characteristics built in accordance with the teachings of the present invention , using 0 . 5 micron based flash semiconductor fabrication technology available today , which for example has an i / v slope of approximately 20 uamps / volt with the zero current intercept ( projected threshold ) at 4 . 25v . in the example shown , the state - to - state separation for a four state cell is 30 uamps , the a / d resolution is 1 uamps and the dynamic range covered is 0 to 128 uamps . this gives about a 1 / 30 resolution of the state to state separation ( 3 . 3 %). a population of cells written into a given intermediate state is confined to a 10 uamp window , i . e . spanning ten steps of resolution . therefore 1 a / d step bit offers a 10 % resolution of the written population distribution , and any common mode shift of that magnitude , over time , can be corrected in 10 % resolution steps . therefore , for 4 - state a 7 bit a / d is suitable . the situation is similar for the eight state example of fig4 b , except state to state separation is 15 uamps , and a / d resolution is 0 . 5 uamps , covering the same 0 to 128 uamps dynamic range . this offers the same percentage of the population resolution , for which an eight bit a / d is suitable . the following describes the data flow and handling by the controller for each sector read operation . in order to support high speed , in one embodiment this operation is performed in hardware and / or firmware . for the purposes of the following discussion , the example of 4 - state encoding , with 7 bit sensing resolution ( providing 128 steps on the order of 1 uamp per step ) and ten tracking cells for each of the four states , is used . fig4 a depicts 4 - state encoding with each bit of resolution corresponding to approximately 1 uamp ( therefore about a 100 uamp full range ). in the embodiment depicted in fig4 a , 4 - states are shown , physical states p 0 , p 1 , p 2 , and p 3 . state p 0 is established by setting the cell to have a cell current under read conditions of 90 uamps or more ( e . g . by erasing the cell to that value ). when reading , state p 0 is detected when cell current is 85 uamps or more , thereby allowing a slightly relaxed tolerance for reading than writing . the programming levels for states p 1 , p 2 , and p 3 are also shown in fig4 a , as are the looser read current levels for each of those states . an appropriate guard band is placed between each state such that , for example , a cell current during read between 75 and 85 uamps is too ambiguous to be associated with either of adjacent states p 0 and p 1 . the operation of this embodiment will now be described with respect to the flowchart of fig5 and the diagram of fig6 . first , the reference tracking cells &# 39 ; data is shifted into the controller , one 8 bit set ( or byte ) for each cell . this data is then processed as illustrated in more detail in the flowchart of fig7 , starting with the first tracking cell group assigned to logical state l0 as described in table 2 . the function of these bits is to establish the optimum compare point for the l0 state by first establishing where the center of the population of tracking cells placed into the l0 state is . this can be accomplished on the ten cells per state population by continuously summing each successive data of the ten l0 cells , giving accumulation of those ten cells &# 39 ; data . it is desirable to maintain a max and min register concurrently , in order to minimize chance of error from an isolated , errant cell , either high or low . this is done by comparing each successive piece of data to the previously stored comparator data and at each compare operation storing the higher ( lower ) into the max ( min ) comparator . once data from all ten cells have shifted in , it is processed to establish the filter point , for example by subtracting the max and the min from the sum and dividing the result by 8 ( i . e . shifted to right three times ), giving the average storage level of the l0 assigned tracking cells . rounding to the nearest number is , in one embodiment , accomplished by shifting to the right three times but temporarily storing the third bit shifted and then summing this bit with the shifted value . this is then repeated for the l1 , l2 and l3 tracking cell population , at which point the system has determined the physical to logical conversion for each state . in one embodiment , this conversion is performed by ordering the l0 , l1 , l2 , and l3 states into descending order , and then matching this to the corresponding physical state assignment as shown in table 2 . for example , if l0 happens to correspond to physical state p 0 it will have the highest value of the four states , if l0 corresponds to physical state p 1 it will have the next highest value , and so forth , and likewise for states l1 , l2 , and l3 . if after ordering the order is l0 , l1 , l2 , l3 then state assignment # 1 of table 2 was used . on the other hand , if the order is l1 , l2 , l3 , l0 the assignment # 2 was used , and so forth per table 2 . in this embodiment , the optimum discrimination points between the four physical levels , p 0 , p 1 , p 2 , and p 3 are established by calculating the midpoints between p 0 and p 1 , p 1 and p 2 , and p 2 and p 3 . slightly better precision is achieved by postponing the division by 8 for the individual ten cell groups until after summing p 0 and p 1 , p 1 and p 2 , etc ., at which point the average of p 0 and p 1 is obtained by summing p 0 and p 1 and dividing by 16 ( shifting four to the right with provisions for rounding ) and similarly for p 1 and p 2 , and p 2 and p 3 , thereby establishing three compare values , c 1 , c 2 , c 3 , respectively , which are shown in fig4 a as current points 80 , 50 , and 20 between states p 0 , p 1 , p 2 , and p 3 . this then gives the optimum compare or filter points for the rest of the sector &# 39 ; s data , which is now shifted in . as data is passed through , it is sifted through a set of comparators ( for example , as described later with reference to the flowcharts of fig5 and 7 ) set at those compare points to establish their state ; i . e . higher than c 1 , ( making it state p 0 ), between c 1 and c 2 ( making it p 1 ) between c 2 and c 3 ( making it state p 2 ) or lower than c 3 ( making it state p 3 ). these are then translated to their corresponding logical states , based on the specific logical to physical assignment used , as discussed above . in one embodiment , compare points c 1 , c 2 , c 3 , loaded into the comparators are adaptive in nature , established by the sector itself via the tracking cells . in this way the sensing tracks the properties of the population of cells within the sector , their operating voltage and temperature conditions , history and wear , and any common mode drift , as for example may arise from detrapping of gate oxide trapped charge , accumulated during write cycling . since such detrapping is also present in the tracking cells , they establish the optimum point for sensing , whatever the degree of detrapping , provided their conduction remains within the dynamic range of cell state sensing capability ( i . e . ability to still discriminate between the various states ), and the mechanism is truly common mode , with minimal dispersion . in one embodiment , this adaptive adjustment of the compare points is performed in a continuous , real time manner . in an alternative embodiment , the optimum compare points for the l0 state as well as the other states l1 - l3 are established periodically as part of a maintenance operation , and not in real time as actual data is being read , to reduce impact on system performance . this latter approach improves performance by eliminating the repetitive overhead time associated with processing the tracking cell data . in one embodiment , it is invoked on a predetermined read interval basis as part of a read / margins checkout , and / or invoked in the rare event of read marginality or failure . this gives the ability to recover data or restore margins through data rewrite using the most optimum read reference conditions via the tracking cells . in one embodiment , a sector is broken down as shown in fig6 , to include user data and overhead bytes . the overhead bytes include a plurality of reference tracking cells for monitoring the condition of one or more cells known to be programmed to each of the logical states in the multi - state memory . the overhead also includes , if desired , header information such as address information , ecc bits , bit and / or sector mapping related information , and counts of the number of writes to the sector . referring again to fig5 , as the rest of the sector &# 39 ; s data is read and processed using the compare points established based on the referenced tracking cells &# 39 ; characteristics , a decision is made as to whether the data is acceptable or not . if not , gross defect management is invoked , such as described in u . s . pat . no . 5 , 602 , 987 . on the other hand , if the data is acceptable , a decision is made as to whether the data is “ clean ”, i . e . of a sufficiently high quality that there no data margin or ecc related problems . if the answer is yes , the data is sent out to the host without further intervention ; conversely if the answer is no ( i . e . the data is not clean ), the necessary error correction or “ clean up ” step is invoked thereby not only sending the data out to the host but also insuring that the corrected data is clean upon subsequent reads . as described above , one feature derived from this invention is the ability to concurrently determine not only the data itself but also the “ quality ” of each data point , or its margin , with respect to the above described compare points . even when a bit of data is read correctly , if it gets too close to a compare point , it may become unreliable sometime in the future , giving erroneous readings due to noise sensitivity , additional margin shift , or change in operating conditions arising from power supply or temperature variation . therefore , the quality measurement achieved by this invention provides a failure look - ahead capability , something dealt with in prior art , using special read - under - margin operations . such prior art read - under - margin operations generally involve multiple pass reads , invoked under special conditions or circumstances , and requiring special circuitry ( which may include controlled changes to reference / sensing circuitry or special cell biasing operation ) to establish the needed margin differentials . often , the accuracy or resolution of such differential means is limited , forcing larger margins than absolutely required . in the case of multi - state , this would dictate wider memory threshold voltage windows per state , and consequently wider voltage separation between states , thereby resulting in fewer states available for a given cell &# 39 ; s dynamic voltage range , and consequent lower memory storage density per cell . however , with the novel approach of the present invention , the margin or “ quality ” of the data is a natural byproduct of each read operation , requiring no special modes or events to initiate it , and allowing the system to instantly react to any detection of marginal data . in essence , the capability of a “ look ahead data recovery ” is automatically included each read operation . however , instead of such margining operation being considered a very rare operation for a very rare event , in accordance with the present invention , the trade - off made in order to achieve high density multi - state is to allow a substantially higher incidence of such marginality , with such marginality being made manageable by providing a measure of this marginality as part of the standard read operation . in one embodiment , the specific way such marginality detection is implemented includes , around each of the compare values c 1 , c 2 , c 3 , an additional pair of values c 1 + del , c 1 - del , c 2 + del , etc ., shown in fig4 a as “ poor margin filter ”, and associated comparators ( not shown ). any data falling between the compare points c 1 , c 2 , c 3 and their associated +/− del points is tagged as marginal ( e . g . if state p 2 , which falls between compare values c 2 and c 3 , is detected to be between c 2 and c 2 - delta or c 3 + delta and c 3 , it is then tagged as marginal ). consequently , each piece of 4 - state data can have a three bit result , the first two bits , a and b , for the actual data and a third bit , q , for its marginality or “ quality ” ( e . g . 0 if ok and 1 if marginal ), as depicted in table 3 . in one embodiment , the quality of the data includes additional information , for example whether the sensed parameter ( e . g . cell current ) is too high or too low with respect to the center of that state &# 39 ; s population ( e . g . for state p 2 , if found between c 2 - delta and c 2 it is too high , whereas if between and c 3 and c 3 + delta it is too low ). this allows clean up reaction conditional on its direction of marginality . for example , if a memory cell &# 39 ; s marginality is a consequence of being shifted towards being too heavily programmed , the course of action is to re - erase and program that data as is part of a full sector data scrub operation . on the other hand , if a memory cell &# 39 ; s marginality is such that it is shifted towards being too heavily erased , recovery of proper margin for the state of the memory cell is accomplished by programming only that one memory cell slightly in order to regain its needed margin or “ quality ”. an example of the latter is the case of relaxation of trapped channel electrons ( which can accumulate after a large number of writes to a cell or a group of cells ) which causes cell margins to drift from a more to a less heavily programmed condition . in such a case , it is sufficient to add some programming operations to regain cell state margins ; no sector erase before programming is required . in one embodiment , a count is stored within each sector as part of the sector &# 39 ; s header whose function is to be incremented each time a corrective action associated with a read scrub takes place . once this count reaches a maximum allowed level , cmax , the corrective action invoked is to map out the marginal / failing bits , whereas prior to reaching this cmax value , data is rewritten without such mapping . this embodiment preserves the sector longer prior to the entire sector being retired from service , by avoiding nuisance marginalities resulting in excessive bit and sector mapping , while filtering out the truly bad bits which should be mapped out . once the cmax count is reached for a sector and the failing marginal bit is mapped out , the counter is reset to zero and the procedure is repeated . writing the multi - state data is now described with reference to the exemplary circuit diagram of fig8 and the associated flow chart of fig9 . with reference to fig8 , the components located within the dashed line indicate components which are replicated for each sector . following the data unconditional sector erase , data is written into that sector on a chunk by chunk basis . starting with the first chunk , the first intermediate state , state p 1 , is placed into the programmed state , which is initiated by using a short , low voltage vcg pulse ( for example approximately 4 usec at 2v control gate bias ) followed by a verify read against a reference current set at the level appropriate for state p 1 . for bits within the chunk targeted to receive this programming , but which become sufficiently programmed , an internal circuit locks out further programming of those bits , while targeted cells , still insufficiently programmed , experience the next programming pulse , which is of the same width as the first , but has incrementally higher vcg ( e . g . 200 mv higher ), again followed by verify . this sequence of programming with incrementally higher vcg followed be verify continues until all state p 1 cells targeted within the chunk are verified , or until a maximum vcg is reached ( in which case defect management is invoked ). then the next intermediate state , state p 2 , is written , in similar fashion to the first intermediate state p 1 , but using the reference current setting associated with that state , and starting with a vcg level appropriate for reliably programming that state in the shortest time . this procedure is repeated for each state until all states in the chunk are programmed and verified , and the whole process repeated on the remaining chunks on a chunk by chunk basis . an alternative embodiment , depicted in the flowchart of fig1 , provides an increase in speed . in this embodiment all states within a chunk of bits are programmed concurrently in a single vcg staircase progression as follows . the data to be written into the chunk is shifted into the corresponding registers ( e . g . register 43 of fig8 ), exactly mirroring the readout operation , and the corresponding bit rs latch 46 is set enabling its associated bit line driver . associated with each physical data state , p 0 , p 1 , p 2 , p 3 is its register count and corresponding current level . after each programming pulse the reference current staircase is invoked in analogous fashion to the read operation , with the master counter concurrently incremented . a comparator circuit associated with each register ( formed of transfer gate 41 and xor gate 42 ) compares the input data ( i . e . count ) stored in register 43 to that of master counter 44 . when a match occurs , the program lockout feature upon verify is enabled . actual lockout only occurs when the corresponding cell is sufficiently programmed to pass read verify with respect to the associated reference current setting , ( i . e . programmed into the associated physical state ). once verify is successful , nand gate 45 resets rs latch 46 , disabling its associated bit line driver 47 , and resulting in all subsequent programming of that cell being disabled for the remainder of the sector write operation . if verify fails , the cell will receive the next vcg incremented programming pulse followed again by the scanned current source / master counter verify procedure . unlike reading , which calls for use of the entire current staircase to resolve the state to full analog precision , the write / verify operation only needs to use those reference current settings and associated counts specific to the set of memory states , e . g . specific to states p 1 , p 2 , p 3 as predefined ( p 0 , being the erased state , is excluded and inhibited from programming from the outset ). this helps speed up the verify process by having three settings in the case of 4 - states , in place of 128 settings exemplified for the read operation of fig4 a , where 128 settings allows for quality determinations to be made . therefore , as illustrated in the example of fig1 , each verify consists of a three step staircase operation in which the first step consists of setting up ( e . g . rapidly incrementing up to ) the first reference current level associated with physical state p 1 , including concurrently setting up the master counter ( e . g . counting ) to the corresponding counter value , performing a read / sense operation , and locking out from further programming any cells which both match their register value to that of the master counter and are read as programmed ( with respect to the corresponding reference current setting ). each following step of the three step operation consists of setting up ( e . g . rapidly counting up to ) the next data current level and corresponding reference current setting and repeating the read / sense operation , identically to the first step , until all three steps are completed . note that it may not be necessary to have a full match of the 8 bits , only that a sufficient number of msb ( most significant , or of highest current weight bits ) match . this is most applicable when there are much fewer allowed states and corresponding cell current targets than resolution of the a / d . in this case , as long as the msb bits uniquely differentiate each of the various states ( e . g . there are a minimum of two msb bits for 4 state and 4 msb bits for 16 states ) only those msb bits are required for the exclusive or . this will save some area associated with exclusive or circuitry , but does restrict somewhat the current assignment flexibility for each state . this program / 3 - step verify procedure is repeated , with vcg incremented in each subsequent program step , until all cells in the chunk are verified or max vcg level is reached , as described previously . this entire operation is then repeated for all remaining chunks of the sector , at which point sector multi - state date writing is complete . a significant advantage of this novel approach is that it can be extended to a large number of multi - states ( e . g . 16 ) without substantially impacting write performance , other than that required for improved resolution ( e . g . more and smaller vcg steps , or lower drain programming voltage vpd , to slow down programming rate ), and the additional time needed to sense / verify each of the additional states . the latter , being a read operation , tends to be much faster than programming , and therefore should not substantially impact write performance . an alternative embodiment which speeds up the verify process is depicted in the diagram of fig1 . in place of the single adjustable reference current source , multiple current sources ( or parallel tap points of a master current source ) are used . in one embodiment , the number of current sources is ( n − 1 ), where n is the number of states , since a current point is not needed for the fully erased state . a data - in register of size k is used for each cell in the chunk , where 2 { circumflex over ( )} k = n . the information written into the data register by the controller at the start of write is used to select one of the n − 1 current levels during verify , dependent on the particular state . upon verify , all cells of the chunk are compared simultaneously to their corresponding particular reference target in a single verify operation , locking out further programming , on a cell by cell basis , if successful . this allows full verify to complete in one parallel operation , as opposed to the multi - step serial operation in the previously described embodiment , substantially improving verify speed . the cost is the requirement of the multi - current sources , counting and associated selection circuitry within each bit of the chunk . as in the multi - step embodiment , the requirement of data - in register can be served by a portion ( e . g . the msb portion ) of the existing readout register . the exclusive or used in the embodiment of fig8 is now replaced with straight decoding to select the appropriate current source . an additional feature of the adaptive multi - state discrimination sensing of the present invention is the ability to put bounds to extreme states , an upper bound for the highest state ( e . g . physical state p 0 ) and lower bound for the lowest state , assuming that this lowest state is not already in cutoff . when the extreme states ( as for example reflected within a subset of the tracking cells ) cross those bounds , the data is deemed to be outside the limits of safe detectability vis a vis available dynamic range , and sector data either needs to be refreshed ( rewritten ) or the sector mapped out , replacing it with a spare sector . however , this does not eliminate the need for maintaining a cumulative count of the number of write operations experienced ( referred to as “ hot count ”) per sector , since there is no warning at the time of writing that , once written , such excessive shift may occur . such warning is the function of a “ hot count ceiling ”; to put an upper bound to the amount of cumulative cell wear allowed , forewarning the possibility of excess trapped charge and associated margin loss due to its subsequent detrapping , termed relaxation . if such relaxation exceeds a critical value , the resulting common mode shift of all cells ( noting that some form of data state rotation is being used to keep wear on all cells within the sector uniform ) within the sector , typically from less conductive to more conductive levels , becomes sufficiently large to prevent discrimination between the highest two states ( fully erased state and state just below it ); i . e . drift exceeds dynamic range of the system . in order to avoid such failure , sectors cycled to such high trapping levels must be retired . the hot count is an indirect indicator of such trapping , since in addition to the number of cycles experienced , cumulative trapping is sensitive to other factors such as duty cycle of the write operation , time between writes , operating and non - operating temperature exposure , etc . ; i . e . history / details . when hot count is used as criteria for mapping out a sector , it must assume worst case conditions to insure no failure . however in practice , systems using such memories rarely , if ever , experience such worst case history exposure under actual application . therefore , mapping out of a sector based on cumulative hot count is often excessively premature for practical applications . an alternative embodiment uses a “ twin - cell ” trapping gauge included within each sector , whose function is to detect directly the amount of channel trapping shift which is responsible for the relaxation . this provides a direct measure of the amount of wear actually seen by cells in the sector , comprehending both cumulative write cycles or hot count and history of sector exposure . only when this cell &# 39 ; s shift reaches a critical value will the sector be retired , and no hot count information is required to make this decision . this allows much higher endurance capability in actual system use than can be safely provided via hot count because , unlike hot count which can only provide a general indication of cumulative wear ( since it cannot gauge wear directly , only exposure ), and therefore the hot count must be heavily guardbanded ( i . e . allowing minimum number of writes to accommodate worst case wear ), the twin cell &# 39 ; s direct measure of wear can minimize the amount of such endurance guardband . one embodiment of a twin - cell of the present invention is depicted in fig1 and , consists of a cell 600 having a single floating gate 601 but two separate sensing channels , one channel 602 being a read / write channel ( r / w ), the other channel 603 being a read - only ( ro ) channel . cell 600 is designed to match actual memory cells , e . g . by taking two adjacent memory cells and tying their floating gates together . programming of cell 600 is performed through the read / write channel by raising bit line bl 2 to a programming voltage ( for example about 7v ), and grounding bit line bl 1 , while bit line bl 0 is floated ( or grounded ). in this way , all the stress and trapping associated with hot electron programming is confined to the read / write channel 602 . using the a / d read of read / write channel 602 followed by a / d reading of read only channel 603 and finding the difference ( e . g . by subtracting ) gives a measure of channel trapping ( delta ). early in a sector &# 39 ; s life , with low cycling exposure , this delta is close to zero , while with progressive cycling the difference grows , with the read only channel 603 giving higher a / d counts ( appearing more erased ) compared to read / write channel 602 . the state set and used for useful comparison is , in one embodiment , a middle intermediate state , offering both the widest range and the average wear of a cell . when the delta exceeds a critical value ( e . g . 20 counts in example of fig5 a and 5 b , corresponding to a cell current shift of 20 uamps and 10 uamps for the four and eight state encoding , respectively ) the sector is at its limit with respect to wearout / relaxation or other potential read and reliability problems and is retired . in summary , key points described thus far in this specification for supporting high density multi - state are : 1 . parallel , full chunk , a / d conversion of multi - state data , with adequate resolution to provide analog measure of the encoded states ; 2 . master reference cell ( s ) whose prime function is to provide optimum dynamic range for comparator sensing ; 3 . logical to physical data scrambling to provide both intra - sector wear leveling and increased endurance capability of about twofold . 4 . intra - sector tracking cell groups , one for each state , included in each sector to provide optimum compare points for the various states , and able to adapt to any common mode shifts ( e . g . relaxation ). it also provides translation of data rotation . a ) to , on - the - fly , find midpoints of each tracking cell group , b ) with which to establish data state discrimination and marginality filter points , c ) through which sector data is passed , giving both the encoded memory state , and its quality ( marginality ), for each physical bit , d ) optionally , to decide what actions must be taken to clean up ( scrub ) marginal bit data based on the quality information ( e . g . do full sector erase and rewrite versus selective write , only ). 6 . optionally to include a small counter on each sector which is incremented each time a read scrub is encountered . when the count reaches maximum allowed , marginal bit ( s ) are mapped out rather than rewritten and counter is reset to 0 . this provides a filter for truly “ bad ” bits . 7 . same means are applied in reverse to write multi - state data back into a sector , using the same circuitry as used for read but operated in reverse , to provide self - consistent data encoding . in addition , two alternative embodiments for performing verification are taught : 7a . using a reference current staircase to sequentially scan through the range of states , conditionally terminating each cell as the current step corresponding to its target data is presented to the sensing circuit . 7b . using a full set of n − 1 reference currents of the n possible states to simultaneously verify and conditionally terminate all cells . 8 . twin - cell option can be included in each sector to provide deltavt shift level associated with cycling driven trapping and channel wearout , triggering sector retirement before detrapping shifts exceed read dynamic range or other potential read errors . this replaces hot count based sector retirement , greatly increasing usable endurance . an important goal for multi - state is achieving competitive speed to two - state devices , with respect to both write ( data programming ) and read . the reason that maintaining comparably high performance is difficult for multi - state , as compared to binary encoded data , originates from the considerably tighter margin requirements associated with multi - state encoding ( given a limited total memory window budget ), coupled with the fact that the information content per cell increases only logarithmically for a linearly increasing number of multi - state levels ( i . e . 2 n levels gives only n bits of information ). so along with margins , performance becomes a victim of the diminishing returns associated with increasing levels of multi - state . in the embodiment discussed above with reference to fig1 , write performance is heavily impacted by having to progressively and carefully go through each state , the progression requiring a sequential , multiple pulse / check methodology to carefully set the state , although in several embodiments verification speed can be increased , as discussed above . for example , to implement 4 - state : erase sets up physical state p 0 ; a first vcg staircase of up to 7 pulse / check steps sets up physical state p 1 ; followed by a second group of up to 6 pulse / check steps to set up physical state p 2 ; terminated with a last programming step to set up physical state p 3 ; giving a total of 14 pulses to write two bits of information , 7 pulses per bit , in place of the one pulse per bit for writing binary . projecting this to 8 level multi - state , the total number of pulses would be more than 30 , a further slowdown to more than ten pulses per bit . thus far , read performance has not been impacted for two reasons . the first is the feature of concurrent multi - state sensing using multi - leg cell current mirroring to n − 1 sense amps ( e . g . three sense amplifiers for 4 - state ). the second is the stream read feature appropriate for mass data storage , wherein , other than latency , the actual cell read time is hidden by the stream read implementation which simultaneously shifts out a large chunk ( e . g . 256 bits ) of previously read data while current data is being sensed . for more aggressively scaled multi - state implementations , both of the above features will become inadequate . with respect to the first , the use of static current sensing becomes increasingly unattractive , both because of increasing ir drops with physical scaling and increased memory window requirements while sensing margins decrease , and because of the higher power consumption associated with high value multiple current levels . a more attractive way to sense multi - states is via voltage margining , which requires only minimal cell current ( as for example using dynamic type sensing ), but dictates stepping through the range of control gate voltage margin levels spanning the states ( for n states , this means a minimum of n − 1 steps ), an example of which is given in the above referenced analog dynamic - type sensing embodiment . this impacts the stream read feature however , because now the time consumed in actually stepping through the various margin levels , followed by sensing , increases greatly . when combining this with progressive demand for higher - still data rates in mass storage , it will become increasingly difficult to exploit stream read to achieve enhanced performance . in addition , write performance can also be significantly impacted by internal read speed limitations , since read is an integral component in reliably setting the individual states ( via program / verify loops ), as well as for post write sector data checking . so with more aggressive use of multi - state for scaling , based on the above scenario , performance will continue to decline . the above referenced analog sensing embodiment improves performance by supporting a large degree of parallelism . greater parallelism is one way to retard the decline in performance associated with increasing numbers of cell states . however , the use of a virtual ground array ( imposing a separation between simultaneously addressable cells ) plus the constraint of a 512 byte sector size granularity , places a limit on how far parallelism can pushed . the embodiments of this invention described in the following section offer a solution to the above performance limitations , by substantially cutting down the number of discrete steps required for both programming and read , while preserving the desirable features associated with analog / voltage margin sensing taught by the present invention . given that a dominant controlling element allowing differentiation between the various multi - state levels is the control gate ( or equivalently termed steering gate ), the key to reducing the number of discrete steps used for both read and write is to simultaneously apply , to the full group ( chunk ) of cells , control gate voltage values associated with each cell &# 39 ; s particular data state requirements , on a cell by cell basis . in a row oriented sector , in order for the control gate to be individually adjustable for each cell , it cannot run in the row line direction , since it then becomes common to all cells which are to be simultaneously operated on . rather , it needs to run in the column ( bit line ) direction , which allows it to both be individually adjustable on a cell by cell basis , and individually responsive to the sensing result on the associated cell bit line . the basic elements of one embodiment of such a cell are shown in fig1 . since control gate 71 runs parallel to bit lines 72 - 1 and 72 - 2 , control gate 71 cannot also serve as the select line ( which is the usual case in eprom and flash memories ), since unique cell selection along a bit line dictates that the select line run perpendicular to the bit line . this forces the select line to run in a different layer , which in one embodiment is a poly 3 line with the control ( steering gate ) being a poly 2 line and the floating gate built from poly 1 . specific exemplary embodiments of cell structures suitable for use in conjunction with this aspect of the present invention are described later . a cell as in fig1 is read using the control gate in an a to d type binary search , as illustrated in the exemplary embodiment of fig1 , and the flowchart of fig1 . each sensing circuit consists of sense amplifier ( sa ) comparator 81 , having one input lead which receives an input signal from memory cell 99 via bit line 82 - 2 , and another input lead receiving an input signal from a global reference circuit ( not shown ) which provides reference signal iref . the output of comparator 81 is used to update a corresponding n - bit control gate register element ( cgre ) 83 , the number of bits governed by required sensing resolution ( e . g . if a 1 in 64 resolution is desired , a six bit register is used ). the value stored in cgre 83 is then used to provide the next control gate read vcg voltage , via the corresponding next step processor ( nsp ) 84 , in a successive approximation scheme . following is an example of the read operation flow , as depicted in the flowchart of fig1 . cgre 83 is a 6 - bit binary register element , with a corresponding dynamic range on the control gate ( via nsp 84 ) of 0v to 7 . 875v in 125 mv steps . read starts with the binary value 100000 ( nold ) loaded into the cgre , giving the midpoint vcg of 4v . the output from sense amp 81 is then fed back into control gate register 83 , via conditional element 89 , according to the relation : in this way , if cell current is higher than iref , the next vcg will be lower , reducing the cell current . along with this next vcg , the next nnew = nold and the next dn = dn / 2 are generated by next step processor 84 . this binary search continues five more times ( for a total of 6 passes ), wherein the last cgre 83 value becomes the digital equivalent of the floating gate memory state . if the memory cell uses an 8 - level ( three logical bits / cell ) multi - state encoding , this gives three bits of resolution between states for state - to - state discrimination , guardbanding , margining , etc . data can then be processed in ways similar to those described in the afore - referenced analog sensing embodiment , the difference here being the rapid binary search methodology ( as opposed to one - step - at - a - time sequential search ), which for 1 in 64 bit resolution represents a 10 × performance improvement ( six steps in place of a possible total of around 64 steps ). in one embodiment , sensing is extended to a full chunk of bits ( e . g . 128 bits per chunk ), wherein each sensing circuit contains its own corresponding sa , cgre , and nsp elements , as is depicted in the embodiment of fig1 , in which the operation of each sensing circuit is conditional on its corresponding memory cell . in this way , the strength of the binary search approach is exploited to recover most of the lost read performance . for example , comparing the above example to a two - state read , assuming that each individual step of the binary search takes a comparable amount of time as that of the two - state sensing , then the total time expended in the multi - state read is equal to 6 binary reads . for 8 - state encoding , three bits of information are extracted , resulting in a read time per logical bit of only twice that of binary state reading . given that margin information is concurrently available as well ( as described above ), this offers an excellent level of read performance , consistent with a stream read implementation . in certain embodiments , the same elements used for reading are also applied to accelerate multi - state programming , again optimized to the targeted memory state on a cell by cell basis , as illustrated in the example of fig1 . here , the cgre x 83 is initialized with the optimum safe starting value for the particular state ( this may come from a set of updatable parameters stored within the sector ). in memory cells whose magnitude of programming ( e . g . programming vt ) increases with increasing vcg , this optimum safe starting point is the highest value of vcg allowable that will not cause the memory cell to program excessively , overshooting its targeted state ( i . e . overshooting its allowed state range ). starting at lower values than this optimum value , while safe , costs more programming time , because the earlier programming pulses do not provide a sufficient magnitude of programming towards the targeted state , thereby decreasing write speed . in one embodiment , a different relationship of vcg with cgre from that of read is used to satisfy dynamic range for programming ( e . g . by adding constant voltage kprog as indicated in the exemplary embodiment of fig1 ). following each programming pulse , a verify operation is performed . in the class of cells described above , if programming margin target is not achieved , the cgre value is incremented by 1 , with a corresponding incremental voltage increase on vcg via nsp element 191 for the next programming step , whereas if margin is reached , further programming on that bit is locked out , by disabling further application of programming voltage on its associated bit line and optionally eliminating application of vcg as well . in one embodiment , this operation is performed simultaneously on all bits within the chunk , each bit starting at its optimal vcg , conditional on its corresponding to - be - programmed data . in this way , programming is completed in about six steps , relatively independent to the level of multi - state ( e . g . 4 , to 8 , or 16 level multi - state cells are , in accordance with this embodiment , programmable in a comparable number of pulses ), in place of the more than 30 programming steps indicated earlier for a fully sequential 8 - level multi - state programming embodiment . this not only represents a 5 × write speed improvement , but given that three bits are being encoded , this gives an effective number of programming / verify passes of two passes per bit , only twice that of binary encoding . since performance of a full write operation includes additional time overhead above and beyond program / verify , this smaller difference in program speed may translate , in practice , to only a minor reduction in overall write speed as compared to binary encoded writing . cell verify can also be made state specific , using the same cgre / nsp engine described above with reference to fig1 , by loading the targeted verify voltage ( i . e . that value corresponding to the to - be - programmed data ) into its associate cgre . in this embodiment , unlike the read operation , for which vcg is changed during the read binary search flow , during the verify operation the state specific vcg verify voltage is kept fixed during the full program / verify flow ( i . e . nsp for verify remains unchanged ). in this way , all cells within a chunk are verified simultaneously , with further programming locked out , on a cell by cell basis , as each cell passes the verify operation . this data conditional , high performance verify embodiment complements the above described high performance , data conditional programming embodiment , offering a highly parallel , fast speed methodology for setting a many level multi - state memory . in one embodiment , in order to better exploit this capability , two different cgre / nsp circuits are used , as illustrated in fig1 . cgre / nsp circuit 91 is used to support programming , and cgre / nsp 92 is used for verify , allowing these two circuits to be multiplexed at high speed onto the control gate when changing between programming and verify operations . although using the individual , cell by cell vcg supply as in this embodiment , offers an excellent approach to supporting a high level of multi - state at high speed , it puts the burden on quickly providing all these vcg voltages . in one embodiment , all the possible voltage steps are generated and available simultaneously on a bus of voltage feed lines . in this embodiment , each cgre value is used to decode which one of these feed lines to connect to its corresponding control gate . this embodiment is attractive when there aren &# 39 ; t too many vgc levels to manage . since in principal only seven compare points are needed for discriminating 8 states ( and only 15 compare points are needed for discriminating 16 states ), this will often be suitable . however , this limits the high speed flexibility to dynamically tune the sense points and determine margins . if the need for attaining such full resolution is very rare ( as for example when ecc indicates a memory state failure or a marginality problem ), an alternative , hybrid embodiment is provided which only demands such capability rarely ( e . g . on the rare ecc flag ). on those rare occasions , those compare points are incrementally shifted to fully resolve the margins , albeit via a more time consuming procedure , because now voltage values will need to be provided which are not included in the limited set of supply levels ( e . g . 7 to 15 levels ) concurrently available . this would dictate temporarily generating new voltage levels , not concurrently available , consuming more time , and potentially breaking up the concurrent parallel chunk operation into operations on individual bits or small groups of bits to feed these specialized voltage levels . in the case where a large number of vcg voltage possibilities and / or all vcg voltage possibilities are required ( i . e . full real - time margining capabilities for full dynamic range flexibility ), one alternative embodiment , similar to the embodiment of fig1 , expands the cgre x 83 and nsp 191 elements to include sample - and - hold circuitry for each sensing circuit , the complement of which are fed by a common , single staircase voltage source . the voltage delivered by each nsp is conditional on its corresponding stored cgre value . care must be taken in such an embodiment to ensure that the dynamic nature of sample and hold circuitry with its potential for drift , and the time requirements for scanning / sampling the full dynamic voltage range , do not cause programming voltage vpg error . the benefit of this embodiment is that it incurs less area and power penalties . it is desired to simultaneously process each of the cgre data , based on the associated sense amplifier result and the previously stored value ( as well as the step in progress in the case of read ), conditional on the operation in progress . this is most complex for read , involving the manipulation for successive approximation ( basically providing up / down counting function , conditional on sensed result and current iteration step ). for programming and verify its requirements are simpler , complexity coming primarily in initializing each of the cgres to the corresponding data values ; once initialized , nothing further is required for the verify , requiring only incrementing by one for each successive programming / verify step in the case of programming . notwithstanding these complexities , required circuit areas and complexity of circuits should not differ substantially from approaches which use multiple sense amplifiers . the prior art approach uses multiple sense amplifiers ( e . g . requiring up to seven sense amplifiers for 8 - level multi - state ). in accordance with this embodiment , the multiple sensing circuits and associated current mirrors and reference legs are now replaced by one sense amplifier circuit , a couple of registers with associated decoder functions , sample and hold circuits , and some glue logic . the other major element of complexity is that of shifting out and processing the large body of data stored in the chunk - wide cgre register . one embodiment used is similar in this regard to that described in the above - referenced analog sensing embodiment . firstly , independent of other considerations , a memory cell must be competitive with respect to physically small size and scalability . beyond that , however , based on the cell requirements described above for a row selectable but column steerable element , as represented in the example of fig1 , the choices are limited . furthermore , in order to realize such a cell / array in minimal area , it must incorporate virtual ground architecture , and this is not just because of the approximately 50 % additional area associated with using the conventional ½ contact per cell array . the joint requirement of bit line and steering line running in the same direction , with the bit line having to physically run above yet periodically dropping below the steering line to contact diffusion , dictates that they run side by side rather than be stacked . whereas this occurs naturally in the virtual ground array , wherein active transistors are laterally displaced from the bit lines , in the conventionally contacted cell array the active transistors , while displaced from the bit line contacts themselves , do lie directly below the bit line conductor . for this reason , select / steering functions in such arrays are generally row oriented , eliminating the conflict . to do otherwise further increases cell area . one memory cell which meets all the above requirements is the virtual ground , split gate cell having column oriented poly 2 steering gates and row oriented poly 3 select gates . for reference purposes this will be referred to as cell embodiment 1 . such a cell can be programmed using either conventional drain side programming , or source side programming , depending on whether the poly 3 select transistor is strongly turned on or throttled down , respectively . erase is also row oriented , using poly 3 as the erase line , thereby achieving the row oriented sector . the source side programming version of this is described in u . s . pat . no . 5 , 313 , 421 , assigned to sandisk corporation . for reference purposes , this version will be referred to as cell embodiment 1 a . another suitable cell is the dual floating gate variant of cell embodiment 1 a , such as is described in copending u . s . patent application ser . no . 08 / 607 , 951 filed feb . 28 , 1996 and assigned to sandisk corporation , which offers a true cross - point cell ( 4 * lambda 2 per physical bit ). for reference purposes this version will be referred to as cell embodiment 2 . however , because of the series nature of the tri - gate structure ( the two floating gate channels being in series ), it is constrained to using source side programming , and will be more limited in how many levels of multi - state are realizable . nevertheless its inherently smaller cell size , self - alignment features and consequent scalability make it equally attractive to the simpler but somewhat larger cell embodiment 1 a . because of the requirement within each cell to have both bit line and steering line ( control gate ) running parallel to each other ( for convenience , their direction henceforth defined as vertical ), this raises the question of bussing / pitch requirements . to achieve a physically minimal cell , this dictates that the lateral extent ( horizontal width ) of the cell must be close to minimum feature pitch ( i . e . about 2 * lambda ), forcing the above two lines to fit in that pitch . at the cell level this is not a problem , since the steering line and bit lines tend to run side by side , and more importantly they are on different layers ( poly 3 and bn +, respectively ) eliminating proximity / overlay constraints . however , going from the local to the global interconnect level is a challenge . for ultra high density flash memory , one way to interface long bit line columns to the memory cell array is via column segmentation . this approach uses the continuous ( vertically ) running metal lines as global bit lines , which drop down periodically to local diffusions serving memory sub - arrays or “ segments ” ( e . g . 16 sectors ) via segment select switching transistors . in this way array segments are isolated from one another , eliminating the large cumulative parasitics of leakage current and capacitance , and providing column associated defect and repetitive disturb confinement . this also provides opportunity for relaxing the pitch requirement of the global bit lines from one per cell to one per two cells , depending on the segment selection approach used ( e . g . u . s . pat . no . 5 , 315 , 541 assigned to sandisk corporation ). with respect to the steering line , first consider the cell / array using cell embodiment 1 , which requires one steering line per column of cells . one possibility is to have this be a continuous global line , i . e . running continuously ( vertically ) through the entire memory array . running through the memory cell sub - array portion poses no obstacles , readily fitting within the existing pitch . however , it may run into obstacles when trying to cross the segment select portions , which bound those sub - arrays . other issues with this approach are the associated large rc time constants ( impacting speed of charging and discharging a long , resistive line ), and the increased array exposure to repetitive disturb . for those reasons , segmentation is also desirable for the steering function . consequently , given that at most one metal line can be run in the pitch of one cell , both global metal bit lines and global steering lines can be shared between pairs of cells . such sharing in the case of a global metal bit line is described in the above referenced u . s . pat . no . 5 , 315 , 541 . it uses a staggered , interlaced segmentation architecture with a transfer network driven by four decode lines per segment pair , thereby allowing each metal bit line to run in the pitch of two cells . similar sharing can also be achieved for the steering lines , an example of which is shown in fig1 ( and this is only one of many possible configurations ). in this embodiment , there are four steering transfer lines driving the transfer matrix , with one global steering line per two cell columns within the segment . when cells are selected , the steering transfer network connects the corresponding local steering lines to unique global steering lines ( e . g . sk connected via sdti 4 )). each selected global steering line is connected in turn by the chunk select ( i . e . column or y - select ) circuitry to the cgre circuitry . those steering lines which are not currently active may be floated or held at ground . if grounded , this raises the possibility of having a subset of the local steering lines , associated with a subset of cells which are not being operated on currently , to be held at ground through appropriate enabling of other sdt lines . an example , referring to fig1 : let sk be the selected global steering line , and sdti 4 be the selected transfer selected line . if it is not desirable to have steering potential applied to unselected cells on the selected row , sdti 3 should be held at ground . however , both sdti 1 and sdti 2 can be turned on allowing the neighboring cells on either side of the selected cell to have grounded steering lines . the reason that it may be undesirable to have unselected cells on selected rows receive high steering potential comes primarily during programming , when channels are conducting . even here however , the bias conditions on unselected cells are interchanged vis a vis source and drain , and see lower drain to source potentials , eliminating parasitic programming . given this , in another embodiment , the four sdt select lines per segment are replaced with a single sdt line , simplifying decoding , and potentially reducing layout area ( although because of narrow cell pitch , area reduction is primarily governed by select transistor and vertical interconnect related dictates ). having floating local steering lines ( e . g . in all the unselected segments ) does raise issues . it is undesirable that any of these lines drift to or are left at such a high potential that they can promote disturbs . however , with properly designed transfer transistors , which remain solidly cut off when unselected , diffusion leakage will maintain floating steering plates at ground ( i . e . at substrate potential ). in addition , by making sure that all actively driven steering lines are fully discharged before isolating them , this will insure that all steering lines are close to ground at all times except when actually selected / driven . in addition to disturbs , large voltages on control gates of unselected cells results in the potential of introducing excessive adjacent cell leakage , impacting proper multi - state setting and sensing . however , this is not an issue for the above - mentioned cell embodiment 1 implementation when voltage sensing is used , by virtue of their poly 3 select function being independent of the sensing related steering function . this allows the select transistor to be throttled down , ( i . e . biased to a minimal turn - on level such as ≦ 5 μamps ), with the state - determining conduction occurring when the control gate reaches or exceeds the floating gate transistor &# 39 ; s turn - on ( or margin ) voltage . this select transistor limited current strategy guarantees that , independent of how strongly conducting the floating gate channel may be , parasitic adjacent cell leakage problems are completely eliminated . the same strategy can be applied to the dual floating gate cell embodiment 2 , as illustrated in fig2 . in this embodiment , the unit memory cell , consisting of two floating gate elements and taking up the pitch of 4 * lambda , has associated with it a single bit line diffusion ( the other bounding bit line diffusion being associated with the neighboring cell ). therefore , global metal bit lines are naturally reduced to one line per 4 * lambda . this also facilitates laying out the segment transistor matrix ( e . g . non - interlaced , fully confined segmentation via a one - to - one segment transistor to local bn + network ), and requires only one segment select line per array segment . the steering transfer matrix is driven by two transfer lines per segment , coupled with global ( metal ) steering lines laid out in the pitch of one line per 4 * lambda . when a transfer line is enabled , it turns on the steering selection transistors for both of the control gates within a cell , for each alternate cell . each of these two control gates within each of the selected cells are driven by a unique global steering line , which , as in the above described cell embodiment 1 case , are driven , in turn , by the segment select and cgre circuitry . also , as in the cell embodiment 1 case , the issue of floating local steering lines exists , with similar resolution . with either cell embodiment , in order to fully capitalize on speed , it is important to make the chunk size as large as possible , maximizing parallelism . because of the low cell read and programming currents inherent to both cell embodiment 1 and 1 a approaches , peak power is not an issue , nor is adjacent cell leakage , which becomes insignificant . consequently , the number of floating gates per chunk which can be simultaneously operated on is limited only by segment decode restrictions . with the segmentation approach described , this allows every fourth floating gate to be addressed and operated on , simultaneously , in both cell variants . in the case of cell embodiment 1 , every fourth diffusion is brought to drain potential , and there are three cells under reversed d / s bias conditions between the drain and the next driven ground . once the first set of cells is completed operation proceeds to the neighboring set . after the fourth such repetition , the full row is completed . in the dual floating gate embodiment 2 case , wherein every other cell is selected , the biasing approach is different . two adjacent diffusions are driven to drain potential followed by two adjacent diffusions driven to ground , with that pattern repeated over and over . in this way global d / s bias is applied in mirrored fashion to every other of the selected cells , resulting in floating gate of odd selected cells being the opposite of the even selected cells . appropriate biases are placed on the global steering lines to satisfy the operation of the targeted floating gates . once done , the bias conditions for both global bit / gnd lines and targeted / untargeted floating gate steering lines are correspondingly interchanged to act on the other floating gate in the selected cells . once finished , similar operation is repeated to the alternate set of cells , completing full row programming in 4 passes . to give an idea of the power of this approach , in a physical row of 1500 floating gate elements , encoded in 8 - state ( three bits per cell ), 375 physical bits or 1125 logical bits are being operated on at one time . assuming it takes nine pulses to complete programming , this gives a programming rate of 125 logical bits or about 16 bytes per programming pulse , plus similar gains in performance achievable for read . existing two - state based flash products , by way of comparison , program around 32 bytes per programming pulse , putting the multi - state approach potentially within a factor of two in write speed . as described above in this portion of this specification , the cell - by - cell column oriented steering approach , realizable in the two source side injection cell embodiments ( standard and dual floating gate embodiments ), increases the performance of high level multi - state significantly , improving both its write and read speed . it achieves this by applying , in parallel , custom steering conditions needed for the particular state of each cell . this offers substantial reduction in the number of individual programming steps needed for write , and permits powerful binary search methodology for read , without having to carry out full sequential search operations . improved performance is further bolstered through increased chunk size , made possible here via the low current source - side injection mechanism , which allows every fourth floating gate element to be operated on , thereby increasing chunk size . although specific examples of array and segmentation architectures have been described , there are a wide variety of alternate options possible which offer similar capabilities . when combining the above concepts with those previously proposed a to d type sensing approaches , which support the greatest density of multi - state or “ logical scaling ” within a cell , this offers a powerful approach to achieving cost reduced , performance competitive mass storage memories , appropriate to the gigabit density generation of products . for example , by achieving effective programming and read rates of about 50 % that of two - state operation , this bridges the gap between multi - state and two - state performance substantially , so much so that when the remaining overhead is included ( i . e . those portions not directly related to chunk read or programming / verify steps ), performance differences from those of two - state can become , for all practical purposes , a non - issue . combining this with the 8 to 16 multi - level ( 3 to 4 bits ) per cell capability , translates to realizing competitively performing ultra - high density mass storage at a fraction of the cost per megabyte ( from one half to one third ), of equivalent binary encoded memory . the independent , bit line oriented steering feature described earlier is , in certain embodiments , exploited to significantly tighten an initially wide erased cell population distribution . in a mass storage memory based on the memory cell / array implementations shown in fig1 and 20 , all cells in a sector or group of sectors are erased simultaneously , by applying a sufficiently high positive bias on the poly 3 erase electrode relative to the poly 2 steering potential . this results in electron tunneling from the poly 1 floating gates to the poly 3 erase anode ( s ), as is described in the aforementioned copending u . s . patent application ser . no . 08 / 607 , 951 . an important feature in this embodiment is the capacitive coupling of the combined channel / drain component . it is designed to have a relatively low coupling to the floating gate as compared to the steering element , thereby having only weak impact with respect to the various cell operations , including erase . for example , if the channel potential during erase is the same as that of poly 2 ( e . g . both at ground ), the channel will provide only a slight assist to the steering gate in the erasing operation , resulting in a slightly stronger erase , while if its potential is more positive than that of the steering gate ( e . g . the steering gate bias is lowered negatively , for example to about − 7v , during erase , with the poly 3 erase level lowered the same amount , while the channel potential remains at ground ), it will contribute slightly less to erase . nevertheless , once the poly 3 is raised to the erasing potential , the main contributor to erasing a cell is the steering element and its potential . this strong dependence on steering gate potential provides a direct means for controlling the degree of erase on each cell , individually , in the column oriented steering embodiment . operation is as follows . at the start of the erase operation , all steering lines are biased at their erase enabling potential ( e . g . − 7v ), and a selected row to be erased ( generally this would be one row of a group of rows targeted for erase ) is pulsed to a sufficiently positive potential ( e . g . 5v ) to start the cell erasing process ( removing a portion of the electrons from some or all of the floating gates ), but which is insufficient to erase any of the cells within that row to the required full erase margin . once pulsing is completed , the row is biased into a read - at - erase - margins condition , and each cell is checked to see whether it has erased to that margin or not . for any cells which have so erased ( as will occur after subsequent erase pulses ), their corresponding steering lines will thereafter be biased into a non - erase - enabling or “ lock - out ” condition ( e . g . at 0v ) for all subsequent erase pulsing to that row during the remainder of that erasing session . this feature can be accomplished by flipping latches associated with each of the bit / steering line columns . if one or more cells are still not sufficiently erased , the erase pulse is repeated , preferably at an incrementally higher poly 3 voltage ( e . g . 0 . 5v higher , although increasing time is used in an alternative embodiment ), again followed by the read - at - erase - margins operation . this pulse / checking loop is repeated as necessary until all cells become sufficiently erased ( or until some other condition such as maximum voltage , pulses , etc . kicks in , at which time defect management options are invoked ), terminating the erase operation to that row . this procedure is then repeated on all the other rows targeted for erase , one row at a time , until all rows / sectors so targeted are erased . in this way all cells in a sector or group of sectors are both sufficiently erased , and confined to a targeted , tight erase distribution . this capability reduces wear under repeated write cycling , thereby increasing endurance . it is especially useful in speeding up multi - state programming operations following erase , since now time does not have to be expended in bringing heavily overerased cells up to that sufficiently erased condition . the drawback of this embodiment is that erasing becomes much more time consuming , replacing potentially one single erase pulse applied to all rows ( or sectors ) simultaneously , with a series of erase pulse / check operations on a row by row basis , since now only a single row can be erased at a time . this approach is most practical when the time associated with erase is hidden , eliminating its impact on write performance . today there are a number of ways in which mass storage systems eliminate erase related performance loss , including erase ahead approaches and dynamic address mapping via ram translation tables . in such systems , a tight erase distribution at the start of write can measurably increase write performance , especially with respect to multi - state . the above discussion assumes that each steering line is uniquely associated with one cell . however , because of layout pitch constraints , especially when implemented in a segmented steering architecture , several cells may share one global steering signal , examples of which are shown in fig1 and 20 , where each pair of cells are associated with one global steering line via steering drive segment transfer select transistors . following are two embodiments utilizing such sharing . one embodiment allows the sharing to take place in each erase operation , erasing all cells in one row simultaneously , as described above . in this case , however , erase lock - out on a group of cells ( or floating gate transistors in the case of dual floating gate cells ) sharing a common steering line can only be invoked when all cells in that group have achieved the required erased state margin . this will result in a fraction of the cells becoming overerased as they wait for the weakest cell in each group to achieve sufficient erasure . for example , if each sharing group consists of four cells , in general three cells will become overerased . fig2 models the impact of this sharing approach on a population of 5000 cells , the erase voltages of which follow a normal distribution with a one - sigma of 0 . 7v . in the case of two - cell sharing , 50 % of the cells will have minimal overerase , and the remainder will follow a normal distribution with a one - sigma of about 1v . comparing this to the original distribution ( i . e . without any lockout ) shows that with lock - out much fewer cells are subjected to overerasure , at any level of overerase ( i . e . they are further up the sigma tail ), and the worst case overerase voltage is about 1 . 3v lower than the original distribution &# 39 ; s worst case overerase of about 4 . 7v . the situation is similar in the case of four - cell sharing , with slightly increased levels of overerase to those of two - cell sharing . a second embodiment takes advantage of the segment level selection capability , thereby completely avoiding the sharing limitation . referring specifically to the previously described embodiments , wherein one global steering line is shared by two local steering lines ( e . g . fig1 and 20 ), the present embodiment exploits the segment steering line addressing capability to only drive one of the two local steering lines in each cell pair ( or half the row &# 39 ; s worth of cells ) during each erase operation . the unaddressed cells &# 39 ; local steering lines are precharged and floated at the non - erase - enabling voltage condition ( e . g . 0v ). once the addressed half row &# 39 ; s worth of cells are taken through their erase / verify / lockout operations to completion , the steering address is shifted to the other , previously unaddressed cell group half , which are then erased to completion , while the first group of cells are maintained in the non - erase - enabling condition . although this approach doubles the total erase time compared to using a single erase pulse for the entire row , it will have no impact to write performance in erase - hidden implementations , while it does maintain the desirably tight erase distribution . in an alternative embodiment , the above controlled overerase methodology is used to write the multi - state data , with the hot electron programming mechanism relegated to the data unconditional preset operation . while optimum write bias conditions and disturb prevention would depend on specific cell and tunneling characteristics , such a tunneling based write approach is made possible by the fundamental cell array architecture , consisting of the independently controllable column steering feature , plus the bit - by - bit lock - out capability of the above disclosed memory concept relating to fig1 and 20 . a variety of alternative embodiments of this invention have been taught , which provide improved performance and cost efficiency for multi - state memory devices and systems . the invention now being fully described , it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the appended claims . all publications and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference . | 6 |
a detailed explanation will be given of an embodiment of the invention in reference to the drawings as follows . a magnetic tape cassette case 10 according to a first embodiment shown in fig1 is capable of accommodating magnetic tape cassettes having at least two kinds of sizes . the accommodating case 10 is capable of accommodating a dlt cassette 80 constituting a large cassette shown by bold lines in the drawing and an lto cassette 90 constituting a small cassette shown by two - dotted chain lines in the drawing . a height dimension of the lto cassette 90 is smaller than that of the dlt cassette 80 . further , the lto cassette 90 is smaller than the dlt cassette 80 in a dimension thereof in a direction of inserting the cassette . the dlt cassette 80 and the lto cassette 90 are formed with recessed portions at the same position when reference faces are constituted by predetermined faces . in this case , recessed portions 80 a and 90 a are formed at the same position of side faces thereof when reference faces thereof are constituted by bottom faces and rear end faces of the cassettes in inserting the cassettes . the recessed portions 80 a and 90 a are inserted with positioning means of a hardware apparatus or the like . the accommodating case 10 is provided with a accommodating portion 11 having an opening 12 capable of bringing in and out the magnetic tape cassettes 80 and 90 and a lid portion 15 connected to the accommodating portion 11 foldably by way of a connecting portion 20 . the accommodating portion 11 is provided with a bottom wall 11 a substantially in a rectangular shape ( substantially in a square shape ), a pair of side walls 11 b and 11 c erected at sides of the bottom wall 11 a opposed to each other and an end wall 11 d erected at a side of the bottom wall 11 a and extended in a direction orthogonal to the side walls 11 b and 11 c . a first locking portion 11 e is provided at aside of the bottom wall 11 a opposed to the side provided with the end wall 11 d . at an inner face of the side wall 11 c on one side , there is provided a positioning projected portion 13 to be fitted to the recessed portion 80 a of the dlt cassette 80 and the recessed portion 90 a of the lto cassette 90 . further , at an inner face of the end wall 11 d , there is provided an auxiliary positioning projected portion 14 which is brought into a recessed portion ( not illustrated ) provided at a front end face of the dlt cassette 80 in the direction of inserting the cassette and is brought into contact with a front end face of the lto cassette 90 in the direction of inserting the cassette . the lid portion 15 is provided with a ceiling wall 15 a having a shape and an area the same as those of the bottom wall 11 a of the accommodating portion 11 . a side of the ceiling wall 15 a is connected to a front end ( upper end ) of the end wall lid of the accommodating portion 11 via the connecting portion 20 . there is provided an end wall , not illustrated , at a side of the ceiling wall 15 a opposed to the side connected to the connecting portion 20 . the end wall is provided with a second locking portion ( not illustrated ) in correspondence with the first locking portion 11 e of the accommodating portion 11 . there are provided side walls 15 b and 15 c at a pair of sides of the ceiling wall 15 a extended in - directions orthogonal to the end wall . further , there is no restriction in modes of the first locking portion lie of the accommodating portion 11 and the second locking portion of the lid portion 15 but there can be exemplified a constitution in which recesses and projections thereof are engaged with each other , a constitution of using a piece of velcro ™ or the like . it is preferable to constitute the first locking portion lie and the second locking portion such that the accommodating portion 11 and the lid portion 15 are capable of being provided with a plurality of engaging portions . for example , there can be constructed a constitution in which at least one of the first locking portion 11 e and the second locking portion is provided with two or more of projected portions and recessed portions . in this case , the connecting portion 20 is formed in a shape of a long strip constituting a long side by a side thereof along an upper end side of end wall 11 d of the accommodating portion 11 . the connecting portion 20 functions as a thin - walled hinge foldable at a plurality of positions thereof . for example , as shown by fig2 there can be formed two pieces of folding lines 20 a and 20 b extended in directions along the long side . when the dlt cassette 80 is contained in the accommodating case 10 having the above - described constitution , the positioning projected portion 13 of the accommodating portion 11 is fitted to the recessed portion 80 a of the dlt cassette 80 to thereby prevent the dlt cassette from playing at inside of the case . meanwhile , the auxiliary positioning projected portion 14 of the accommodating portion 11 is not brought into contact with the surface of the dlt cassette 80 . when the lid portion 15 is folded to the accommodating portion 11 , a folding line is constituted at a portion of the connecting portion 20 on the side of the lid portion 15 . that is , the lid portion 15 is folded by using the folding line 20 a on the side of the lid portion 15 in the folding lines 20 a and 20 b shown in fig2 . then , the ceiling wall 10 a of the lid portion 15 is brought into contact with a ceiling face of the dlt cassette 80 . in this way , by sandwiching the dlt cassette 80 by the ceiling wall 15 a and the bottom wall 11 a , the dlt cassette 80 is restricted from being moved in a height direction ( z direction ) at inside of the case . the dlt cassette 80 is restricted from moving at inside of the case in x - y plane by the positioning projected portion 13 , the side walls 11 b and 11 c and the end wall 11 d of the accommodating portion 11 . meanwhile , when the lto cassette 90 is contained in 10 the accommodating case 10 , the positioning projected portion 13 of the accommodating portion 11 is fitted to the recessed portion 90 a of the cassette 90 and the auxiliary positioning projected portion 14 of the accommodating portion 11 is brought into contact with a surface of the lto cassette 90 to thereby prevent the lto cassette from playing at inside of the case . further , when the lid portion 15 is folded to the accommodating portion 11 , a folding line is constituted at a portion of the connecting portion 20 on the side of the accommodating portion 11 . that is , the lid portion 15 is folded by using the folding line 20 b on the side of the accommodating portion 11 in the folding lines 20 a and 20 b shown in fig2 . then , the ceiling wall 15 a of the lid portion 15 is brought into contact with the ceiling face of the lto cassette 90 . in this way , the lto cassette 90 is sandwiched by the ceiling wall 15 a and the bottom wall 11 a to thereby restrict the lto cassette 90 from moving in the height direction ( z direction ) at inside of the case . the lto cassette 90 is restricted from moving at inside of the case in x - y plane by the positioning projected portion 13 , the side walls 11 b and lic and the auxiliary positioning projected portion 14 of the accommodating portion 11 . according to a accommodating case 30 of a second embodiment shown in fig3 there is provided an expandable and contractable support piece at an inner face of a ceiling wall 35 a . when the dlt cassette is contained at inside of the accommodating case 30 , the ceiling face of the dlt cassette is supported by the support piece 36 in a state of being pressed to contract . when the lto cassette is contained at inside of the accommodating case 30 , the ceiling face of the lto cassette is supported by the support piece 36 in a state of being expanded . a mode of the support piece 36 is not restricted but there can be exemplified a mode comprising an elastic member , or a mode using an expandable and contractable member of a spring or the like . a leaf spring or the like can also be used . further , the invention is not limited to the above - described embodiments but can be modified or changed pertinently . for example , there can be constructed a constitution capable of accommodating three kinds or more of magnetic tape cassettes having different sizes . further , the invention is applicable also to a accommodating case of a magnetic cassette pivotably holding a pair of tape reels at inside of a cassette case . while there has been described in connection with the preferred embodiments of the invention , it will be obvious to those skilled in the art - that various changes and modifications may be made therein without departing from the present invention , and it is aimed , therefore , to cover in the appended claim all such changes and modifications as fall within the true spirit and scope of the invention . as has been explained above , according to a magnetic tape cassette case for accommodating a magnetic tape cassette of the invention , there can be provided the accommodating case for a magnetic tape capable of accommodating the magnetic tape cassettes having different sizes without play . | 6 |
although this invention is applicable to numerous and various types of digital video compression standards , it has been found particularly useful in the environment of the mpeg - 2 standard . therefore , without limiting the applicability of the invention to the mpeg - 2 standard , the invention will be described in such environment . furthermore , while the present invention has been found particularly useful in the environment of video data , and described in such environment , this invention can also be applied to various other types of data , such as but not limited to audio data . in mpeg video decoding , data buffering occurs to maintain a transmission bit rate and a video display rate . pictures vary greatly in the amount of data used to encode them . because of that , the decoding buffer constantly fluctuates with respect to how much data it contains ( buffer fullness ). fig1 shows an example of the fluctuating buffer fullness over time graph with data coming in at a constant bit rate and the buffer read is assumed to be instantaneous . this buffer fullness of the decoding buffer must be carefully monitored to avoid buffer overruns or under runs , because of the adverse impact on video display . to be certain that a given video sequence that is being encoded will not violate the buffer fullness , encoders create a “ virtual buffer ” by employing mathematical equations to determine how much data is entering and leaving a buffer at a given encode rate and at a given buffer size . using an initial buffer fullness , which is the amount of data in the buffer at some starting point , the buffer fullness is continually measured at the completion of each encoded picture . the calculation is made by taking the difference between the initial buffer fullness and the accumulation of the difference of the pictures &# 39 ; actual bit usage and the average of bits per picture , assuming a constant picture target . this calculation is represented as follows n is any number between 0 . 1 and 1 . 0 , e . g ., 0 . 8 , the buffer size is given by the mpeg standard , and e = e +( bits used − ba ) where e is initialized to 0 at start of the encode sequence and is accumulated for the entire video sequence , and ba is average bits per picture . in a video splice , the amount of data that must be used to encode new pictures to be spliced is determined by the state of the virtual buffer at the beginning of the splice ( the start buffer fullness ), and at the end of the splice ( the end buffer fullness ). the spliced pictures must fit into the free number of bits in the buffer precisely . to begin the splice , the users garner the start and end buffer fullness statistics . if encoding of the whole stream is performed concurrently , then the statistics are available from the first pass encode of the video stream . if on the other hand , the encoding of the stream was completed without saving of start and end buffer fullness statistics , then these statistics can be attained by running the encoded stream through a stream analyzer . as is shown in box 10 of fig2 these two parameters , along with the number of new pictures to be encoded and then inserted or spliced into the stream , are passed to the encoder in the second pass encode of the video stream . the encoder translates the buffer fullness and the picture numbers into average picture bits , fig2 box 20 , by converting the change in the number of free bits in the buffer at the start and at the end of splicing and dividing by the number of pictures to splice . these calculations are given by formulas : the change in the average bits per picture based on picture splice is ba ( new ) = ba + ( end bf - start bf ) number of pictures to encode where bf is buffer fullness , ba is the average bits per picture given constant picture target , and ba ( new ) is the change in ba based on pictures to splice . ba is calculated by ba = bit rate ( mbits / sec ) frame rate ( pictures / sec ) as shown in fig2 box 30 , a precise bit allocation for each new picture is calculated by the encoder based on the picture type , group of pictures ( gop ), and other encoding parameters used in bit rate control . in typical ipb encoding , i picture targets are 2 to 5 times larger than p picture targets and 4 to 10 times b picture targets . picture target calculations are based on ba , picture type , and other picture parameters such as picture condition and motion relative to other pictures . to precisely attain these new picture targets fig2 box 40 , the present invention divides the picture by the number of macro blocks in the picture and the number of blocks in the macro block . the picture target is now subdivided into macro block targets target ( mb ) = picture target number of macro blocks the target is further reduced to block targets used to precisely control the number of bits used to encode a picture by target ( blk ) = target ( mb ) number of blocks this result is fed into an apparatus , which guarantees the picture target will not be overrun . such apparatus is described in a related patent disclosure “ a precise bit control apparatus with look - ahead for mpeg encoding ” by john murdock , et al , the entirety of which is incorporated by reference herein . in fig2 box 50 a determination is made whether a target bit size is reached . in the event the target is slightly under run ( it will always be less than or equal to the target , never greater than the target ), as shown in box 60 , padding with zeroes ensures precise target attainment . the formula used is a decision box 70 determines whether there are any more pictures to encode . if there are no more pictures the process terminates with box 90 . however , if there are still more pictures to encode , the process of this invention continuously loops to box 30 to calculate a precise bit allocation for each new picture while there are pictures to be encoded . this newly encoded stream may now be seamlessly spliced into the original stream , occupying the location in the encoded stream of the portion which it replaces at the precise size given by users &# 39 ; input specification . | 7 |
a communication apparatus may include at a final stage of a band control circuit thereof a frame editing circuit that attaches or deletes user identification information , such as a vlan tag , to or from a frame . the band control circuit controls a transmission rate of a frame . in such a case , a problem described below may be likely to occur . since an amount of data of a frame that has undergone a transmission rate control process varies , it is difficult to correctly control a transmission rate of a frame to be transmitted from the communication apparatus . if a communication apparatus includes a frame editing circuit at a front stage of the band control circuit , a problem described below may be likely to occur . types of frames and applications supported by the communication apparatus have been diversified . for example , the frames include asynchronous transfer mode ( atm ) cell , lan frame , ip frame , mpls frame , and provider backbone bridge ( pbb ) frame . layer structure and process content of the frames , and an amount of and structure of data that are to be attached or deleted are different from frame type to frame type . for example , the vlan tag in the lan frame is 4 bytes per tag . the pbb frame has 16 bytes . in order to encapsulate a mac frame of a provider in a mac frame of a client , the pbb frame includes a destination mac address ( 6 bytes ), a transmission source mac address ( 6 bytes ), and the vlan tag ( 4 bytes ). each time a frame is received , the band control circuit checks an upper limit rate set for the destination , and an amount of data that are transmitted up until the present point of time . the band control circuit immediately determines that the upper limit rate is not exceeded if the frame is transmitted . the band control circuit then determines whether to transmit the frame . a complex operation is to be performed by the band control circuit . along with an increase in a traffic amount of packet communications , a demand for faster processing speed is mounting on the band control circuit . under these situations , the band control circuit tends to be a costly circuit . in view of these problems , the band control circuit is implemented in a switch circuit rather than being implemented in each of network if circuits . the switch circuit is a common portion of the communication apparatus and functions as a common circuit having greater versatility without paying particular attention to difference in frame type . this arrangement is effective in terms of costs and operability of the communication apparatus . it is expected that new network applications will be developed from now on . a type of a frame to be processed in a network and an editing process on each frame may respond to such new network applications , and a new function is to be added easily to the communication apparatus . considering the situation , an option described below is more advantageous in terms of costs and operability . more specifically , a new switching circuit having no band control circuit may be developed at low costs first , and later a band control circuit may be additionally implemented in accordance with a frame type and an application to be supported by the apparatus . furthermore , development of an integrated circuit having greater versatility including a high - speed switching circuit and a band control circuit is contemplated for the communication apparatus . in such a case , the integrated circuit may be preferably developed as a general circuit that functions without paying any particular attention to a difference in frame type . it is expected from the overview described above that more communication apparatuses include a frame editing circuit responsive to a frame type arranged at a final stage of a band control circuit that controls a rate of a transmission frame . embodiments of precisely controlling a transmission rate are described below with reference to the drawings . fig4 is a block diagram illustrating a communication apparatus of a first embodiment . fig5 a through 5c illustrate a reception control table , a transmission control table , and a band control table , respectively . fig6 illustrates a format of an in - apparatus frame transferred between an interface ( if ) card and a switching card . the communication apparatus of fig4 transmits and receives a lan frame with a vlan tag . the communication apparatus includes if cards 20 , 30 , and 40 , and a switching card 50 . the communication apparatus also includes a control card ( illustrated in fig2 but not illustrated in fig4 ), and the control card is connected to a control terminal external to the communication apparatus . the if cards 20 , 30 , and 40 are identical to each other in structure , and a port of each card is gigabit ethernet ( registered trademark ) interface and has a data rate of transmission and reception frames of 1 gbps maximum . the if cards 20 , 30 , and 40 , and the switching card 50 are detachable cards . alternatively , the f cards 20 , 30 , and 40 , and the switching card 50 may be a unitary body integrated with a mother board of the communication apparatus . a vlan frame received at a network port of the if card 20 is terminated at a physical / media access control ( phy / mac ) circuit 21 , and then supplied to a reception control circuit 22 . the reception control circuit 22 references the reception control table 23 by a reception port number and a vlan id ( hereinafter referred to as vid ) of a reception frame as an index . the reception control table 23 of fig5 a stores , by a transmission source port number and a vid as an index , v bit , m bit , frame id ( fid ), correction value , destination if card number , and destination port number . the v bit indicates whether the vid is valid or invalid . if v = 0 , the vid is invalid , and if v = 1 , the vid is valid . the m bit indicates whether to multicast a received frame . if the number of transmission destinations of the received frame is one , the m bit is equal to 0 and indicates a unicast transfer . if the number of transmission destinations of the received frame is plural , the m bit is equal to 1 , and indicates a static multicast transfer with point to multi points . if the m bit is equal to 2 , the m bit indicates a multicast transfer of multi points to multi points , which is performed in domain service that is performed through mac address learning . fid is an identifier of a frame to be processed by the communication apparatus , i . e ., fid is a frame identifier . fid is used only within the communication apparatus . the correction value is used for band control , and a unit of the correction value is bit , for example . if the v bit ( valid bit ) of the reception control table 23 is 0 , the reception control circuit 22 discards the received frame for an invalid vid . if the v bit = 1 , the reception control circuit 22 retrieves the frame for a valid vid , and then transfers the retrieved frame to the switching card 50 . the reception control circuit 22 then stores , in an in - apparatus frame header , the m bit , fid , the correction value , the destination if card number , and the destination port number in the reception control table 23 excluding the v bit . fig6 illustrates a format of an in - apparatus frame transferred between the if card and the switching card . the reception control circuit 22 stores the if card number and the port number of the if card having received a lan frame at a transmission source if card number and a transmission source port number in the in - apparatus frame header , respectively . the if card having received the lan frame attaches to the lan frame the in - apparatus frame header to form an in - apparatus frame . the in - apparatus frame is transferred to an if card on a transmitter side via the switching card 50 . the if card on the transmitter side deletes the in - apparatus frame header from the in - apparatus frame , and the lan frame is then output via a port to a network . if the in - apparatus frame received by the switching card 50 has an in - apparatus frame header having m = 0 , the switching circuit 51 determines that the in - apparatus frame is to be unicast transferred . the in - apparatus frame is transferred to a destination card number of the in - apparatus frame header . the band control circuit 52 then performs a band control process on each of combinations of destination if card number and destination port number . if a set transmission rate is exceeded , the band control circuit 52 discards the in - apparatus frame without transferring the in - apparatus frame to the if card . the band control circuit 52 performs the band control process on the transmission rate . the band control circuit 52 periodically references the band control table 53 , and checks the upper limit value of the transmission rate on each of the combinations of transmission source if card number and transmission source port number . the upper limit of the transmission rate is preset on the band control table 53 illustrated in fig5 c with the combination of transmission source if card number and transmission source port number serving as an index . the band control circuit 52 performs the band control process using a token packet method . for example , in 100 mbps , tokens of 100 mbits ( for example , 1 token = 1 bit ) a second are periodically supplied , and accumulated on a token packet . when a frame is received , and then transmitted , an amount of data of the transmission frame ( bit number ) is subtracted from the token packet . if a subtraction operation results in 0 or less in the token packet , the amount of data is not subtracted from the tokens and the frame is discarded . in this way , the transmission frame is controlled not to exceed an upper limit value of 100 mbps . tokens are not accumulated in the token packet limitlessly , but a maximum cumulative amount is typically set on the token packet . when the band control circuit 52 performs the band control process on the transmission frame , the band control circuit 52 adds a correction value stored in the in - apparatus frame header to the bit amount of the reception frame . a transmission control circuit 24 in each if card having received the in - apparatus frame from the switching card 50 references a transmission control table 25 by the destination port number and fid in the in - apparatus frame header as an index . on each of combinations of the destination port number and fid , an edit code for frame editing and vlan tag information for addition setting are preset on the transmission control table 25 of fig5 b . for example , edit code = 0 means that nothing is to be done , edit code = 1 means that a single stack of vlan tag is to be added , edit code = 2 means that two stacks of vlan tags are to be added , edit code = 3 means that a single stack of vlan tag is to be deleted , and edit code = 4 means two stacks of vlan tags are to be deleted . a frame editing circuit 26 performs a frame editing process including adding a vlan tag or deleting a vlan tag in accordance with information of the transmission control table 25 . the lan frame processed by the frame editing circuit 26 is supplied to the transmission control circuit 24 , then is transferred , via phy / mac circuit 21 , to a port having a destination port number in the in - apparatus frame header . according to the embodiment , the vlan tag is an identifier of the frame . alternatively , the vlan tag may be substituted for by one of other identifiers including an mac address , an ip address , and an mpls label . as illustrated in fig4 , a lan frame of vid = 3 received at port # 1 of the if card 20 is transferred to port # 1 of the if card 30 via the switching card 50 . vid = 5 is attached anew to the transmission frame , and is thus transmitted as a two - tag stacked vlan frame . the reception control table 23 of the if card 20 includes items of contents of fig5 a . the transmission control table 25 of the if card 30 includes items of contents of fig5 b . the band control table 53 of the switching card 50 includes items of contents of fig5 c . as illustrated in fig5 a , 0 is set to the m bit in the reception control table 23 with respect to the frame to be unicast transferred . a common id (= 50 ) used in the unicast transfer is set to fid . with the above setting , the frame editing circuit 26 in the if card 30 attaches anew a vlan tag with vid = 5 to a lan frame of vid = 3 received at port # 1 of the if card 20 , thereby increasing an amount of data of the frame by 32 bits . when the band control circuit 52 in the switching card 50 performs the band control process , 32 bits corresponding to the vlan tag are added to the amount of data of the frame in accordance with the correction value attached to the in - apparatus frame header by the if card 20 . for this reason , the rate of the transmission frame output via port # 1 of the if card 30 does not exceed 100 mbps . if the frame editing circuit 26 is present at a stage subsequent to the band control circuit 52 , the in - apparatus frame with the band control correction value in the in - apparatus frame header is transferred . in this way , the band control circuit 52 performs correction control in view of an increase or decrease in the data amount caused by a subsequent frame editing circuit . the band control circuit 52 may perform the band control process precisely on the lan frame transmitted from the communication apparatus . furthermore , the in - apparatus frame header including fid used only within the communication apparatus is attached to the received frame . the switching circuit 51 and the band control circuit 52 in the switching card 50 may thus be developed as a common portion having greater versatility without paying particular attention to frame type difference , such as the lan frame ( with or without vlan tag ), ip frame , and mpls frame . a dedicated if card may be developed to process a frame of a different frame type , or of a different layer structure . fig7 is a block diagram of a communication apparatus of a second embodiment . fig8 a through 8e illustrate a reception control table , a transmission control table , a band control table , and a copy control table . in the second embodiment , a band correction control process is performed for multicast transfer in the communication apparatus . the if card 20 , the if card 30 , and the if card 40 in the second embodiment are identical in configuration to the counterparts in the first embodiment . not that the switching card 50 includes a frame copy control circuit 54 and a copy control table 55 in addition to the switching circuit 51 , the band control circuit 52 , and the band control table 53 . the communication apparatus of fig7 transmits and receives a lan frame with a vlan tag . the communication apparatus includes the if cards 20 , 30 , and 40 , and the switching card 50 . the communication apparatus also includes a control card ( not illustrated ) that is the same as the control card of fig2 , and is connected to a control terminal external to the communication apparatus . the if cards 20 , 30 , and 40 are identical to each other in structure , and a port of each card is gigabit ethernet ( registered trademark ) interface and has a data rate of transmission and reception frames of 1 gbps maximum . the if cards 20 , 30 , and 40 , and the switching card 50 are detachable cards . alternatively the f cards 20 , 30 , and 40 , and the switching card 50 may be a unitary body integrated with a mother board of the communication apparatus . a vlan frame received at a network port of the if card 20 is terminated at the physical / media access control ( phy / mac ) circuit 21 , and then supplied to the reception control circuit 22 . the reception control circuit 22 references the reception control table 23 by a reception port number and a vid of a reception frame as an index . the reception control table 23 of fig8 a stores , by a transmission source port number and a vid as an index , v bit , m bit , fid , correction value , destination if card number , and destination port number . the v bit indicates whether the vid is valid or invalid . if v = 0 , the vid is invalid , and if v = 1 , the vid is valid . the m bit indicates whether to multicast a received frame . if the number of transmission destinations of the received frame is one , the m bit is equal to 0 and indicates a unicast transfer . if the number of transmission destinations of the received frame is plural , the m bit is equal to 1 , and indicates a static multicast transfer with point to multi points . if the m bit is equal to 2 , the m bit indicates a multicast transfer of multi points to multi points , which is performed in domain service that is performed through mac address learning . fid is an identifier of a frame to be processed by the communication apparatus , i . e ., fid is a frame identifier . fid is used only within the communication apparatus . if the m bit is 1 , the correction value , the destination if card number , and the destination port number remain unused . if the v bit ( valid bit ) of the reception control table 23 is 0 , the reception control circuit 22 discards the received frame for an invalid vid . if the v bit = 1 , the reception control circuit 22 retrieves the frame for a valid vid , and then transfers the retrieved frame to the switching card 50 . the reception control circuit 22 then stores , in an in - apparatus frame header , the m bit , and fid in the reception control table 23 excluding the v bit . fig6 illustrates a format of an in - apparatus frame transferred between the if card and the switching card . the reception control circuit 22 stores the if card number and the port number of the if card having received a lan frame at a transmission source if card number and a transmission source port number in the in - apparatus frame header , respectively . the if card having received the lan frame attaches to the lan frame the in - apparatus frame header to form an in - apparatus frame . the in - apparatus frame is transferred to an if card on a transmitter side via the switching card 50 . the if card on the transmitter side deletes the in - apparatus frame header from the in - apparatus frame , and the lan frame is then output via a port to the network . if the in - apparatus frame received by the switching card 50 has an in - apparatus frame header having m = 1 , the switching circuit 51 determines that the in - apparatus frame is to be multicast transferred . the in - apparatus frame is copied under the control of the frame copy control circuit 54 as described below , and the resulting copy is transferred . the band control circuit 52 performs the band control process on each of combinations of destination if card number and destination port number . if a set transmission rate is exceeded , the band control circuit 52 discards the in - apparatus frame without transferring the in - apparatus frame to the if card . the band control circuit 52 performs the band control process on the transmission rate . the band control circuit 52 periodically references the band control table 53 , and checks the upper limit value of the transmission rate on each of the combinations of transmission source if card number and transmission source port number . the upper limit of the transmission rate is preset on the band control table 53 illustrated in fig8 d with the combination of transmission source if card number and transmission source port number serving as an index . the band control circuit 52 performs the band control process using a token packet method . for example , in 100 mbps , tokens of 100 mbits ( for example , 1 token = 1 bit ) a second are periodically supplied , and accumulated on a token packet . when a frame is received , and then transmitted , an amount of data of the transmission frame ( bit number ) is subtracted from the token packet . if a subtraction operation results in 0 or less in the token packet , the amount of data is not subtracted from the tokens and the frame is discarded . in this way , the transmission frame is controlled not to exceed an upper limit value of 100 mbps . tokens are not accumulated in the token packet limitlessly , but a maximum cumulative amount is typically set on the token packet . when the band control circuit 52 performs the band control process on the transmission frame , the band control circuit 52 sums not only the bit amount of the reception frame but also a correction value stored in the in - apparatus frame header . the transmission control circuit 24 in each if card having received the in - apparatus frame from the switching card 50 references the transmission control table 25 by the destination port number and fid in the in - apparatus frame header as an index . on each of combinations of the destination port number and fid , an edit code for frame editing and vlan tag information for addition setting are preset on the transmission control table 25 of fig8 b and 8c . for example , edit code = 0 means that nothing is to be done , edit code = 1 means that a single stack of vlan tag is to be added , edit code = 2 means that two stacks of vlan tags are to be added , edit code = 3 means that a single stack of vlan tag is to be deleted , and edit code = 4 means two stacks of vlan tags are to be deleted . the frame editing circuit 26 performs a frame editing process including adding a vlan tag or deleting a vlan tag in accordance with information of the transmission control table 25 . the lan frame processed by the frame editing circuit 26 is supplied to the phy / mac circuit 21 . the lan frame processed by the frame editing circuit 26 is supplied to the transmission control circuit 24 , then is transferred , via phy / mac circuit 21 , to a port having a destination port number in the in - apparatus frame header . if the m bit in the in - apparatus frame header is “ 1 ” when the in - apparatus frame is received , the switching circuit 51 in the switching card 50 determines that the frame is to be multicast , and starts up the frame copy control circuit 54 . the frame copy control circuit 54 references the copy control table 55 by the if card number and the port number as an index . the copy control table 55 of fig8 e includes a setting field for each port of each if card . set in each field are the presence or absence of a frame copy , and a band control correction value for a frame subsequent to copying . in an x / y format in each setting field , x represents the presence or absence of the frame copy , and the value 0 represents the absence of the frame copy , and the value 1 represents the presence of the frame copy . if the value 1 is set in x , the destination card number and the destination port number in the in - apparatus frame header in the in - apparatus frame subsequent to copying are updated to the card number and the port number in the copy control table 55 . y represents the band control correction value to the in - apparatus frame subsequent to copying . as illustrated in fig7 , a lan frame with vid = 6 received at port # 1 of the if card 20 is multicast in the communication apparatus , thus transferred to port # 1 of the if card 30 and port # 1 of the if card 40 . a tag with vid = 7 is newly added to the frame transmitted to port # 1 of the if card 30 . a tag vid = 6 is deleted from the frame transmitted to port # 1 of the if card 40 . as illustrated in the reception control table 23 of fig8 a , “ 1 ” is set to the m bit in the multicast transfer frame . a common id (= 60 ) used in the same multicast transfer is set to fid . a status “ unused ” is set to the destination if card and the destination port number because no destination is decided yet at this point of time . also , since no destination is decided yet , the status “ unused ” is set to the band control correction value . the transmission control table 25 of the if card 30 includes items of contents of fig8 b . the transmission control table 25 of the if card 40 includes items of contents of fig8 c . the band control table 53 of the switching card 50 includes items of contents of fig8 d . the copy control table 55 of the switching card 50 includes items of contents of fig8 e . the band control table 53 indicates different settings of the transmission rate , i . e ., a transmission rate of 100 mbps for destination port # 1 of a destination card # 2 , and a transmission rate of 200 mbps for destination port # 1 of a destination card # 3 . in this case , the frame copy control circuit 54 references the copy control table 55 by fid of the in - apparatus frame header as an index . the copy control table 55 includes information that is used to copy the in - apparatus frame with fid = 60 . in the copy control table 55 of fig8 e , port # 1 of the if card 30 (# 2 ) and port # 1 of the if card 40 (# 3 ) are set as output destinations . the frame copy control circuit 54 performs the copy process . in the copy process , the destination if card number , the destination port number , and the band control correction value of the copy control table 55 are set in the in - apparatus frame header of the copied in - apparatus frame . subsequent to frame copying , a 32 bit value corresponding to an added vlan tag with vid = 7 is added to the amount of frame data of the in - apparatus frame addressed to port # 1 of the if card 30 . the band control circuit 52 then performs the band control process so that the transmission rate does not exceed 100 mbps . a 32 bit value corresponding to a deleted vlan tag with vid = 6 is subtracted from the amount of frame data of the frame addressed to port # 1 of the if card 40 . the band control circuit 52 thus performs the band control process so that the transmission rate does not exceed 200 mbps . according to the second embodiment , to multicast a frame within the communication apparatus , the frame is copied , a band control correction value is added to the copied frame as an in - apparatus frame , and the in - apparatus frame is then multicast transferred . precise band control is thus performed on the lan frame transmitted from each port of the communication apparatus . fig9 is a block diagram of a communication apparatus of a third embodiment . fig1 a through 10d illustrate a band control table and a transmission control table . fig1 a through 11d illustrate a band control table , a copy control table , and a mac control table . fig1 illustrates a format of an in - apparatus frame transferred between the if card and the switching card . a bridge apparatus learns a transmission source mac address of a lan frame together with the transmission source card number and the transmission source port number into a mac table . when the lan frame having the mac address as a destination mac address is received , the bridge apparatus determines a destination of the received lan frame from content learned from the mac table . since the bridge apparatus determines the destination by learning the content in the mac table , it is difficult to set the band control correction value in the table beforehand as in the first and second embodiments . in the third embodiment , band correction control is preformed on a multi - point service where the mac address is learned ( i . e ., in a multicast transfer of multi points to multi points ). the if cards 20 , 30 , and 40 in the third embodiment are identical in structure to the counterparts in the first embodiment , but note that the switching card 50 includes a mac table control circuit 56 and a mac table 57 in addition to the switching circuit 51 , the band control circuit 52 , the band control table 53 , the frame copy control circuit 54 , and the copy control table 55 . the communication apparatus of fig9 transmits and receives a lan frame with a vlan tag . the communication apparatus includes the if cards 20 , 30 , and 40 , and the switching card 50 . the communication apparatus also includes a control card ( not illustrated ) that is the same as the control card of fig2 , and is connected to a control terminal external to the communication apparatus . the if cards 20 , 30 , and 40 are identical to each other in structure , and a port of each card is gigabit ethernet ( registered trademark ) interface and has a data rate of transmission and reception frames of 1 gbps maximum . the if cards 20 , 30 , and 40 , and the switching card 50 are detachable cards . alternatively the f cards 20 , 30 , and 40 , and the switching card 50 may be a unitary body integrated with a mother board of the communication apparatus . a vlan frame received at a network port of the if card 20 is terminated at the physical / media access control ( phy / mac ) circuit 21 , and then supplied to the reception control circuit 22 . the reception control circuit 22 references the reception control table 23 by a reception port number and a vid of a reception frame as an index . the reception control table 23 of fig1 a stores , by a transmission source port number and a vid as an index , v bit , m bit , fid , correction value , destination if card number , and destination port number . the v bit indicates whether the vid is valid or invalid . if v = 0 , the vid is invalid , and if v = 1 , the vid is valid . the m bit indicates whether to multicast a received frame . if the number of transmission destinations of the received frame is one , the m bit is equal to 0 and indicates a unicast transfer . if the number of transmission destinations of the received frame is plural , the m bit is equal to 1 , and indicates a static multicast transfer with point to multi points . if the m bit is equal to 2 , the m bit indicates a multicast transfer of multi points to multi points , which is performed in domain service that is performed through mac address learning . fid is an identifier of a frame to be processed by the communication apparatus , i . e ., fid is a frame identifier . fid is used only within the communication apparatus . the learning correction value is used for learning band control , and a unit of the learning correction value is bit , for example . if the m bit is 2 , the correction value , the destination if card number , and the destination port number remain unused . if the v bit ( valid bit ) of the reception control table 23 is 0 , the reception control circuit 22 discards the received frame for an invalid vid . if the v bit = 1 , the reception control circuit 22 retrieves the frame for a valid vid , and then transfers the retrieved frame to the switching card 50 . the reception control circuit 22 then stores , in an in - apparatus frame header , the m bit , fid , and learning correction value in the reception control table 23 excluding the v bit . fig1 illustrates a format of an in - apparatus frame transferred between the if card and the switching card . the reception control circuit 22 stores the if card number and the port number of the if card having received a lan frame at a transmission source if card number and a transmission source port number in the in - apparatus frame header , respectively . the reception control circuit 22 further stores a learning band control correction value at the learning correction value of the in - apparatus frame header . the if card having received the lan frame attaches to the lan frame the in - apparatus frame header to form an in - apparatus frame . the in - apparatus frame is transferred to an if card on a transmitter side via the switching card 50 . the if card on the transmitter side deletes the in - apparatus frame header from the in - apparatus frame , and the lan frame is then output via a port to the network . if the in - apparatus frame received by the switching card 50 has an in - apparatus frame header having m = 2 , the switching circuit 51 determines that the in - apparatus frame is to be multicast transferred . the in - apparatus frame is copied under the control of the frame copy control circuit 54 as described below , and the resulting copy is transferred . the band control circuit 52 performs the band control process on each of combinations of destination if card number and destination port number . if a set transmission rate is exceeded , the band control circuit 52 discards the in - apparatus frame without transferring the in - apparatus frame to the if card . the band control circuit 52 performs the band control process on the transmission rate . the band control circuit 52 periodically references the band control table 53 , and checks the upper limit value of the transmission rate on each of the combinations of transmission source if card number and transmission source port number . the upper limit of the transmission rate is preset on the band control table 53 illustrated in fig1 a with the combination of transmission source if card number and transmission source port number serving as an index . the band control circuit 52 performs the band control process using a token packet method . for example , in 100 mbps , tokens of 100 mbits ( for example , 1 token = 1 bit ) a second are periodically supplied , and accumulated on a token packet . when a frame is received , and then transmitted , an amount of data of the transmission frame ( bit number ) is subtracted from the token packet . if a subtraction operation results in 0 or less in the token packet , the amount of data is not subtracted from the tokens and the frame is discarded . in this way , the transmission frame is controlled not to exceed an upper limit value of 100 mbps . tokens are not accumulated in the token packet limitlessly , but a maximum cumulative amount is typically set on the token packet . when the band control circuit 52 performs the band control process on the transmission frame , the band control circuit 52 sums not only the bit amount of the reception frame but also a correction value stored in the in - apparatus frame header . the transmission control circuit 24 in each if card having received the in - apparatus frame from the switching card 50 references the transmission control table 25 by the destination port number and fid in the in - apparatus frame header as an index . on each of combinations of the destination port number and fid , an edit code for frame editing and vlan tag information for addition setting are preset on the transmission control table 25 of fig1 b , 10 c and 10 d . for example , edit code = 0 means that nothing is to be done , edit code = 1 means that a single stack of vlan tag is to be added , edit code = 2 means that two stacks of vlan tags are to be added , edit code = 3 means that a single stack of vlan tag is to be deleted , and edit code = 4 means two stacks of vlan tags are to be deleted . the frame editing circuit 26 performs a frame editing process including adding a vlan tag or deleting a vlan tag in accordance with information of the transmission control table 25 . the lan frame processed by the frame editing circuit 26 is supplied to the transmission control circuit 24 , then is transferred , via phy / mac circuit 21 , to a port having a destination port number in the in - apparatus frame header . if the m bit in the in - apparatus frame header is “ 1 ” when the in - apparatus frame is received , the switching circuit 51 in the switching card 50 determines that the frame is to be multicast , and starts up the frame copy control circuit 54 . the frame copy control circuit 54 references the copy control table 55 by the if card number and the port number as an index . the copy control table 55 of fig1 b includes a setting field for each port of each if card . set in each field are the presence or absence of a frame copy , and a band control correction value for a frame subsequent to copying . in an x / y format in each setting field , x represents the presence or absence of the frame copy , and the value 0 represents the absence of the frame copy , and the value 1 represents the presence of the frame copy . if the value 1 is set in x , the destination card number and the destination port number in the in - apparatus frame header in the in - apparatus frame subsequent to copying are updated to the card number and the port number in the copy control table 55 . y represents the band control correction value to the in - apparatus frame subsequent to copying . as illustrated in fig9 , a lan frame having a destination mac address ( labeled da ) # a , a transmission source mac address ( labeled sa ) # b , and vid = 8 is received via port # 1 of the if card 20 , and port # 1 of the if card 30 and port # 1 of the if card 40 are flooded with the lan frame . a vlan tag with vid = 9 is newly added to a frame to be transmitted via port # 1 of the if card 30 . a vlan tag with vid = 8 is deleted from a frame to be transmitted via port # 1 of the if card 40 , and the frame is thus transmitted without vlan tag . the transmission source mac address # b is learned from the mac table 57 of the switching card 50 . as illustrated in fig1 a , m = 2 is set in the reception control table 23 with respect to a multi point service lan frame as a mac address learning target . the m bit equal to 2 indicates a service , such as the multi point service , where the mac address learning is to be performed . a learning correction value is set in the reception control table 23 . a common id (= 70 ), which is used in the same multi point server , is set for fid . the learning correction value is a correction value that is applied when a frame having that vid is output from a reception port . the learning correction value is newly additionally set to the in - apparatus frame header as illustrated in fig1 . the vlan tag is deleted from the multi point service frame when the multi point service frame is received , and a frame without vlan tag is then transferred within the communication apparatus . a frame format of the multi point service frame having a plurality of input points is consistently used in the communication apparatus so that the band control process of the switching card 50 and the frame editing process of the transmitter side if card are thus facilitated . when the frame with vid = 8 is received , the vlan tag of the frame is deleted by the if card 20 . when the if card 20 receives an in - apparatus frame with fid = 70 from the switching card 50 , and then transfers the in - apparatus frame to port # 1 thereof , vid = 8 is attached to the in - apparatus frame . as illustrated in the reception control table 23 of fig1 a , + 32 is set for the learning correction value . when the switching card 50 receives a frame with m = 2 , the mac table control circuit 56 references the mac table 57 by the transmission source mac address of the received frame as an index . the mac table 57 of fig1 c and 11d stores a learning flag g , if card number , if port number , and learning correction value by the mac address as an index . the learning flag g = 0 indicates an unlearned state , and the port serves as a target of flooding . the learning flag g = 1 indicates a learned state . the if card number and port number learned are stored for the destination if card number and the destination port number in the in - apparatus frame header . this in - apparatus frame is transmitted to the if card of the destination if card number . in the embodiment , the switching card 50 receives the in - apparatus from the if card 20 , and then determines whether the transmission source mac address # b has been learned . at this point of time , however , the mac address # b has not been learned , and the if card number , the if port number , and the learning correction value in the mac table 57 are invalid as illustrated in fig1 c . since the switching circuit 51 floods ports of if cards with the received frame , the frame copy control circuit 54 references the copy control table 55 by fid in the in - apparatus frame header as an index . information used to copy a frame with fid = 70 is stored in the copy control table 55 . three ports , i . e ., port # 1 of the if card 20 (# 1 ), port # 1 of the if card 30 (# 2 ), and port # 1 of the if card 40 (# 3 ), are set as output destinations in the copy control table 55 of fig1 b . the frame copy control circuit 54 performs the copy process . in the copy process , the destination id card number , the destination port number , and the band control correction value of the copy control table 55 are set in the in - apparatus frame header of the copied in - apparatus frame . the frame copy control circuit 54 compares “ the destination card number and the destination port number ” with “ the transmission source card number and the transmission source port number .” if the two pairs of numbers match , the frame copy control circuit 54 does not perform the copy process . this arrangement controls a retransmission of the received frame to the transmission source port . the band control circuit 52 and the band control table 53 perform the band correction control process on the copied lan frame intended for the if card 30 and the if card 40 in accordance with the correction value set in the copy control table 55 . an accurate transmission rate is thus assured . concurrently , the mac table control circuit 56 learns the transmission source mac address # b of the frame into the mac table 57 . the transmission source card number , the transmission source port number , and the learning correction value in the in - apparatus frame header are learned together into the mac table 57 . the mac table 57 includes contents of fig1 d . the mac table control circuit 56 performs an aging process on the mac table 57 periodically . the aging process is an update process on which the data corresponding to the transmission source mac address is deleted in the case that the frame with the transmission source mac address has not been received at intervals of an aging time . after the mac address # b is learned , a lan frame with two stacks of vlan tags with vid = 9 and vid = 8 having the destination mac address # b may be received via port # 1 of the if card 30 . the two stacks of vlan tags with vid = 9 and vid = 8 are deleted from the frame , and a resulting frame without vlan tag is transferred to the switching card 50 . the switching card 50 reads the mac table 57 by the mac address # b as an index . since the mac address # b has been learned , contents of fig1 d written on the mac table 57 are read . the in - apparatus frame of fig1 d is transferred to port # 1 of the if card 20 (# 1 ) without being flooded . the learning correction value (=+ 32 ) of fig1 d is set for the band control correction value or the learning correction value in the in - apparatus frame header of the frame , and is then supplied to the band control circuit 52 as a band control correction value . the band control circuit 52 performs the band correction by adding + 32 as the learning correction value of the mac table 57 of fig1 d to the amount of data of the frame . even if a lan frame with a vlan tag with vid = 8 attached thereto is output via port # 1 of the if card 20 , an accurate transmission rate is assured . even in the multi point service where the mac address is to be learned , a correction value that accounts for a predicted format of a frame to be transmitted is set beforehand as learning information , and is learned in conjunction with the learning of the mac address . an accurate transmission rate is thus assured through the band correction control . when a lan frame of fig3 a and 3b is transferred over a transmission line , a minimum inter - frame gap of 20 bytes takes place between frames . a user or an operator , who operates a network , may wish to account for the gap in band calculation . in such a case , a correction value to be set in each table of fig9 may include a gap of + 20 bytes . in the first through third embodiments , the control card in the communication apparatus automatically calculates the correction value in accordance with setting content as to whether the vlan tag is attached or deleted , and then sets the resulting correction value . in the fourth embodiment , the user or the network operator sets any correction value . more specifically , from the control terminal 14 connected to the control card as illustrated in fig2 , the operator inputs any correction value for each of the if card number , the port number , and the vid using a usable command . the control card then sets the band control correction value in the reception control table 23 , the copy control table 55 , and the mac table 57 . any correction value may be set from outside the communication apparatus , and the band control appropriate for the network specifications is thus performed . the communication apparatus including the frame editing circuit arranged at the final stage of the band control circuit performs an accurate transmission rate control to each of the frame transferred , and may provide improved performance and reliability . all examples and conditional language recited herein are intended for pedagogical purposes to aid the reader in understanding the invention and the concepts contributed by the inventor to furthering the art , and are to be construed as being without limitation to such specifically recited examples and conditions , nor does the organization of such examples in the specification relate to a showing of the superiority and inferiority of the invention . although the embodiments of the present invention have been described in detail , it should be understood that the various changes , substitutions , and alterations could be made hereto without departing from the spirit and scope of the invention . | 7 |
“ channel rate ” is the bit rate of a particular stream , channel , etc ., for example , a single television transmission , a file transfer , a database transaction . “ link rate ” is the bit rate which a network device ( host , router , switch ) can or must sustain over an individual link ( pair of wires , coaxial cable , optical fiber ). this rate is an upper bound on the channel rate . it also has a major influence on the cost of interface hardware and of network protocol hardware and software . “ aggregate rate ” is the maximum total network capacity , expressed as a sum of the link rates for the maximum number of links that may be transmitting simultaneously . for networks implemented as buses or rings or using single frequency wireless broadcasting , the link rate is identical to the aggregate rate . conversely , conventional telephone switching systems provide aggregate rates much higher than the rate of any link . referring now to the figures , fig1 shows a data communications network according to one embodiment of the invention . a first local area network ( lan ) 100 is illustrated , including a host computer or processor 10 which is connected by a wired communications link 11 to a number of stationary access points or base stations 12 , 13 . other base stations 14 can be coupled to the host computer 10 through the base stations 12 , 13 or by an rf link . each one of the base stations 12 , 13 , 14 is coupled by an rf link to a number of remote mobile units 15 . in one embodiment , the remote mobile units 15 are hand - held , battery - operated data terminals or voice communication handsets such as described in u . s . pat . no . 5 , 029 , 183 ; and u . s . ser . no . 08 / 794 , 782 , filed feb . 3 , 1997 , and u . s . ser . no . 09 / 008 , 710 , filed jan . 16 , 1998 , all assigned to the assignee of the instant application and incorporated herein by reference . various other types of remote terminals may be advantageously employed in a system having features of the invention . these remote terminals ordinarily would include data entry facilities such as a magnetic card reader or the like , as well as a display ( or printer ) for indicating to a user information detected , transmitted and / or received by the terminal . in this embodiment used as an illustrative example , there may be from one up to sixty - four of the base stations ( three stations being shown in fig1 ) and up to several hundred of the remote units . of course , the network may be expanded by merely changing the size of address fields and the like in the digital system , as will appear , but a limiting factor is the rf traffic and attendant delays in waiting for a quiet channel . the first lan 100 may be coupled to additional lans 200 , 300 , 400 etc . through controllers such as bridges 50 , 60 , etc . or routers 55 , 65 , 75 , 85 , 95 , 45 , etc . this communications network as seen in fig1 would ordinarily be used in a manufacturing facility , office building complex , warehouse , retail establishment , or like commercial facility or combination of these facilities , where the data - gathering terminals would be used for inventory control in stockroom or receiving / shipping facilities , at checkout ( point of sale ) counters , for reading forms or invoices of the like , for personnel security checking at gates or other checkpoints , at time clocks , for manufacturing or process flow control , and many other such uses . the mobile units 15 may advantageously be hand - held , laser scanning bar - code reader data terminals , or bar - code readers of the ccd or wand type , and may be portable or stationary , rather than hand - held . the mobile units 15 may also be voice communication handsets , pagers , still image or video cameras , or any combination of the foregoing . other types of data gathering devices may be utilized as terminals and use the features of the invention , such as temperature , pressure , or other environmental measuring devices , event counters , voice or sound activated devices , intrusion detectors , etc . more specifically , fig1 illustrates a distributed computing environment or physical layer with clients and servers interconnected through a network link , although additional clients and servers as well as other types of nodes , may be distributed along the network link as well . as used in this specification , the term “ client ” will generally denote a user of some type . the term “ server ” includes any device directed for controlling and coordinating shared usage of a network resource , such as a storage disk or printer . the next osi layer , the data link layer , is directed to the transmission of data streams that enable communication among the nodes at the physical layer , and is commonly referred to as medium access . bits of information are typically arranged in logical units known as frames or envelopes . these envelopes define the protocol which the physical nodes use to intercommunicate . ethernet as defined in ieee standard 802 . 3 , token ring as defined in ieee standard 802 . 5 , and fiber distributed data interface ( fddi ) are examples of popular frame / physical protocols used in networking systems . typically , the envelopes are divided into segments including a header , a trailer , and a data segment . the header includes information such as the physical address of the destination node , which enables any given node to direct a communication to another specified node number . the trailer usually provides some type of parity or other data integrity check to ensure proper data transmission . finally , the data segment includes the information embedded and passed down from the higher osi layers . the network layer builds on the data link layer and is directed to the routing of information packets among the physical nodes . fig2 shows a block diagram of a typical ofdm transceiver known in the prior art . in a transmitter path , binary input data is first encoded using a convolutional encoder 101 . the coding rate is ½ or 24 mbit / s at a quadrature amplitude modulation ( qam ) of 16 bits , or is ¾ or 36 mbit / s at 16 qam . the coding rate is ⅔ or 48 mbit / s at 64 qam , or is ¾ at 54 mbit / s at 64 qam . the coded output data is interleaved at interleaver 102 to get the benefit of time and frequency diversity . after interleaving , the binary data is mapped on qam symbols at a mapper 103 . these qam symbols are then converted from serial to parallel at converter 104 with a block length equal to the number of subcarriers . as previously noted , an ofdm symbol has 48 data subcarriers and 4 carrier pilot subcarriers . for each block of data , the inverse fast fourier transform ( ifft ) 105 is calculated with a size that is larger than the number of subcarriers to make an output spectrum with low enough out - of - band radiation . the ifft output is converted from parallel to serial at converter 106 after which the final ofdm symbol is formed at circuit 107 by adding a cyclic extension and a windowing function . the cyclic extension should be at least two times the expected delay spread in order to reduce intersymbol interference to an acceptable level . the digital data is then applied to a digital to analog converter ( dac ) 108 , and then to an rf transmitter 109 . in the receiver path , a signal is received by rf receiver 110 , and converted into digital data by an analog to digital converter ( adc ) 111 . timing and frequency synchronization is performed at circuit 112 to recover the ofdm signal , and the cyclic extensions are then removed at circuit 113 . a serial to parallel conversion is made at converter 114 , with the block length equal to the number of subcarriers . for each block of data , the fast fourier transform ( fft ) is calculated at calculator 115 . the fft output is converted from parallel to serial at converter 116 after which the qam symbols are demapped at demapper 117 . the interleaving process is reversed at deinterleaver 118 , and the qam symbols are decoded at decoder 119 into the binary output data . fig3 a shows a packet structure of a frame in an ieee 802 . 11a system . a ppdu frame consists of a plcp preamble and signal and data fields as shown . the receiver uses the preamble to acquire the incoming ofdm signal and synchronize a demodulator in the receiver . a plcp header contains information about the psdu from the sending ofdm phy . the plcp preamble and the signal field are always transmitted at 6 mbps , binary phase shift keying ( bpsk )- ofdm modulated using a convolutional encoding rate r = ½ . the plcp preamble field is used to acquire the incoming signal and train and synchronize the receiver . the plcp preamble is depicted in fig5 a and includes ten short symbols ( 1 - 10 ) as defined above , a medium symbol ( ½ ) as defined above , and two long symbols ( 1 , 2 ) as defined above . to repeat , if the duration of each short symbol is 0 . 8 μs , then the medium symbol has a duration of 1 . 6 μs , and each long symbol has a duration of 3 . 2 μs . according to the prior art , the short symbols are used to train the receiver &# 39 ; s automatic gain control ( agc ) and obtain a coarse estimate of the carrier frequency and the channel . the long symbols are used to fine - tune the frequency and channel estimates . twelve subcarriers are used for the short symbols and fifty two subcarriers for the long symbols . the training of an ofdm receiver is typically accomplished over several of the short symbols and typically not less than the duration of two short symbols . the plcp preamble is bpsk - ofdm modulated at 6 mbps . the signal field is a 24 - bit field which contains information about the rate and length of the psdu . the signal field is convolutional encoded rate ½ , bpsk - ofdm modulated . in the field , there are four bits ( r 1 - r 4 ) used to encode the rate , twelve bits are defined for the length , one reserved bit , a parity bit , and six “ 0 ” tail bits . the mandatory data rates for ieee 802 . 11a - compliant systems are 6 mbps , 12 mbps , and 24 mbps . the length field is an unassigned 12 - bit integer that indicates the number of octets in the psdu . the data field contains a 16 bit service field , the psdu , six tail bits , and pad bits . a total of six tail bits containing 0s are appended to the ppdu to ensure that the convolutional encoder is brought back to zero state . the determination of the number of bits in the data field , the number of tail bits , the number of ofdm symbols , and the number of pad bits is defined in the ieee 802 . 11a standard . the data portion of the packet is transmitted at the data rate indicated in the signal field . all the bits transmitted by the ofdm signal in the data field are scrambled using a frame - synchronous 127 - bit sequence generator . scrambling is used to randomize the service , psdu , pad bit , and data patterns , which may contain long strips of binary 1s or 0s . the tail bits are not scrambled . the scrambling polynomial for the ofdm phy is : s ( x )= x − 7 + x − 4 + 1 . the initial state of the scrambler is randomly chosen . prior to scrambling the ppdu frame , the seven least significant bits of the service field are reset to 0 in order to estimate the initial state of the scrambler in the receiver . all information contained in the service , psdu , tail , and pad fields are encoded using a convolutional encoding rate of r = ½ , ⅔ or ¾ corresponding to the desired data rate . convolutional encoding is generated using the following polynomials ; g 0 = 133 8 and g 1 = 171 8 of rate r = ½ . puncture codes are used for the higher data rates . industry standard algorithms , such as the viterbi algorithm , are recommended for decoding . fig3 b shows the ofdm symbol structure . here t is the fft duration and t g is the guard time . each ofdm symbol is windowed by a raised cosine window to reduce the out - of - band radiation . the purpose of the guard time and the cyclic prefix is to prevent both intersymbol interference ( isi ) and intercarrier interference ( ici ). to illustrate this , three subcarriers are depicted in more detail in fig3 c . an ofdm receiver uses only a part of this signal to calculate the fft . in the fft interval , every subcarrier has exactly an integer number of cycles , which ensures orthogonality . for each multipath component , there will be an integer number of cycles within the fft interval , as long as the multipath delay does not exceed the guard time . hence , there is no interference between symbols or between subcarriers . thanks to the guard time and cyclic prefix , the wideband multipath fading is experienced in ofdm as a set of narrowband fading subcarriers without isi or ici . the effect of narrowband fading is that the received subcarriers have different amplitudes , and some may be almost lost in deep fades . in order to become insensitive to such deep fades , forward error correcting coding is used . by proper coding and interleaving across the subcarriers , the ofdm link performance is dependent on the average received power , rather that the worst case lowest power in deep fades . turning to fig4 an arrangement according to the present invention seeks to improve the timing synchronization as performed in block 112 in the prior art ofdm transceiver depicted in fig2 . as will be explained below , this invention achieves timing synchronization over the course of one short symbol in the preamble of a received ofdm signal , thus allowing such functions as , for example , antenna selection , to be performed reliably before the preamble has passed . an incoming ofdm signal is input to an analog - to - digital converter ( a / d ) 201 which is sampled at a frequency f a of 40 million samples per second ( msps ). the sampled signal is applied to an automatic gain controller ( agc ) 202 which supplies iterative feedback to an rf circuit for gain control , and is also applied to an i / q sequencer 202 ′ for non - coherently converting the real intermediate a / d frequency samples into i and q signals having baseband and other frequency components . the i and q signals are passed through low pass filters ( lpf ) 203 , 204 for removing unwanted frequencies and forming a continuous baseband output signal of baseband i / q channels at a 20 mhz rate . filtering at a sampling rate of 40 msps shortens the impulse response . a decimater ( d ) 205 reduces the sampling rate in half to 20 msps by removing every other sample . a buffering circuit 206 holds the short , medium and long symbols of the preamble of the ofdm received signal . the buffer output is applied to a first multiplier 208 to which the gain of an agc circuit 207 is applied . the output of the first multiplier 208 is applied to a second multiplier 209 to which the output of a frequency synchronizer 210 is applied . the output of the second multiplier 209 is applied to a fast fourier transform ( fft ) circuit 211 which performs a fast fourier transform on the incoming signal at 16 or 64 complex point processing at a burst processing rate of 40 mhz . the output of the fft circuit 211 is applied to a third multiplier 212 to which the output of a summer 213 is applied . the output of the third multiplier 212 is applied to a constellation processing circuit 214 operative for performing logical processing of { fraction ( 12 / 52 )} of the subcarriers of the short and long symbols . one output of the constellation processing circuit 214 is applied to a discriminator ( dsl ) 215 of short and long symbols , the output of the discriminator being fed back to the fft circuit 211 to switch between short and long symbols . another output of the constellation processing circuit 214 is applied to a timing synchronizer circuit 216 in accordance with this invention which acquires the ofdm boundaries of the short and long symbols and provides a fractional bin timing pulse for output to the summer 213 , and another output of circuit 214 is fed to the input of the frequency synchronizer 210 . still another output of the constellation processing circuit 214 is applied to an error compensation circuit 217 having a first output to an antenna selection circuit 218 , a second output to the agc circuit 207 for providing iterative feedback to the fft circuit 211 through the multiplier 208 , and a third output to a channel estimation circuit 219 operative for looking at the channel in use and assigning a bin weight for application to the summer 213 . the timing synchronizer 216 of this invention has another output connected to the buffer 206 for adjusting the timing prior to reaching the fft circuit 211 . this is an integer sample timing correction . the final timing adjustment is provided after the fft circuit 211 at the multiplier 212 . this is a fractional sample timing correction . the transformation of a signal x ( i ) for i = 0 , . . . n − 1 x ( k ) = ∑ i = 0 n - 1 x ( i ) exp ( - j ik 2 π / n ) for k = 0 , … n - 1 which takes n discrete samples of the signal x ( i ) to n samples x ( k ) is called the discrete fourier transform ( dft ). the heterodyne principle is that a shift in time of the signal x ( k + m ) is equivalent to a complex exponential multiplication of the transform hence , a time delay is derived at the output of the fft circuit 211 when multiplied by the complex exponential . the time delayed signal represented by the short symbols in the ofdm preamble can be used to estimate the time delay as a common phase rotation . this time estimate represents both the integer sample timing correction and the fractional sample timing correction . hence , without a prior knowledge of frequency or timing , signal samples are buffered and applied to , for example , a 16 point fft . an average differential angle is computed according to the following equation : ( i + 1 j · q ) = 1 10 [ ∑ f = 1 f = 5 smask ( f ) · smask ( f + 1 ) · fft16 f · fft16 f + 1 _ + ∑ f = 10 f = 14 smask ( f ) · smask ( f + 1 ) · fft16 f · fft16 f + 1 _ where smask ( f ) is a masking function of the bits of the short symbols which provides sign information to map all points to the same quadrant , and where each pair of points ( f , f + 1 ) is equally spaced apart . each pairwise combination of the product of one fft for one point and of the conjugate fft for the other point in a respective pair is a bin , and is summed for points 1 - 5 and 10 - 14 . points 6 - 9 represent noise and are not summed . the arctangent of the average differential angle is calculated , and then scaled , in this case , by multiplying by the factor { fraction ( 16 / 360 )} in order to obtain the timing estimate . the integer part represents whole sample offsets or coarse timing , while the fractional part represents fine tuning . more specifically , in contrast to the prior art in which at least the durations of at least two short symbols were used to obtain timing synchronization information , this invention proposes to use only the duration of one short symbol by subjecting the one short symbol to the fourier transform processing of the fft circuit 211 and by calculating the time delay or spread between a sample point and a reference point to determine the phase error . reference is now made to fig5 b which schematically depicts the processing flow during receipt of the preamble of the ofdm signal depicted in fig5 a . during the first short symbol , automatic gain control is performed by the agc 202 of fig4 . during the second short symbol , buffering is performed by the buffer circuit 206 . during the third short symbol , the fourier transform circuit 211 , the constellation processing circuit 214 and the synchronizing circuits 210 , 216 perform their respective functions . this is sufficient time for an antenna to be selected by the selection circuit 218 . the remaining short symbols represent a safety margin to repeat any of the foregoing functions , or to perform new ones . in accordance with this invention , the receiver has two antennas a and b , and it is desired to choose between them . hence , as shown in fig5 b , the second antenna b can be processed during short symbols 3 , 4 and 5 with an overlap during short symbol 3 . the selection between antennas a and b occurs during short symbol 6 . this leaves short symbols 7 - 10 as a safety margin to repeat any of the foregoing functions , or to perform new ones . again , this is accomplished because only the duration of one short symbol is needed to achieve timing synchronization . for completeness , fig5 b depicts that , during the medium symbol , the discrimination between short and long symbols is performed by the dsl circuit 215 . the two long symbols are used to refine timing , frequency and channel estimates . the faster timing synchronization of this invention can be used for other functions different from antenna selection . for example , higher order constellation processing could be performed by circuit 214 , or a longer range could be acquired for the antenna , or the signal to noise ratio generated by the error compensation circuit 217 could be increased . it will be understood that each of the elements described above , or two or more together , also may find a useful application in other types of constructions differing from the types described above . while the invention has been illustrated and described as embodied in timing synchronization in ofdm communications receivers , it is not intended to be limited to the details shown , since various modifications and structural changes may be made without departing in any way from the spirit of the present invention . without further analysis , the foregoing will so fully reveal the gist of the present invention that others can , by applying current knowledge , readily adapt it for various applications without omitting features that , from the standpoint of prior art , fairly constitute essential characteristics of the generic or specific aspects of this invention and , therefore , such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims . what is claimed as new and desired to be protected by letters patent is set forth in the appended claims . | 7 |
fig1 is a diagram of a multimedia playback system 100 according to a first embodiment of the present invention . the system 100 shown in fig1 comprises a demultiplexer ( demux ) 110 , for receiving a data stream and splitting the stream into audio data and video data . the demux 110 is coupled to an audio decoding block 120 having at least fast forward or slow forward functionality . the demux 110 is further coupled to a video decoding block 130 having at least fast forward or slow forward functionality . the demux 110 , the audio decoding block 120 , and the video decoding block 130 are coupled to a decision block 140 . the audio data and video data respectively contain audio playback time information , called the audio presentation time stamp ( a - pts ) and video playback time information , called the video presentation time stamp ( v - pts ). the decision block 140 compares both the a - pts and the v - pts with a determined value of the system 100 , and utilizes the comparison result to set an audio adjustment signal for setting the audio encoding block 120 and a video adjustment signal for setting the video encoding block 130 . the adjustment signals are for instructing the video decoding block 130 and / or the audio decoding block 120 to perform fast forward or slow forward operation . please note that , in the following embodiments , both the audio encoding block 120 and the video decoding block 130 have slow forward and fast forward functionality . this is not a limitation of the present invention , however , and it is possible that each block has various combinations of fast forward and slow forward functionality . the various possible embodiments are detailed below : 1 ) audio decoding block has fast forward and slow forward functionality , and video decoding block only has fast forward functionality . 2 ) audio decoding block has fast forward and slow forward functionality , and video decoding block only has slow forward functionality . 3 ) video decoding block has fast forward and slow forward functionality , and audio decoding block only has fast forward functionality . 4 ) video decoding block has fast forward and slow forward functionality , and audio decoding block only has slow forward functionality . 5 ) audio decoding block only has fast forward functionality , and video decoding block only has fast forward functionality . 6 ) audio decoding block only has slow forward functionality , and video decoding block only has slow forward functionality . in fig1 the determined value of the system 100 is obtained by utilizing a program clock reference ( pcr ). the decision block 140 further comprises an audio decision block 150 and a video decision block 160 . the audio decision block 150 and the video decision block 160 both obtain the pcr directly and the audio decision block 150 utilizes an audio clock in the audio decoding block 120 to clock the pcr . in this embodiment , the pcr of bit 41 ˜ bit 9 is utilized for correction of the system time clock ( stc ). the audio decision block 150 then compares the pcr with the a - pts and determines if a relation between the two values is greater than a determined value . if the inequality is true , the audio decision block 150 will calculate an adjustment signal and output it to the audio decoding block 120 . the audio decision block 150 also utilizes the sampled pcr and the audio clock to create a new reference source clock stc - e for determining the video adjustment signal . an exemplary new reference source clock stc - e is calculated from the following equation when the stc rate is 90 khz : stc - e = pcr sampled ( bit 41 ∼ bit 9 ) + rate stc f s × delta audio output where stc - e represents the determined value , rate stc represents the stc rate , f s represents an audio output sampling frequency , and delta audio output represents the number of audio samples sent after pcr sampled . the video decision block 160 then compares the v - pts with the stc - e for obtaining a video adjustment signal that is then output to the video decoding block 130 . once the audio decoding block 120 and the video decoding block 130 receive the adjustment signals they will respectively decode audio and video streams by fast forwarding or slow forwarding according to the adjustment signals . the audio decision block 150 and video decision block 160 then output an audio adjust complete and a video adjust complete signal to report to the decision block 140 . fig2 is a diagram of a system 200 according to a second embodiment of the present invention . the system 200 comprises a system time clock ( stc ) 270 . the pcr , or a system clock reference ( scr ) is clocked by the stc 270 , thereby updating the stc 270 . the audio decision block 250 then compares the updated stc with the a - pts and the video decision block 260 compares the updated stc with the v - pts to determine if a relation between the stc and the pts is above a certain determined threshold , wherein the threshold can be related to input buffer size or output buffer size of the audio decoding block 220 and video decoding block 230 respectively . if this inequality is found to be true , the decision block 240 will utilize the pts and the stc to determine adjustment signals , for selectively fast forwarding or slow forwarding the audio stream and / or the video stream . once the audio decoding block 220 and the video decoding block 230 have respectively adjusted the audio stream and the video stream , they each send a recognition signal to the decision block 240 . an exemplary audio adjustment signal is determined by the following equation when the decoding rate is 48 khz and the frequency of the stc is 90 khz : audio adjustment factor = ( stc - pts audio ) × freq decode rate stc × n , where pts audio represents the audio playback time information , freq decode represents the audio decoding sampling frequency , rate stc represents the stc rate , and n represents a least sample number for fast forward or slow forward operations . the audio adjustment signal can also be determined by the following equation : audio adjustment factor = ( stc - pts audio ) × freq decode rate stc × n f , where pts audio represents the audio playback time information , freq decode represents the decoding frequency , rate stc represents the stc rate , and n f represents samples decoded of one frame . an exemplary video adjustment signal is determined by the following equation when the video decoding rate is 30 frames per second : video adjustment factor = ( stc - pts video ) × rate decode rate stc × n v , where pts video represents the video playback time information , rate decode represents the video decoding frame rate , rate stc represents the stc rate , and n v represents a least frame number for fast forward or slow forward operations . an advantage of some embodiments of the present invention is that the decoding blocks can separately fast forward or slow forward the data according to the adjustment factor . therefore , if the sync error is significantly large , rather than fast forwarding one data stream and creating a noticeable ‘ jump ’ in transmission , one data stream can be fast forwarded and one data stream can be slow forwarded , to make the effect less significant . a further advantage of some embodiments of the present invention is that either decoding block ( i . e . the audio decoding block or the video decoding block ) can perform the fast forward / slow forward processes , thereby having greater flexibility . fig3 is a diagram of a third embodiment of the system 300 according to the present invention . in fig3 , the desired decision block is only implemented by an audio decision block 350 for adjusting the audio stream . the adjusted audio stream is then utilized to calibrate the video stream by updating a - stc ( audio system time clock ) based on a - pts ( audio presentation time stamp ), and providing the a - stc to the video decoding block 330 as reference . in a situation where the audio stream lags the video stream by a significant amount , the audio decision block 350 can determine to fast forward the audio stream by half the number of frames the audio stream lags by , and then utilize the audio stream timing to slow forward the video stream by the remaining half of the frames . in this way , a large sync error can be made less noticeable to the user . please note that the principle involved in this embodiment is the same as in the above two embodiments . the difference is that the audio decision block 350 only controls the audio stream timing directly , and the audio decoding block 320 then controls the video stream timing . the utilization of the audio decoding block 320 to calibrate the video decoding block 330 is merely one embodiment of the present invention , and is not a limitation . in fig3 , the demux 310 extracts program clock reference ( pcr ), which is sent to the audio decision block 350 , an audio stream sent to the audio decoding block 320 , and a video stream sent to the video decoding block 330 . the audio decoding block 320 receives the a - pts and sends it to the audio decision block 350 . the audio decision block 350 receives the pcr , compares the a - pts with the pcr and utilizes the comparison result to send an adjustment signal to the audio decoding block 320 . the adjustment signal is then utilized to update an audio system time clock ( a - stc ), which is in turn utilized for calibrating the video decoding block 330 . the equation for updating the audio system time clock 370 used by the update unit 370 is the same as that utilized in the embodiment shown in fig2 . fig4 is a diagram of system 400 according to a fourth embodiment of the present invention . this embodiment is largely similar to the embodiment in fig3 , except in this embodiment the decision block is only implemented by a video decision block 460 for adjusting the video stream , and the adjusted video stream is then utilized to calibrate the audio stream . in this embodiment the pcr and a video - sync clock and the pcr is then utilized to update a video system time clock ( v - stc ), which is utilized to calibrate the audio stream . an exemplary equation for updating the v - stc performed in the update unit 470 is as follows : as the operation of this embodiment can be clearly understood by referring to fig4 together with the description of the third embodiment , further detail is omitted for brevity . the slow forward and fast forward operations will now be described in more detail . an advantage of the present invention is that it utilizes the existing fast and slow forward functions of a standard player to achieve the audio / video synchronization goal . this therefore negates the need for complicated circuitry or execution codes . fig5 is a diagram of a first embodiment of the audio decoding block 120 , 220 , 320 . the audio decoding block 120 , 220 , 320 comprises : an input buffer 520 ; an output buffer 540 ; an audio buffer scheduler 510 ; a decoding block 530 ; and an output module 550 . the audio adjustment signal and the a - pts are sent to the audio buffer scheduler 510 . the audio buffer scheduler 510 sets a pointer to indicate which blocks of the input buffer 520 should be sent to the decoding block 530 . the decoding block 530 further receives a - pts information from the audio buffer scheduler . if the audio data precedes the video data , a slow forward operation needs to occur . in this case , the pointer is latched at a certain block , and no more blocks are sent to the decoding block 530 until instructed by the audio buffer scheduler 510 . if the audio data lags the video data , a fast forward operation needs to occur . in this case , the pointer is moved ahead a certain number of blocks , and the currently indicated block is sent to the decoding block 530 . the blocks in between will not be sent to the decoding block 530 . in this way , data can be fast forwarded or slow forwarded . the decoding block 530 sends a decoding complete signal to the audio buffer scheduler 510 after each frame of audio data is decoded . decoded frames are then sent to the output buffer 540 , and then to the output module 550 for being output as the decoded audio signal . the decoding block 530 also sends a - pts information to the output module 550 . the output module 550 optionally passes an audio output clock along with the a - pts to the audio decision block . fig6 is a diagram of a second embodiment of the audio decoding block 120 , 220 , 320 . the second embodiment comprises the same components as the first embodiment ; however , in this embodiment , the audio buffer scheduler 610 sets a pointer to indicate which blocks in the output buffer 640 should be sent to the output module 650 . all blocks in the input buffer 620 are sent to the decoding block 630 , decoded and sent to the output buffer 640 . the output buffer 640 receives a signal from the audio buffer scheduler 610 . if the audio data precedes the video data , a slow forward operation needs to be performed . in this case , the pointer is latched at a certain block , and only released after an instruction by the audio buffer scheduler 610 . at this point , blocks buffered in the output buffer 640 are sent to the output module 650 . if the audio data lags the video data , a fast forward operation needs to be performed . the pointer is moved forward a certain number of blocks , and the block currently indicated by the pointer will be sent to the output module 650 . the previous blocks will not be sent to the output module 650 . please refer to fig7 and fig4 . fig7 is a diagram of a third embodiment of the audio decoding block . please note that this embodiment corresponds to the audio decoding block 420 of the system 400 detailed in fig4 . the a - pts is sent to the audio buffer scheduler 710 , which sets a pointer for determining which blocks in the input buffer 720 will be sent to the decoding block 730 . the decoding block 730 decodes the blocks and sends them to the output buffer 740 . the audio buffer scheduler 710 sets a second pointer for determining which blocks in the output buffer 740 will be sent to the output module 750 . the output module receives v - stc from the update unit 470 shown in fig4 , and sends an adjusted a - pts ( the a - pts corresponding to the current audio output ) to the audio buffer scheduler 710 . fig8 is a diagram of a first embodiment of the video decoding block please note that this embodiment corresponds to the video decoding block 130 , 230 , 430 . the operation of the video decoding block 130 , 230 , 430 is the same as the audio decoding block 120 , 220 , 320 shown in fig6 . the video decoding block 130 , 230 , 430 comprises : an input buffer 820 ; an output buffer 840 ; a video buffer scheduler 810 ; a decoding block 830 ; and an output module 850 . the video buffer scheduler 810 sets a pointer for determining which blocks in the output buffer 840 will be sent to the output module 850 . the operation of the video decoding block 130 , 230 , 430 is the same as the audio decoding block 120 , 220 , 320 shown in fig6 , and further description is therefore omitted for brevity . please refer to fig9 and fig3 . fig9 is a diagram of a second embodiment of the video decoding block , corresponding to the video decoding block 330 shown in fig3 . the video decoding block 330 in fig9 comprises the same components as the video decoding block 130 , 230 , 430 in fig8 , except that , in fig9 , the video buffer scheduler 910 sets a first pointer for indicating which blocks in the input buffer 920 will be sent to the decoding block 930 , and sets a second pointer for determining which blocks in the output buffer 940 will be sent to the output module 950 . the output module receives a - stc from the update unit 370 shown in fig3 , and utilizes the a - stc to send an adjusted v - pts ( the v - pts corresponding to the current video output ) to the video buffer scheduler 910 . please refer to fig1 . fig1 is a diagram of a third embodiment of the video decoding block , corresponding to the video decoding block 130 , 230 , 430 . the operation of the video decoding block 130 , 230 , 430 is the same as the audio decoding block 120 , 220 , 320 shown in fig5 . the video decoding block 130 , 230 , 430 comprises : an input buffer 1020 ; an output buffer 1040 ; a video buffer scheduler 1010 ; a decoding block 1030 ; and an output module 1050 . the video buffer scheduler 1010 sets a pointer for determining which blocks in the input buffer 1020 will be sent to the decoding block 1030 . the operation of the video decoding block 130 , 230 , 430 is the same as the audio decoding block 120 , 220 , 320 shown in fig5 , and further description is therefore omitted for brevity . it is an advantage of the system that the video stream and audio stream can be separately adjusted to achieve synchronization of the data streams . it is a further advantage that the video stream and audio stream can be adjusted simultaneously in order to achieve the smoothest synchronization . those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention . accordingly , the above disclosure should be construed as limited only by the metes and bounds of the appended claims . | 7 |
referring first to fig1 , an embodiment of a vaporizing device 10 is shown , consistent with an embodiment of the present application . devices according to the present application may include a tank 30 and a power component 50 , e . g ., battery component . the tank 30 may be configured to fit within a slot 54 of the power component 50 such that at least a portion of the tank 30 is adjacent to the power component 50 ( see , e . g ., fig1 ). the power component 50 may have a generally ergonomic shape for fitting in the palm of a user &# 39 ; s hand ( see , e . g ., fig2 ). the vaporizing device 10 may have dimensions that allow a user to carry the device in a pocket of a piece of clothing . fig3 a , 3b , and 4 - 6 show different views of an exemplary vaporizing device 20 according to the present disclosure , which may be substantially similar to the vaporizing devices 10 shown fig1 and / or 2 . as shown , the tank 30 may fit into a slot 54 of the power component 50 in an upright position . the dimensions and shape of the slot 54 may generally correspond to the dimensions of the tank 30 , e . g ., both the slot 54 and the tank 30 may be generally cylindrical in shape . when the tank 30 is secured in the slot 54 , the power component 50 may provide power to an atomizer of the tank 30 to generate vapor . the mouthpiece 32 of the tank 30 may extend above the top surface 58 of the power component 50 for access by a user . while fig1 and 3a - 3b each show the portion of the tank 30 within the respective slots 54 as entirely surrounded , in some embodiments the slot 54 of the power component 50 may only partially surround the tank 30 , e . g ., wherein the slot 54 has an opening along the side , such as a slit extending along the entire length or part of the length of the slot 54 . at least a portion of the tank 30 may be at least partially or completely transparent to allow the user to view the liquid contents therein . in some embodiments , the slot 54 may be configured to allow a user to monitor the level of liquid in the tank 30 . for example , the portion of the frame 52 that defines the top of the slot 54 may have a curved or tapered surface 56 , such that the top of the slot 54 may be tapered to expose all or a portion of the length of the tank 30 ( e . g ., exposing all or a portion of a reservoir inside the tank , wherein the reservoir contains the liquid to be vaporized ). in some embodiments , as shown in fig8 , for example , a portion of the tank 30 from the mouthpiece 32 to a middle or lower area 36 of the tank 30 may be visible when the tank 30 is disposed in the slot 54 . the portion of the frame 52 that defines the slot 54 additionally or alternatively may be at least partially or completely transparent so that all or most of the tank 30 can be viewed . the tank 30 may be secured to ( e . g ., locked into ) and electrically connected to the power component 50 by any suitable connection ( s ). for example , the power component 50 may include threads complementary to threads of the tank 30 for connecting the tank 30 to a battery or other power source within the power component 50 . in some embodiments , the tank 30 may include a 510 threaded portion , a ce - 4 type of threaded connection , or a ce - 5 type of threaded connection , and the power component may include complementary threaded portions or types of threaded portions . in some embodiments , a bottom surface of the tank 30 may include a threaded portion that screws into the slot 54 of the power component 50 . for example , the slot 54 of the power component 50 may have a closed bottom to limit displacement of the tank 30 in the slot 54 . the wall 62 at the closed bottom of the slot 54 may include an electrical connector 64 to couple with a connector of the tank 30 , e . g ., for supplying power from the battery to the tank 30 ( e . g ., to the atomizer of the tank ). fig4 shows a top view of the power component of fig3 a and 3b , wherein the bottom wall 62 of the slot includes a standard 510 threaded connector 64 for receiving a tank 30 with a complementary 510 threaded portion . in other embodiments , a side of the tank 30 may have threads complementary to threads in an adjacent surface of the power component 50 . for example , the power component 50 may have a threaded portion along a side surface thereof . tanks suitable for the present disclosure include prefilled tanks and refillable tanks . exemplary tanks may be about 13 mm or about 14 mm in diameter . in some embodiments , the vaporizer device 10 or 20 may include an adapter fixedly or detachably coupled to a surface of the slot 54 for connecting the tank 30 to the power component 50 . the power component 50 may include a battery 76 ( as shown , for example , in fig6 ), e . g ., a rechargeable battery . in some embodiments , for example , the power component 50 may include a lithium - ion battery , e . g ., a 1100 mah or 2200 mah li - ion battery . fig6 shows an exploded view of the power component 50 of fig3 a and 3b , including a frame 52 , a battery / battery cell 76 ( hereinafter battery 76 ), and a cover or shroud 78 ( hereinafter shroud 78 ). the battery 76 may be removable or non - removable . for example , the battery 76 may be fixedly attached to the frame 52 such that the battery 76 may not be removed from the power component 50 . in some embodiments , the frame 52 may completely surround the battery 76 , e . g ., such that a user may not be able to access the battery 76 . the frame 52 may contain various electronic components of the device , such as e . g ., microprocessors , leds , sensors , etc . the shroud 78 also may be removable or non - removable . for example , the shroud 78 may be fixedly attached to the battery 76 and / or frame 52 . in some embodiments , the shroud 78 may be removable , e . g ., allowing a user to exchange shrouds 78 of different colors or designs ( see , e . g ., fig1 and discussion below ). in some embodiments , the battery 76 may provide a voltage ranging from about 1 . 5 v to about 5 . 0 v , such as about 3 . 7 v . in some embodiments , the battery 76 may have a 3 . 7 v output that may be increased to 4 . 2 v , e . g ., with a booster circuit , providing 13 . 6 w . the vaporizer device 10 or 20 may be configured to power an atomizer in the tank 30 down to about 1 . 0ω . the power component 50 may include a power button , e . g ., for activating the battery . for example , the frame 52 may include a power button operably coupled to the battery 76 , such that pressing the power button causes the battery 76 to supply voltage for vaporizing liquid in the tank 30 , e . g ., via a heating element in an atomizer of the tank 30 . additionally or alternatively , the power component 50 may be configured such that pressing one or more portions of the shroud 78 radially inward activates the battery 76 ( e . g ., similar to clicking a computer mouse ). thus , for example , a user may squeeze one or both sides of the shroud 78 while holding the vaporizing device 10 or 20 in his / her hand in order to generate vapor . in some embodiments , the power component 50 may include a port 80 for connection to an external power supply for recharging the battery 76 . for example , the power component 50 may include a usb or micro - usb charging port 80 , e . g ., as shown in fig5 . the port 80 may have any suitable location along the power component 50 , such as , e . g ., the bottom surface 68 , the top surface 58 , the side surface ( opposite the slot 54 for receiving the tank 30 ), the front surface , or the back surface . fig5 shows a bottom view of the power component 50 of fig3 a and 3b , wherein a base portion 66 of the power component 50 , below the slot 54 for the tank 30 , includes a micro - usb connector 82 . a micro - usb cable 84 may be connected to the connector 82 , as shown in fig9 . the power component 50 may include multiple charging ports 80 . vaporizing devices 10 or 20 according to the present disclosure may be configured to stably sit on a desktop or other generally flat surface . in some embodiments , the power component 50 may include one or more leds , e . g ., as indicator lights . when the battery power is at or above a threshold level , the led ( s ) may be one color ( e . g ., white ), and when the battery power drops below the threshold , the led ( s ) may change to a different color ( e . g ., red ). the leds may be lit when the vaporizing device 10 or 20 is activated or may only be lit when the power component 50 is connected to a power supply ( e . g ., via a usb or micro - usb cord ). additionally or alternatively , the leds may be configured to flash . for example , the leds may briefly or continuously flash when the vaporizing device 10 or 20 is turned on or off . the base portion 66 of the power component 50 may be at least partially transparent to a user to see light from leds within ( see , e . g ., fig7 c , 7d , 7e and 9 ). the power component 50 and / or tank 30 may be made of any suitable materials or combination of materials , including , but not limited to , glass , metal , plastics and other polymers and thermopolymers . as mentioned above , in some embodiments , the power component 50 may include a cover or shroud 78 , which may be removable / replaceable from the power component 50 ( as shown in fig1 ). for example , the shroud 78 may be configured to snap onto the power component 50 ( e . g ., snap onto a frame 52 or housing of the power component 50 ), and may be removed by pulling the shroud 78 away from the power component 50 . any other suitable connections for securing the shroud 78 to the power component 50 may be used . the shroud 78 may allow for the power component 50 to have different colors and / or designs , according to the user &# 39 ; s preferences . fig7 a - 7e and 8 - 12 illustrate additional features and characteristics encompassed by the present disclosure . fig7 a and 7c , for example , shows exemplary dimensions of a power component 50 ( 75 mm + 38 mm + 20 mm ). the power component 50 may have any other suitable dimensions . referring to fig1 a and 10b , a comparison of a wand - like vape pen 100 to a vaporizing device 20 of the present disclosure is shown , e . g ., illustrating that embodiments of the present disclosure may have relatively more compact dimensions . the following provides some exemplary features of power components 50 and vaporizing devices 10 or 20 according to the present disclosure . power components 50 and vaporizing devices 10 or 20 according to the present disclosure may include at least one , some , or all of the features listed below . it is understood that additional embodiments and combinations of features are encompassed by the disclosure herein . compact size , fits in the palm of your hand and is easily pocketable — no more wands micro - usb charging port — port is on the side so the unit can be recharged in the upright position 3 . 7 v output — could be increased to 4 . 2 v ( with booster circuit ) providing 13 . 6 w when used with a prefilled tank ( pft ) ( 13 tpm ) replaceable cover — different colors are available ( see , e . g ., fig1 ). the foregoing description is provided to enable any person skilled in the relevant art to practice the various embodiments described herein . various modifications to these embodiments will be readily apparent to those skilled in the relevant art , and generic principles defined herein can be applied to other embodiments . thus , the claims are not intended to be limited to the embodiments shown and described herein , but are to be accorded the full scope consistent with the language of the claims . all structural and functional equivalents to the elements of the various embodiments described throughout this disclosure that are known or later come to be known to those of ordinary skill in the relevant art are expressly incorporated herein by reference and intended to be encompassed by the claims . moreover , nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims . | 7 |
referring to fig1 , a process proposed here is described for creating a mems device having a trench and including electrical elements in the side walls of the trench . subsequently , with reference to fig2 and 3 it is described how this technique can be used to produce a mems device which is an embodiment of the present invention , simply by producing a trench of a different shape which defines a laterally movable element . fig1 is composed of rows ( a ) to ( d ). in each row of the figure , the right part is a top view of a wafer and includes a dashed line . the left part of the row is a cross - sectional view along the corresponding line . the bottom part of fig1 is a key indicating the meaning of the shading used in the figure . the starting point of the method is a ( 100 ) n - type wafer 1 . as shown in fig1 ( a ), short bar - shaped trenches 3 are formed in the wafer 1 using a drie process . the trenches 3 should be slightly deeper than the in - plane structure to be formed . the high aspect - ratio trenches 3 are partially refilled with lpcvd ( low pressure chemical vapor deposition ) polysilicon 5 . then , the poly silicon is thermally oxidized . by volume expansion of the oxidized poly silicon , the trenches are fully refilled and insulated by the sio 2 . this is the stage shown in fig1 ( a ). thermal oxidation is performed and then patterning is performed at the backside of the wafer ( the bottom as shown in representations on the left of fig1 ). then , anisotropic wet etching is performed at the backside until the bottom of sio 2 - refilled trench 3 is exposed . subsequently the wafer is oxidized and patterned at its top side , and p + is selectively doped in regions 7 ( e . g . by ion implantation or pre - deposition ) and then is driven into the top surface ( e . g . by a high temperature process which causes an oxidation on the surface ). then contact holes 9 are opened through the oxide generated in the drive - in process , as shown in fig1 ( b ). using photo - resist as a mask , structural trenches 11 are drie formed in the mems structure . the sio 2 layer at the backside provides the etching stop for the trench etching . the trenches 11 cut across the ends of the sio 2 - refilled trenches 3 and the p + patterns 7 . the device is then placed in a boron rich atmosphere and , under high temperature conditions , boron diffuses into the sidewalls , to form piezoresistors and capacitive electrodes 13 , as shown in fig1 ( c ). since the trenches 11 cuts the ends of the sio 2 - refilled trenches and the p + patterns , adjacent piezoresistors and capacitive electrodes 13 on the sidewall are electrically isolated by a combination of the insulated - trenches 5 and the boron - diffusion - formed p - n junctions along the sidewall . electrical transfer from the sidewall to wafer surface is achieved via the intersection between the regions 7 and 13 . subsequently , aluminium interconnects 15 are formed by deposition followed by a lift - off technique , and the sio 2 layer at the backside is stripped by plasma etching to release the mems structure . the completed structure is shown in fig1 ( d ). we now turn to a use of the method described above for the creation of a mems device which is the embodiment of the invention . the embodiment is shown in perspective view in fig2 , and is an integrated in - plane cantilever with piezoresistive sensing and capacitive actuating elements integrated on trench - sidewalls . the embodiment is formed from a substrate 20 through which a trench 22 is formed to define a cantilever 21 surrounded by a frame 23 . the upper surface of the substrate is thus partitioned into the upper surface of the cantilever 21 and the upper surface of the frame 23 . the mems device is mirror symmetric about the length direction of the cantilever 21 , but in fig2 a nearside portion of the frame 23 is treated as transparent to explain the structure more clearly . the cantilever is free to vibrate in the direction marked in fig2 as the “ lateral moving direction ”, which is within the plane of the upper surface of the cantilever 21 . some portions 25 of the upper surface of the substrate 20 have been doped with p + dopant ( i . e . boron ). during the formation process ( as described above ) some of the doping atoms diffuse into the lateral surfaces of the cantilever 21 and of the cantilever base , where they produce a piezoresistor layer 27 for differential sensing . furthermore , diffusion of the dopant into the trench walls of the frame 23 produces electrostatic actuating plates 29 on the inwardly facing lateral surfaces of the frame for actuation of the cantilever 21 . before the formation of the trench 22 , sio 2 elements 28 were formed within the substrate extending transverse to the surface ( and corresponding to the sio 2 bodies 5 of fig1 ). in the completed mems device of fig2 the piezoresistor layer 27 intersects with some of these sio 2 elements 28 , and is thus divided into separate piezoresistor sensors 25 . similarly , the electrostatic actuation plates intersect with others of the sio 2 elements 28 and are divided into individual actuation electrodes 29 . lateral deflection of the cantilever 21 can be electro - statically driven by the electrodes 29 and measured by the piezorestive sensors 27 on the side walls . this kind of structure with both sensing and actuating functions can be used straightforwardly in many mems applications such as inertial sensors and resonators , etc . the process steps to produce the mems device of fig2 are described as follows with reference to fig3 . items present in both fig2 and 3 are labelled by the same reference numerals . ( 1 ): the starting material for the fabrication process is a 4 - inch ( 100 ) wafer with n - type substrate 20 doped at a level in the range 1 to 5 ω · cm . first , deep trenches 30 perpendicular to the substrate are etched by induction coupled plasma ( icp ) drie ( with alcatel 601e etching system ). the etching depth is 50 μm - deep and 3 . 5 μm - wide . after drie , the by - product polymer compound generated during the drie is stripped by a cleaning sequence as follows : the wafer is wet cleaned with ekc265 solution at 70 ° c . for 30 minutes . then an oxygen - plasma etch of 10 minutes is used for dry cleaning . after the wafer 20 is cleaned , a 300 nm - thick layer of silicon dioxide 31 is thermally grown on it . then the trenches 30 are partly refilled with conformal poly - silicon 33 by lpcvd . the deposition is processed under 630 ° c . for the thickness of 850 nm . the structure at this time is shown in fig3 ( a ) and 3 ( b ), which show respectively cross - sections along the lines a - a ′ and b - b ′ in fig2 . ( 2 ): the trenches 30 are fully refilled and sio 2 - insulated by volume expansion due to oxidization of the poly - silicon 33 . to reduce thermal stress , the oxidation temperature is set as 950 - 1000 ° c . the insulated trench 30 is fully refilled without void throughout the trench cross - section to create sio 2 bodies 28 . during the poly silicon oxidation , a thick sio 2 layer is also formed on both sides of the wafer . after patterning at the backside , tmah anisotropical etching from the backside thins down the substrate under the cantilever regions until the bottom of the insulated trenches 30 is reached . for a 400 μm - thick wafer , the backside etching is about 350 μm in depth . the sio 2 layer covering the front wafer surface can protect the front side from the backside etching . then , the frontside sio 2 is stripped by buffered hf except for the areas of the insulated trenches 30 . the structure at this time is shown in fig3 ( c ) and 3 ( d ), which show respectively cross - sections along the lines a - a ′ and b - b ′ in fig2 . ( 3 ): a 300 nm - thick sio 2 layer is thermally grown on both sides of the wafer . after patterning at the front side , a region 25 of the front of the wafer is heavily doped with boron . as described above with reference to fig2 , the p + regions 25 provide electrical transference from the wafer surface to the sidewalls of the trenches produced later in the fabrication process . either an implantation or a diffusion process can be used for this p + doping . during drive - in , a new layer of sio 2 grows over the doping regions 25 . the heavy doping level is set at a sheet resistance of about 20 ωcm . during the heavy doping , the backside is protected by the existing sio 2 layer 37 . the structure at this time is shown in fig3 ( e ) and 3 ( f ), which show respectively cross - sections along the lines a - a ′ and b - b ′ in fig2 . ( 4 ): contact - holes 38 are opened in the sio 2 layer for the latter aluminum interconnection . then , 5 . 5 μm - wide trenches 22 are produced using an icp process with photo - resist 39 as the mask . this produces the & lt ; 110 & gt ;- oriented cantilever 21 . the trench etching is stopped automatically at the backside sio 2 - layer 37 . these structural trenches 22 are cut across the surface p + areas 25 with the p + cross - sections exposed at the sidewall - surface for later electric transference . the structural trenches 22 also cut cross the previously formed sio 2 - trenches 30 . the oxide 28 filled in the insulated trenches 30 should be partially exposed outside of the trench - sidewalls so as to ensure electric isolation on the trench sidewall . the structure at this time is shown in fig3 ( g ) and 3 ( h ), which show respectively cross - sections along the lines a - a ′ and b - b ′ in fig2 . ( 5 ): the surface cleaning process used in step ( 1 ) is used again for stripping the deposited compound residues generated in the icp process . boron diffusion for the trench sidewalls is performed by placing the device in a boron - rich atmosphere at a predetermined temperature . the wafer surface and backside are protected from diffusion by the existing sio 2 layers 35 , 37 with the exception of the contact holes 38 . the diffusion at the contact holes 38 has little influence as the p + areas are already heavily doped . after boron diffusion on the sidewalls , both piezoresistors 27 and self - testing electrodes 29 are formed on the trench - sidewalls and electrically isolated by the combination of the sio 2 - insulation elements 28 as well as p - n junctions along the sidewalls formed by the boron - diffusion . the electric transference from trench sidewall to wafer surface is simultaneously completed via the overlaps between the sidewall diffusion regions 27 , 29 and the surface p + doping regions 25 . during the drive - in phase of the sidewall diffusion , nitrogen is first introduced and switched to oxygen at the last minutes in order to grow a thin sio 2 layer on the sidewall for surface passivation and protection of the sidewall piezoresistors . the structure at this time is shown in fig3 ( i ) and 3 ( j ), which show respectively cross - sections along the lines a - a ′ and b - b ′ in fig2 . ( 6 ): reactive ion etching ( rie ) is used to remove the thin oxide layer in the contact holes 38 while the relatively thick oxide layer at other areas remains . then aluminum is sputtered onto the structure and patterned with a photoresist lift - off technique to provide interconnections 40 . after aluminum sintering , the cantilever 21 is freed by rie stripping the sio 2 layer 37 from the backside of the wafer . the structure at this time is shown in fig3 ( k ) and 3 ( l ), which show respectively cross - sections along the lines a - a ′ and b - b ′ in fig2 . fig4 shows sem images of a device fabricated as described above . the lower resolution image fig4 ( c ) shows the overall cantilever structure . fig4 ( d ) shows the cantilever base area , and in particular two sio 2 isolation bodies 28 near the base of the cantilever . fig4 ( a ) shows the tip of the cantilever , and fig4 ( b ) shows an intermediate region along the cantilever . both views fig4 ( a ) and 4 ( b ) show further sio 2 isolation bodies 28 . we now turn to experiments characterising the devices pictured in fig4 . firstly , the electrical characteristics of the fabricated devices are evaluated . a negative electrical potential is supplied to the aluminium contacts of the piezo - resistive elements 27 relative to the substrate . as shown in fig5 , the measured linear i - v property of the sidewall piezoresistor elements 27 indicates ohmic contact of the sidewall - to - surface electric transference . the sheet resistivity is about 200ω . the electrical isolation provided by the sio 2 - refilled trenches and the sidewall - diffused p - n junction is also evaluated . a potential difference is applied to two adjacent electrodes 29 , and the current between them is measured . the result is plotted on fig5 , which shows that the breakdown voltage is higher than 50v . such an electrical isolation is good enough for most mems operations . additionally , the electromechanical performance of the fabricated cantilever is characterized . firstly , a static measurement is performed in which a dc voltage is applied to electrostatically actuate the cantilever beam 21 and the piezoresistive response of the piezoresistors 27 is recorded and plotted in fig7 ( a ). as shown in fig7 ( a ), the measured piezoresistive output rises in proportion to the square of the actuating voltage , which agrees well with analytical predictions . secondly , a dynamic test is performed , in which a differential ac voltage signal of 15 ± 10 cos ωt ( v ) is applied to the electrodes 29 , and thus used to drive the cantilever beam . the measured piezoresistive response is plotted in fig7 ( b ), and shows a 3 . 2 mv peak output at a resonant frequency of 96 . 6 khz . these results also match well with analytical predictions ( shown in the dotted line ). the main method steps of the embodiment discussed above in relation to fig3 are summarized in the flow diagram of fig8 . note that the embodiments described above employ both piezoresistive sensor elements and actuator elements . however , the invention is not limited in this respect , and alternative useful devices may be formed in which only one of these two types of elements is formed . an advantage of using both is that it makes possible a self - calibration in which the sensor elements detect a motion caused by the actuator elements , so that the properties of the device can be measured . although only a single embodiment of the invention has been illustrated in detail , many variations are possible within the scope of the invention , as will be clear to a skilled reader . for example , whereas the cantilever 21 of fig2 is arranged for motion in a single direction , in other embodiments the movable portion of the device may be arranged for motion in 2 directions in the plane of the substrate ( e . g . by an appropriate shaping of the trench 22 , and provision of the piezoresistors and actuating electrodes at locations along the trench which respectively sense and produce these two motions ) and / or for motion also in a direction out of the plane of the substrate ( e . g . using motion sensors and / or actuating elements on the surface of the substrate ). in this case , the cantilever may be formed with a more complex configuration , e . g . comprising a comb , beam and / or plate . devices in which the movable portion can be moved in 2 or 3 directions are useful , for example , for multi - axis sensing applications . the design of movable portions which are capable of such motion are known in the literature , and these designs may readily be combined with the techniques disclosed herein for formation of the sensor elements and actuator elements . g . kovacs , n . maluf , k . e . petersen , “ bulk micromachining of silicon ,” proceedings of the ieee , vol . 86 , no . 8 , pp . 1536 - 1551 , 1998 . b . diem , m . t . delaye , f . michel , s . renard , and g . delapoerre , “ soi ( simox ) as a substrate for surface micromachining of single crystalline silicon sensors and actuators ,” in tech . dig . transducers &# 39 ; 93 , yokohama , japan , 1993 , pp . 233 - 236 . k . a . shaw , z . l . zhang , and n . c . macdonald , “ scream i : a single mask , single - crystal silicon , reactive ion etching process for microelectromechanical structures ,” sens . actuators a , 40 , pp . 63 - 70 , 1994 . n . c . macdonald , “ scream microelectromechanical systems ,” microelectronic engineering , 32 , pp . 49 - 73 , 1996 . u . sridhar , h . lau , l . liu , “ trench oxide isolated single crystal silicon micromachined accelerometer ,” in tech . dig . ieee iedm - 1998 , san francisco , calif ., 1998 , pp . 475 - 478 . s . lee , s . park , dong - il cho , y . oh , “ surface / bulk micromachining ( sbm ) process and deep trench oxide isolation method for mems ,” tech . dig . ieee iedm - 1999 , washington d . c ., 1999 , p . 701 - 704 . s . park , j . kim , d . kwak , h . ko , w . carr , j . buss , dong - il cho , “ a new isolation method for single crystal silicon mems and its application to z - axis microgyroscope ,” tech . dig . ieee iedm - 2003 , washington d . c ., 2003 , p . 969 - 972 . j . dong , x . li , y . wang , d . lu , and s . ahat , “ silicon micromachined high - shock accelerometers with a curved - surface - application structure for over - range stop protection and free - mode - resonance depression ,” j . micromech . microeng ., vol . 12 , pp . 742 - 746 , 2002 . a . partridge , j . reynolds , b . w . chui , e . chow , a . fitzgerald , l . zhang , n . maluf , t . kenny , “ a high - performance planar piezoresistive accelerometer ,” j . microelectromech . syst ., vol . 9 , pp . 58 - 66 , 2000 . | 1 |
in the present invention the amino acids are identified by the conventional three - letter abbreviations as indicated below : ______________________________________ alanine ala arginine arg asparagine asn aspartic acid asp cysteine cys glutamic acid glu glycine gly histidine his leucine leu lysine lys methionine met ornithine orn phenylalanine phe proline pro serine ser threonine thr tryptophane trp tyrosine tyr d - tyrosine tyr valine val______________________________________ the present invention relates to highly sensitive fluorescent probes which allow for rapid and precise characterization of neurotensin receptor binding properties on whole cells . the fluorescent compounds of the present invention have the following general formula : ## str3 ## r is a polypeptide moiety which consists essentially of an amino acid sequence selected from the group consisting of : ## str4 ## in accordance with the present invention , each of the amino acid residues identified at positions 1 to 8 may be substituted by lys or orn . further , the amino acid sequence of the polypeptide moiety in accordance with the present invention may be lengthened at the n - or c - terminal as long as the neurotensin - like biological activity is preserved . in accordance with the present invention , the expression neurotensin - like biological activity is intended to mean that the polypeptide induces biological effects similar to those of neurotensin and / or binds with high affinity and selectivity to the neurotensin receptor . r 1 is a fluorophore moiety selected from the group consisting of fluorescein , such as fluorescein isothiocyanate , 5 - carboxy - fluorescein , 6 - carboxy - fluorescein , rhodamine , such as tetramethyl rhodamine isiothiocyanate , blue fluorescent , such as bodipy ™, and texas red . in accordance with the present invention , other fluorophores may be used where neurotensin - like biological activity is preserved . in accordance with the present invention , the fluorophores may be linked to the polypeptide moiety at position ranging from 1 to 8 via a thiocarbamyl bond , where x is sulfur , or a peptide bond , where x is oxygen . the preferred compound in accordance with the present invention is n - fluoresceyl thiocarbamyl - glu 1 ! neurotensin ( n - ftc - glu 1 ! nt ) as shown in fig1 . although there have been previous attempts at conjugating peptides with fluorescein , n - ftc - glu 1 ! nt is the first example of a successful conjugation of fluorescein with the tridecapeptide neurotensin . the salient features of one compound of the present invention are : ( 2 ) the purification of the conjugated compound to approximately 99 % purity allowing for optimal detection sensitivity ; ( 3 ) the similarity of its pharmacological properties with those of the native peptide ; and ( 4 ) the fact that it is 100 % non - toxic and has a demonstrated shelf life of at least one year . the fluorescent peptide compounds of the present invention offer a new , inexpensive and highly sensitive tool for biochemical , pharmacological and anatomical studies of the neurotensin receptor in both brain and peripheral tissues . the present fluorescent probes offer several advantages over the use of radioactive compounds . the compounds of the present invention do not have any of the common drawbacks of radioactive molecules such as short half - life , high cost and slow detection yield ( which may imply weeks of photographic exposure ). further , they compensate for two major shortcomings of current neurotensin radioactive probes : their low specific activity ( which admittedly is higher with iodinated than tritiated ligands , but also entails greater biohazards ) and the fact that they essentially provide static information ( i . e . information that is not applicable to studying living processes in real time ). in addition to providing a non - radioactive approach to the characterization of neurotensin receptors , the fluorescent compounds of the present invention may be used for a number of additional applications unsuited to radioactive probes . these include the following : ( 1 ) these fluorescent compounds may be readily applied to the isolation of neurotensin - receptor expressing cells , using flow cytometric cell - sorting methods . similarly , receptor binding studies may be carried out on whole cells by flow cytometry . ( 2 ) the fluorescent compounds of the present invention may be used for real time visualization of physiological processes ( receptor aggregation , capping and internalization ) using confocal laser microscopy on brain slices or in cell culture preparation . the same technique may be used for distinguishing cell surface with respect to intracellular components . ( 3 ) confocal microscopic visualization of the bound fluorescent compounds may be combined with that of other cell markers ( e . g . biocytin ™, lucifer ™ yellow ) for identification of neurotensin receptors on electro - physiologically recorded cells . it may also be conjugated to the immunocytochemical characterization of the cells and / or compartments harboring the labeled receptors , using appropriate fluorescent - tagged antibodies . in accordance with one embodiment of the present invention , n - ftc - glu 1 ! nt is prepared according to the following procedure . glu 1 ! nt was synthesized by solid phase technique using a scheme based on t - boc chemistry / acid labile amino acid protecting groups . after deprotection of the last n - amino group , acylation was performed by fluorescein isothiocyanate ( fitc , sigma , 6 - fold excess ) in anhydrous dimethylformamide ( dmf ) containing 5 % n , n - diisopropylethylamine ( diea ) for 2 hours at room temperature with stirring . completion of the coupling was ascertained by a ninhydrin colorimetric test . the acyl - peptide - resin intermediate was then extensively washed with dmf and dried in vacuo . it was submitted to hydrogen fluoride cleavage to deprotect amino acid side chains and to cleave the fluorescein thiocarbamyl ( ftc ) peptide from the resin . the ftc - peptide was solubilized in trifluoroacetic acid ( tfa ) and subjected to rotary evaporation in vacuo . it was then purified by preparative high pressure liquid chromatography ( hplc ) on a parsil 10 ods - 3 whatman ™ column ( 10 - um particle size ; 2 . 2 cm × 50 cm ), using a binary solvent system consisting of 0 . 01 % aqueous tfa , ph 2 , 9 and acetonitrile ( ch 3 cn )- 0 . 01 % tfa and an appropriate gradient . elution of the peptide was monitored at 214 nm . collected fractions were readily screened by analytical hplc using both uv and fluorescence detection ( excitation , 338 nm ; emission , 425 nm ), pooled accordingly , evaporated in vacuo to remove ch 3 cn and lyophilized twice . the purified n - ftc glu 1 ! nt was analyzed for homogeneity by analytical hplc on a u bondapak ™ c 18 column ( 10 - um particle ; 0 . 39 cm × 15 cm ) using appropriate linear gradients of 0 . 01 % aqueous tfa , ph 2 . 9 and 0 . 01 % tfa - ch 3 cn and 0 . 01m ammonium acetate and ch 3 cn ( fig3 where the position of glu 1 ! nt and its fluorescent analog ftc glu 1 ! nt are indicated on the profiles ). its amino acid composition was assessed by quantitative amino acid analysis after acidic hydrolysis in vacuo ( 6n hcl , 110 ° c ., 18 h ) and carboxypeptidase y ( cpy ) digestion ( 6 u / 0 . 3 umole , 37 ° c ., 48 h ). the site of attachment of the fluoresceyl derivative molecule to the neurotensin n - terminus was identified as nα - glu 1 . the structure of the fluorescent peptide was confirmed by mass spectral analysis . the degree of homogeneity was determined by u . v . and fluorescence detection to 99 %. the modification of semi - protected neurotensin with fitc yielded a selective incorporation of one mole fitc / mole unprotected peptide . n - ftc - glu 1 ! nt was evaluated to be pure as indicated by a single elution peak from reverse - phase hplc allowing for optimal detection sensitivity ( fig2 ). the molecular weight of n - ftc - glu 1 ! nt is 2080 . the coumpound is freely soluble in distilled water or aqueous buffer , and is stable if protected from light and maintained at 4 ° c . finally , ftc - nt is 100 % non - toxic . the binding of monoiodo 125 i - tyr 3 - neurotensin was performed on purified brain membranes from adult male mice as described previously ( sadoul j . l . et al ., biochem . and biophys . res . comm ., 1984 , 120 ( 1 ): 206 - 213 ). briefly , membranes were incubated with 0 . 1 nm of radiolabeled peptide in the presence of varying concentrations of n - ftc - glu 1 ! nt in 50 mm tris hcl ph 7 . 5 containing 0 . 2 % bovine serum albumin and 1 mm 1 , 10 - phenanthroline . the reaction was carried out for 20 minutes at 22 ° c . and stopped by the addition of 2 ml ice - cold buffer . membranes were then subjected to immediate filtration over gelman ™- filters ( millipore ™) under vacuum using a millipore ™ filtration apparatus . they were then thoroughly washed and their radioactivity content was measured in a gamma counter . the data were expressed as the percentage of specific binding of the radioligand in the absence of competitor . ic 50 values were obtained graphically and then corrected for the occupancy by the labeled ligand to obtain k i values . the k i values presented are the geometric mean anti - log of averaged log ( k i ) values !± sem . the data were analyzed on an ibm / xt microcomputer using ebda / ligang programs . as can be seen in fig4 the fluorescent analogue completely displaces specific 125 i - tyr 3 - neurotensin binding in a dose dependent manner . scatchard analysis of the data indicates that the binding is virtually the same as that of native neurotensin with an ic 50 of 0 . 55 nm and a pseudo - hill coefficient of approximately 1 . in vitro labeling of neurotensin receptors on rat brain tissue sections rats were sacrificed by decapitation , the brains were rapidly removed , blocked in the coronal plane and frozen at - 40 ° c . 25 μm - thick frozen sections of the substantia nigra were cut on a cryostat and incubated with 10 - 4 - 10 - 6 m fluoro - neurotensin diluted in binding buffer ( ph 7 . 4 ). the incubations were performed at 4 ° c . in the dark for 60 minutes to allow for equilibration , after which the sections were rapidly rinsed in phosphate - buffered - saline ( 4 × 60 seconds each ), dipped in double - distilled water , and air dried under a cool stream of air . the distribution of the fluorescent labeling was examined under a leica diaplan ™ microscope using a high pressure 100 - w mercury lamp and the appropriate dichroic filter combinations for excitation / emission of fluorescein ( 485 / 520 nm ). controls for these experiments included : ( 1 ) examination of sections incubated in the absence of the fluorescent ligand to determine background autofluorescence , and in the presence of a 1000 - fold excess of unlabeled ligand for the determination of the non - specific binding ; and ( 2 ) examination of regions of the nervous system known to be devoid of neurotensin receptors . the anatomical distribution of specifically bound fluorescent ligand in the ventral midbrain tegmentum is illustrated in fig5 . in the substantia nigra pars compacta the label is seen to be selectively accumulated over nerve cell bodies and proximal dendrites . the labeled neurons are ovoid and fusiform in shape with their long axis oriented parallel to the dorsal surface of the pars reticulata . in the latter , the label is mainly confined to a few scattered perikaria , however several labeled processes are seen to radiate from the cells in the pars compacta . in the ventral tegmental area , the labeling is intense and associated with both nerve cell bodies and surrounding neuropil . in the parabrachial pigmentous division , the labeling is interrupted by areas devoid of label corresponding to the trans - tegmental fiber bundles . the fluorescent labeling was no longer apparent in sections incubated with an excess of unlabeled neurotensin . no autofluorescence was observed except a few orange spots in some cells , typical of lipofuscin aggregates . hybridomas cells ( sn6 ) were produced by the fusion of embryonic septal cells with murine neuroblastoma and generously provided by hammond et al . ( science , december 1986 , 234 : 1237 - 1240 ). sn cells were grown in petri dishes ( 100 mm 2 ) in dubelcco &# 39 ; s modified eagle &# 39 ; s medium ( dmem ) containing 44 mm nahco 3 and 10 % fetal calf serum ( gibco brl ) in a humidified atmosphere of 90 % air , 10 % co 2 at 37 ° c . for flow cytometry , the cells ( 1 × 10 6 cell / 0 . 1 ml ) were washed in pbs and incubated with various concentrations of fluoro - neurotensin in hepes - tris - buffer , ph 7 . 4 , in the presence ( non - specific ) or the absence ( total binding ) of a 100 - fold excess of unlabeled neurotensin . after incubation at 40 ° c . or 20 ° c . for 1 hour , the cells were washed and analyzed with a becton - dickinson ™ facscan flow cytometer and consort 30 software . flow cytometric histograms of n - ftc - glu 1 ! nt binding to sn6 cholinergic hybrid cells are illustrated in fig6 . the majority ( 97 . 4 %) of the cells displayed specific fluoro - neurotensin binding at both 4 ° c . and 20 ° c . saturation of the binding was both time and temperature dependent . maximal binding densities were higher at 4 ° c . than at 20 ° c ., presumably reflecting a down regulation of cell surface receptors subsequent to internalization . confocal microscopic visualization of neurotensin binding sites on cholinergic hybrid cells . sn6 cholinergic hybrid cells were incubated with n - ftc - glu 1 ! nt , under the same conditions as above and the distribution of bound fluorescent molecules was analyzed by confocal microscopy . confocal imaging was performed with a leica ™ confocal laser scanning microscope configured with a leica diaplan ™ inverted microscope ( equipped with a 40 × npl oil immersion fluotar objective of 1 . 30 numerical aperture ), an argon ion laser ( 488 nm ) with an output power of 2 - 50 mw , and a vme bus with an mc 68020 / 68881 ™ computer system integrated to an optical disc for image storage . all image generating and processing operations were performed on a leica ™ confocal laser microscope software . optical scanning images ( 512 × 512 pixels ) of cultured cells were made at 0 . 1 μm intervals for a total of 26 sections per scanning sequence . from this data volume , a single composite image of each cell was generated using extended focus image construction . confocal laser microscopic examination of cells incubated with fluoro - neurotensin at 4 ° c . showed prominent staining of the cell borders , suggesting confinement of the label to the cell membrane . upon warming of these cells up to 37 ° c . for 10 minutes , the surface fluorescence intensity diminished and multiple small , bright fluorescent particles appeared in the cytoplasm . after 30 min at 37 ° c ., these fluorescent endosome - like elements accumulated and formed a perinuclear ring as illustrated in fig2 . while the invention has been described with particular reference to the illustrated embodiment , it will be understood that numerous modifications thereto will appear to those skilled in the art . accordingly , the above description and accompanying drawings should be taken as illustrative of the invention and not in a limiting sense . | 2 |
the embodiments of the present invention are described with reference to the drawings . fig2 a , 2 b and 2 c are sectional views of an ic substrate formed with over voltage protection functions according to an embodiment of the present invention . as shown in fig2 a , a first conductor layer is formed to be a grounding conductor layer ( 23 ) on a substrate ( 22 ). the first conductor layer is formed on a lower surface ( 22 b ) of the substrate and extends through the substrate to its upper surface ( 22 a ). one or more terminals ( 27 ) are formed on the upper surface of the substrate . as shown in fig2 b , one or more variable resistance material layers ( 24 ) are formed to overlay the terminals of the grounding conductor layer ( 23 ) so as to form connection with the grounding conductor layer . in addition , a plurality of second conductor layers ( 21 ) are formed to be upper electrodes . the second conductor layers overlay on the variable resistance material layers ( 24 ) so as to form connection with each of the variable resistance material layers . fig2 c is a sectional view of an ic chip ( 20 ) disposed on the substrate . a chip ( 20 ) is connected with the upper electrodes ( 21 ) by soldering , and a protection layer ( 25 ) is added to the chip to prevent from dust and moisture . fig2 d is a top view of the invention in fig2 a . fig2 e is a top view of the invention in fig2 b . fig3 shows another embodiment of connecting an ic chip with the upper electrodes by wire bonding . a first conductor layer is formed to be a grounding conductor layer ( 33 ) on a substrate ( 32 ). the first conductor layer is formed on a lower surface ( 32 b ) of the substrate and extends through the substrate to its upper surface ( 32 a ). one or more terminals are formed on the upper surface of the substrate , one or more variable resistance material layers ( 34 ) are formed to overlay the terminals of the grounding conductor layer ( 33 ) so as to form connection with the grounding conductor layer . in addition , a plurality of second conductor layers ( 31 ) formed to be upper electrodes . the second conductor layers overlay on the variable resistance material layers ( 34 ) so as to form connection with each of the variable resistance material layers . a chip ( 30 ) is connected with the upper electrodes ( 31 ) wire bonding ( 38 ) and a protection layer ( 35 ) is added to the chip ( 30 ) to prevent from dust and moisture . fig4 is a sectional view of an ic substrate with over voltage protection functions according to another embodiment of the present invention . as shown in fig4 , one or more variable resistance material layers ( 44 ) are formed on a substrate . the variable resistance material layers are disposed on the lower surface ( 42 b ) of the substrate . a grounding conductor layer ( 43 ) is formed to be a grounding terminal . the grounding terminal is disposed on the lower surface of the substrate and extends to overlay on each of the variable resistance material layers . a plurality of conductor layers ( 41 ) are formed to be electrodes . the conductor layers are disposed on the upper surface ( 42 a ) of the substrate , and extend through the substrate to its lower surface so as to form connection with each of the variable resistance material layers . a chip ( 40 ) is connected with the conductor layers ( 41 ) by soldering at ( 48 ). fig5 is a sectional view of an ic substrate with over voltage protection functions according to further another embodiment of the present invention . as shown in fig5 , a grounding conductor layer ( 53 ) is formed on a substrate to be a grounding terminal . the grounding terminal is disposed on the lower surface ( 52 b ) of the substrate . one or more variable resistance material layers ( 54 ) are disposed through the substrate and are connected with the grounding conductor layer . a plurality of conductor layers ( 51 ) are formed to be electrode terminals . each of the conductor layers are disposed on the upper surface ( 52 a ) of the substrate , and overlays each of the variable resistance material layers and is connected with them . when a surge pulse occurs , the energy of the surge pulse will enter the electrode terminals ( 51 ) to propagate to the grounding terminal ( 53 ) through the variable resistance material layers ( 54 ). because the nature of the variable resistance materials and its structure , the energy of the surge pulse will be released evenly to the grounding lines and thus , the ic device ( 50 ) will not be damaged and the object to protect the ic device is achieved . fig6 a and 6 b are top views of a multi - layer ic substrate formed with over voltage protection functions according to an embodiment of the present invention . as shown in fig6 a , one or more grounding conductor layers ( 83 ) are formed on a first substrate ( 821 ) to be grounding terminals , which extend to a upper surface ( 821 a ) of the first substrate and is disposed on the lower surface ( 821 b ) of the first substrate , thereby forming one or more terminals ( 87 ) on the upper surface of the first substrate . one or more variable resistance material layer ( 84 ) are formed on the first substrate ( 821 ) and overlay the terminals of grounding conductor layers ( 83 ) appeared on the substrate and are connected with each of the grounding conductor layers . a plurality of first conductor layers ( 811 ) are formed on the upper surface of the first substrate ( 821 ). each of the conductor layers ( 811 ) is disposed on the substrate and overlays on each of the variable resistance material layers ( 84 ), so as to form an electrical connection with each of the variable resistance material layers . the plurality of first conductor layers ( 811 ) extend through the first substrate ( 821 ), and terminals ( 87 ) of the first conductor layer ( 811 ) appear on the upper and lower surfaces of the first substrate ( 821 ). as shown in fig6 b , a plurality of second conductor layers ( 812 ) are formed on a second substrate ( 822 ) to be electrode terminals . the plurality of second conductor layers extend through the second substrate ( 822 ), and terminals ( 87 ) of the second conductor layer appear on the upper surface ( 822 a ) of the second substrate ( 822 ). the second substrate ( 822 ) is disposed on the upper surface of the first substrate ( 821 ), wherein the first conductor layers ( 811 ) are electrically connected with the second conductor layers ( 812 ). in fig6 b , an ic chip ( 80 ) is disposed on the second substrate ( 822 ), and is connected with the second conductor layers by soldering at ( 88 ). a protection layer ( 85 ) is added to the second substrate . fig7 a , 7 b and 7 c are sectional views of forming a multi - layer ic substrate formed with over voltage protection functions according to an embodiment of the present invention . as shown in fig7 a , a plurality of first conductor layers ( 611 ) are formed on a first substrate ( 621 ). each of the first conductor layers ( 611 ) is disposed through the first substrate , and terminals of the conductor layer appear on the upper surface ( 621 a ) and lower surface ( 621 b ) of the first substrate ( 621 ). a plurality of second conductor layers ( 612 ) are formed on a second substrate ( 622 ). each of the second conductor layers ( 612 ) is disposed through the second substrate ( 622 ), and terminals of the conductor layer ( 612 ) appear on the upper surface ( 622 a ) and lower surface ( 622 b ) of the second substrate ( 622 ). holes are formed in the second substrate ( 622 ) and filled with one or more variable resistance material layers ( 64 ). the variable resistance material layer ( 64 ) is disposed through the second substrate ( 622 ). terminals of the variable resistance material layers appear on the upper surface of the second substrate . a grounding conductor layer ( 63 ) is formed on the second substrate ( 622 ) to be a grounding terminal , which is disposed on the lower surface of the second substrate . a plurality of third conductor layers ( 613 ) are formed on a third substrate ( 623 ) to be electrode terminals . the plurality of third conductor layers are disposed through the third substrate and on the upper ( 623 a ) and lower surfaces ( 623 b ) of the third substrate . as shown in fig7 b , the second substrate ( 622 ) overlays the first substrate ( 621 ). the lower portion of the variable resistance material layers ( 64 ) is connected with the grounding conductor layer ( 63 ). the terminals ( 612 ) of the second conductor layer on the lower surface of the second substrate are connected with the terminals ( 611 ) of the first conductor layer on the upper surface of the first substrate ( 621 ). the third substrate ( 623 ) overlays the second substrate ( 622 ). the third conductor layer ( 613 ) is connected with the variable resistance material layer ( 64 ) and the terminals ( 612 ) on the upper surface of the second conductor layer ( 612 ), respectively . as shown in fig7 c , an ic chip ( 60 ) is disposed on the third substrate ( 623 ). the chip ( 60 ) is connected with the upper electrodes by soldering . a protection layer ( 65 ) is added to prevent from dust and moisture . please note that the variable resistance material layers can be made of non - linear resistance materials . fig8 a , 8 b , 8 c , 8 d and 8 e are sectional views of a ball grid array ( bga ) ic package formed with over voltage protection functions according to an embodiment of the present invention . fig8 f is a top view of a bga ic package formed with over voltage protection functions according to an embodiment of the present invention . as shown in fig8 a , a plurality of grounding conductor layers ( 731 a , 731 b , 731 c ) are formed on a bga ic package to be grounding terminals . each of the terminals is disposed on the surface of the bga ic package . as shown in fig8 b and 8 f , one or more variable resistance material layers ( 74 ) are formed on the plurality of grounding conductor layers ( 731 a , 731 b ). each of the variable resistance material layers is disposed on the terminals of the grounding conductor layers ( 731 a , 731 b ) and is connected with each of the grounding conductor layers . as shown in fig8 c , a plurality of variable resistance material layers ( 74 ) are connected with electrode terminals ( 71 ) and grounding conductor layers ( 731 a , 731 b ). as shown in fig8 d , a second protective layer ( 76 ) is disposed on the electrode terminals and the variable resistance materials layers . fig8 e is a sectional view of an embodiment of the present invention after solders are added on the electrode terminals and the grounding conductor layers . fig9 a and 9 b are sectional views of the ic substrate with over voltage protection functions according to an embodiment of the present invention . as shown in fig9 a , a plurality of grounding conductor layers ( 93 ) are formed on a substrate ( 92 ). one or more variable resistance material layers ( 94 ) are formed on the plurality of grounding conductor layers ( 93 ). each of the variable resistance material layers is disposed on the grounding conductor layers ( 93 ) and is connected with each of the grounding conductor layers . a plurality of variable resistance materials layers ( 94 ) are connected with electrode terminals ( 91 ) and the grounding conductor layers ( 93 ). a protection layer ( 95 ) is formed as a chamber by the upper half and the bottom half . the substrate ( 92 ) is disposed in the bottom half of the protection layer ( 95 ). a plurality of electrodes ( 96 ) are disposed on the sidewalls of the bottom half of the protection layer . the plurality of electrodes ( 96 ) are connected with the electrode terminals ( 91 ) by wire bonding ( 99 ). as shown in fig9 b , a chip ( 90 ) is disposed over the substrate and is connected with the electrode terminals . the upper half of the protection layer is connected with the bottom half of the protection layer to form the ic substrate . fig1 a , 10 b , 10 c , 10 d , 10 e and 10 f are sectional views of an ic substrate formed with over voltage protection functions according to an embodiment of the present invention . according to an embodiment of the present invention , a method for forming an ic substrate with over voltage protection functions comprises the following steps . as shown in fig1 a and 10 b , one or more desired holes are formed in the substrate ( 102 ) by laser or punching . as shown in fig1 c , the holes are filled variable resistance material layers ( 104 ). as shown in fig1 d , a lower electrode ( 103 ) is formed on the substrate . the lower electrode ( 103 ) overlays each of the variable resistance material layers ( 104 ) and is connected with the variable resistance material layers ( 104 ). as shown in fig1 e , a plurality of upper electrodes ( 101 ) are formed on the upper surface ( 102 a ) of the substrate ( 102 ). said upper electrodes ( 101 ) overlay each of the variable resistance material layers ( 104 ) and are connected with the variable resistance material layers ( 104 ). said upper electrodes and lower electrodes are formed by printing or metal foil pressing . fig1 f is a sectional view of an ic chip ( 100 ) disposed on the substrate ( 102 ). although the invention has been disclosed in terms of preferred embodiments , the disclosure is not intended to limit the invention . the invention still can be modified or varied by persons skilled in the art without departing from the scope and spirit of the invention which is determined by the claims below . | 7 |
major elements of the invention are indicated in the drawings by numerals as follows : referring now to the drawings wherein like reference numerals designate identical or corresponding parts throughout the several views and more particularly to fig1 wherein the system and method of the present invention are illustrated . a dehydrated hydrocarbon fluid mixture gas stream inlet which contains high levels of carbon dioxide flows by way of inlet gas stream 14 and enters an inlet cross heat exchanger 16 for conditioning . the resulting cooled inlet stream 18 enters a reboiler cross heater 20 for further conditioning , producing a conditioned inlet stream 22 . stream 22 may be further cooled using a chiller . if the pressure of conditioned inlet stream 22 exceeds the critical pressure , either a joule - thomson expander or a turbo - expander can be used to reduce the pressure of conditioned inlet stream 22 . the energy from the expander can be used for compression or for generating electricity . upon completion of the cooling process and pressure reduction processes , the hydrocarbon fluid mixture gas stream is properly conditioned for distillation separation . a distillation separation system that produces a high yield of liquid co 2 is preferred . the primary reason for selecting distillation for the bulk removal of co 2 is its ability to remove the co 2 as a liquid . conditioned inlet stream 22 is distilled in distillation column 24 producing a liquefied co 2 bottom product stream 26 and a distillation overhead stream 28 ( containing significant amounts of co 2 ). the distillation overhead stream 28 is combined with permeate stream 30 from the membrane unit 48 producing combined condenser inlet stream 32 . this stream 32 is cooled by primary condenser 34 producing a primary condenser outlet stream 36 . this stream 36 enters a primary reflux drum 38 producing a hydrocarbon vapor stream 40 and a primary reflux liquid stream 42 . this liquid stream 42 flows back to distillation column 24 by gravity or is pumped by primary reflux pump 44 to enter a top tray of distillation column 24 as reflux . the hydrocarbon vapor stream 40 is sent to membrane unit 48 for further co 2 removal . hydrocarbon vapor stream 40 enters permeate cross heat exchange 5 q and is warmed prior to entering membrane unit 48 . the membrane unit may be a single stage or multiple stages depending on the application , in addition , the permeate pressure of the membrane stages can be different to optimize compressing the permeate gas . membrane separation produces a hydrocarbon product stream 52 and permeate stream 54 . for this example , permeate stream 54 is compressed in a compressor 56 producing a compressed permeate stream 58 . this stream 58 is divided into first and second permeate cross heat exchanger feed streams 60 and 62 . these streams are cooled by permeate cross heat exchanger 50 and hydrocarbon product cross heat exchanger 66 producing permeate cross heat exchanger outlet stream 64 and hydrocarbon product cross heat exchanger outlet stream 68 that combine to form permeate stream 30 . permeate stream 30 is then combined with distillation overhead stream 28 from the distillation column overhead to form combined condenser inlet stream 32 . permeate stream 54 could also be removed for disposal or for further processing instead of being utilized for reflux enhancement . the co 2 bottom product stream 26 may be pumped to an elevated pressure using pump 70 into stream 72 . thermal energy from the pumped co 2 bottom product stream 72 is then recovered using reboiler cross heater 20 to cool inlet stream 18 . the reboiler separator inlet stream 76 enters a reboiler / separator 74 . the vapor from reboiler / separator 74 , stream 78 , is returned to the bottom of distillation column 24 . the liquid from reboiler / separator 74 , stream 80 , is split into a primary co 2 refrigerant stream 82 for chilling , with the balance , stream 84 remaining as a co 2 liquid product stream . primary co 2 refrigerant stream 82 is reduced in pressure with a primary refrigerant pressure reduction device 86 producing primary condensed refrigerant inlet stream 88 . this stream 88 enters primary condenser 34 providing cooling sufficient to produce the required reflux liquid stream 42 . primary condenser refrigerant outlet stream 90 leaving primary condenser 34 enters inlet cross heat exhange 16 as an economizer to cool the inlet gas . the co 2 gas stream leaving inlet cross heat exchange 16 as a gas stream 92 can be compressed to combine with liquid co 2 product stream 84 or can be used as a co 2 gas product stream . for a typical application with an inlet gas of 58 % co 2 at 610 psia , the process , as shown in fig1 , produces a hydrocarbon product containing 10 % co 2 at 565 psia and recovers 89 . 9 % of the hydrocarbon in the inlet gas stream . the co 2 gas product stream contains 92 . 8 % co 2 and recovers 89 . 1 % of the co 2 at 200 psia . the co 2 liquid product stream contains 92 . 8 % co 2 and recovers 3 . 7 % of the co 2 at 610 psia . this gives a total recovery of co 2 for this example of 92 . 8 %. a significant demand for energy in any co 2 removal process producing gaseous co 2 is compression of the co 2 . co 2 compression can be the limiting factor for projects requiring co 2 at elevated pressures such as enhanced oil recovery , or re - injection of the co 2 to eliminate venting to the atmosphere . the compression requirements for this process are less than that for traditional distillation processes , since the co 2 product streams are produced at a relatively high pressure , and no external refrigeration is required . referring now to fig2 , wherein like reference numerals designate identical or corresponding parts , a dehydrated hydrocarbon fluid mixture inlet gas stream 14 that contains carbon dioxide enters inlet cross heat exchanger 16 for cooling . the resulting cooled inlet stream 18 enters a reboiler cross heater 20 for further cooling , producing conditioned inlet stream 22 which may be further cooled using a chiller . if the pressure of conditioned inlet stream 22 exceeds the critical pressure , either a joule - thomson expander or a turbo expander can be used to reduce the pressure thereof energy from an expander can be used for compression of the permeate gas or for generating electricity . upon completion of the cooling process and pressure reduction process , the hydrocarbon fluid mixture is properly conditioned for distillation separation . a distillation separation system that produces a high yield of liquid co 2 is preferred . the primary reason for selecting distillation for the bulk removal of co 2 is its ability to remove the co 2 as a liquid . conditioned inlet stream 22 is then distilled in distillation column 24 producing a co 2 bottom product stream 26 and a distillation overhead stream 28 , which contains significant amounts of co 2 . the distillation overhead stream 28 is cooled by primary condenser 34 producing primary condenser outlet stream 36 that enters primary reflux drum 38 producing a hydrocarbon vapor stream 40 and a primary reflux liquid stream 42 . this primary reflux liquid stream 42 is combined with secondary reflux liquid stream 104 from the secondary reflux drum 96 . the combined reflux liquid stream 106 flows to a top tray of distillation column 24 as a reflux . hydrocarbon vapor stream 40 from primary reflux drum 38 is combined with secondary hydrocarbon vapor stream 118 and enters permeate cross heat exchanger 50 and is warmed prior to entering membrane unit 48 . the membrane unit 48 may be single stage or multiple stages depending on the application . in addition , the permeate pressure of the membrane stages can be different to optimize compressing the permeate gas . separation in membrane unit 48 produces a hydrocarbon product stream 52 and a permeate stream 54 . stream 54 is then compressed in compressor 56 producing compressed permeate stream 58 that is cooled by heat exchangers 50 and 66 producing permeate stream 30 . the permeate stream 30 is then partially condensed using secondary condenser 98 producing secondary condenser outlet stream 102 . secondary reflux drum 96 produces secondary hydrocarbon vapor stream 118 and secondary reflux liquid stream 104 . vapor stream 118 is combined with vapor stream 40 from primary reflux drum 38 . the combined stream is feed to membrane unit 48 . secondary reflux liquid stream 104 is combined with pumped primary reflux liquid stream from primary reflux drum 38 to provide the combined reflux liquid stream 106 that feeds onto an upper tray in distillation column 24 . the liquefied co 2 bottom product stream 26 may be pumped to an elevated pressure using pump 70 . thermal energy from the pumped bottom product stream 72 is then recovered using heat exchanger 20 to cool inlet stream 18 . the high concentration reboiler separator inlet stream 76 leaving heat exchanger 20 enters reboiler / separator 74 . the vapor from reboiler / separator 74 , stream 78 is returned to the bottom of distillation column 24 . liquid from reboiled / separator 74 is split into secondary co 2 refrigerant stream 108 and reboiler separation liquid stream 80 . stream 108 is reduced in pressure with a secondary refrigerant pressure reduction device 110 providing secondary condenser refrigerant stream 112 that enters secondary condenser 98 providing cooling sufficient to produce the required reflux stream 104 that is fed to distillation column 24 . the secondary refrigerant outlet stream 114 leaving secondary condenser 98 is combined with primary refrigerant outlet stream 90 and enters inlet cross heat exchange 16 as an economizer to cool the inlet gas to the process . co 2 gas leaving heat exchange 16 as product 92 can be compressed to combine with liquid co 2 stream 84 or retained as a co 2 gas product stream . for a typical application with an inlet gas of 58 % co 2 at 610 psia , the process as shown in the drawing produces a hydrocarbon gas product containing 10 % co 2 at 565 psia and recovers 91 % of the methane in the inlet . the co 2 product gas stream contains 92 . 8 % co 2 and recovers 88 . 2 % of the co 2 at 200 psia . the co 2 liquid product stream contains 92 . 8 % co 2 and recovers 4 . 6 % of the co 2 at 610 psia . this gives a total recovery of co 2 for this example of 92 . 8 %. a significant demand for energy in any co 2 removal process producing gaseous co 2 is compression of the co 2 . co 2 compression can be the limiting factor for projects requiring the co 2 at elevated pressure such as enhanced oil recovery , or re - injection of the co 2 to eliminate venting to the atmosphere . the compression requirements for this process are less than that for a traditional distillation process since the co 2 product streams are produced at a relatively high pressure and no external refrigeration is required . while the invention has been described with a certain degree of particularity , it is manifest that many changes may be made in the details of construction and the arrangement of components of the equipment and systems used in the invention , as well as the steps and sequence thereof , of practicing the methods of the invention without departing from the spirit and scope of this disclosure . it is understood that the invention is not limited to the embodiments set forth herein for purposes of exemplification , but is to be limited only by the scope of the attached claim or claims , including the full range of equivalency to which each element or step thereof is entitled . | 8 |
fig1 provides a perspective view of one configuration of a battery power supply unit 20 forming a part of a first configuration of an illumination device or system . this illumination device or system will occasionally be referred to in the following description as the nano - lux system . the nano - lux system has two configurations ; one of these configurations is a single headlight configuration , while the other configuration is a double or dual headlight configuration . the power supply unit 20 , as illustrated , includes a cylindrical aluminum tube 22 ( the nano - tube assembly ), forming a lightweight and attractive outer skin , that is open at both ends , a battery jack holder 24 secured to a first of the tube ends , and an end cap 26 secured to a second of the tube ends located opposite the first end . the holder 24 may be connected by threads to the first tube end for easy removal and replacement , and the end cap 26 may also be connected by threads to the second tube end . the jack holder 24 or the end cap 26 could be bonded , glued , or otherwise secured to its respective tube end rather than connected by threads . snap fit connections or other connection types are also useable . the cross sectional view provided by fig2 also shows the holder 24 and the end cap 26 at opposite ends of the tube 22 . fig2 further illustrates a battery tube 28 received within the outer aluminum tube 22 . to facilitate assembly , the battery tube can be constructed from multiple tube parts , such as the parts 28 a , 28 b shown . the battery tube 28 and other power supply unit parts , as illustrated , are designed and dimensioned to receive four serially arranged aa batteries 30 , although other configurations are possible . in its assembled condition , the power supply unit 20 has a printed circuit board ( pcb ) plate 32 interposed between a radially inwardly projecting shoulder 34 of the battery jack holder 24 and the adjacent first tube end . a brass connect ring ( not indicated ) is also located at the first tube end . the pcb plate 32 supports a jack pcb 36 as well as a jack 40 , provided in a socket adapted to receive a mating plug ( not shown in fig2 ) of a wire or cable . this wire or cable may lead to an appropriate tail light ( or the headlight , if desired ), enabling power to be supplied to the tail light ( or the headlight ) by the unit 20 . preferably , a rubber plug 38 encloses the socket when the wire or cable is not used in order to prevent contamination of the socket by dirt , water , and so on . in the configuration shown , the end cap 26 supports a pcb 42 by which the batteries 30 are connected to a harness cord exiting the end cap 26 , as will be described below . an electrical conductor such as the harness cord 166 shown in fig1 may be used as an interconnecting element . in one preferred configuration , the battery jack holder 24 , the end cap 26 , the battery tube 28 , and the pcb plate 32 are formed of a common thermoplastic material such as acrylonitrile butadiene styrene ( abs ). the pcbs 36 and 42 may be of a woven glass and epoxy prepreg type , such as fr4 d / s . the headlight assembly 50 shown in perspective in fig3 includes an aluminum case 52 with spaces or channels within which a decorative insert 54 and a light holder 56 can be fixed by snap connections , screws , or the like . the case 52 , the insert 54 , and the light holder 56 are secured by the screws , the snaps , or other connections to a cylindrical headlight housing 57 . various conventional components are received within the housing 57 . these components are best seen in the cross sectional view provided by fig4 , and include a jack 58 , which may be brass , an abs jack holder 60 , a brass / nickel connect pin 62 , an abs pin cover 64 , an aluminum screw element 66 , an abs lens holder 68 , a clear lens 72 , a light emitting diode or similar light source 74 , an aluminum radiator 76 , and a fr4 d / s pcb 77 . another clear lens 70 is located at a front end of the headlight assembly 50 . a first lens housing 140 , within which the lens 70 is mounted , is threadedly received within a forward end of the cylindrical housing 57 . a second lens housing 142 , within which a wide angle lens 150 ( fig3 ) is mountable , for example , is threadedly receivable within the forward end of the first lens housing 140 . for reasons that will become apparent , the second lens housing 142 will also be referred to below as a “ clear filter ” housing . by way of the threaded connection between the clear filter housing 142 and the first lens housing 140 , the interchangeable wide angle lens 150 , which converts the narrow beam of light traveling from the light source 74 through the clear lenses 70 and 72 into a wide angle beam , can be mounted in position at the forward end of the headlight assembly 50 . a receptacle 144 is located at a rearward end of the cylindrical headlight housing 57 in order to receive the jack connector of a harness extending , for example , between the jack 40 of the power supply unit 20 and the jack 58 of the headlight assembly 50 . also visible in fig4 are certain other components , such as a bicycle grip or holder 78 , having an appropriate contour , a bicycle housing element 80 , and a mounting bracket 82 , which are all secured together and which cooperate in a manner to be described to mount and retain the headlight assembly 50 in position on bicycle handlebars or other tubular components . additional description of these elements is presented below . with minimal modification to the grip holder 78 , the headlight assembly could also be mounted on a handlebar stem . the mounting bracket 82 defines a recurved , hook - shaped protrusion 90 at one end , as illustrated in fig6 - 8 . to secure the mounting bracket 82 to the bicycle housing element 80 , the protrusion 90 is hooked around a flange 92 projecting from a front end of the housing element 80 , pivoted into position , and secured by an appropriate fastener , such as a screw ( not shown ) receivable in a bore 94 extending through the mounting bracket 82 and the housing element 90 and into the grip or holder 78 . a set screw or positioning pin 96 can facilitate alignment of the bracket 82 and the housing element 80 . as shown in fig3 and 5 , the light holder 56 defines oppositely extending flanges 84 at its forward portion . these flanges are slidable into and out of grooves 86 defined in the mounting bracket 82 . the grooves 86 are visible , for example , in fig7 and 8 . once the flanges 84 are inserted into the grooves 86 , the headlight assembly 50 as a whole can be moved rearward relative to the mounting bracket 82 until a back edge 85 of one of the flanges 84 engages with a cam 100 defined on a release pin 102 , which is movable transversely in appropriate holes or recesses 104 provided in the mounting bracket 82 . lateral edges of an upstanding central portion 106 defined on the mounting bracket 82 serve to guide movement of the headlight assembly 50 by engagement with inner surfaces of the flanges 84 . after engagement between the appropriate flange 84 and the cam 100 , the headlight assembly 50 is retained in position , inter alia , by frictional engagement between the flanges 84 and the grooves 86 . the release pin 102 assists a user in disengaging the headlight assembly 50 from the mounting bracket 82 . the cam 100 is shaped so that transverse movement of the release pin 102 in an appropriate direction , by being pressed or pulled by a user , at least partially ejects the flanges 84 from the grooves 86 to provide at least partial disengagement of the assembly 50 and bracket 82 . full disengagement may then be completed manually . a mounting strap 110 is clamped or otherwise retained between adjacent surfaces of the bicycle housing element 80 and the grip or holder 78 . the mounting strap 110 is formed of an appropriate elastic material , and , in a conventional manner , can be wrapped around a bicycle handlebar or other tubular component to secure the grip or holder 78 in position . the mounting strap 110 includes a forward strap portion 112 with teeth 114 defined thereon and a rearward strap portion 116 terminating in a knob assembly 120 . the knob assembly 120 includes a central knob mount 124 defined at or secured to the end of the rearward strap portion 116 , a rotatable knob 126 , and a locket 128 by which the rotatable knob 126 is secured but permitted to rotate relative to the central knob mount 124 . when wrapping the strap 110 around the bicycle handlebar , a user inserts an end 122 of the forward strap portion 112 into a slot 125 extending through the knob assembly 120 . threads 130 defined on a circumferential interior of the knob 126 are receivable in the spaces defined between the teeth 114 on the strap portion 116 so that , by rotation of the knob 126 , the mounting strap 110 can be tightened around or released from the bicycle handlebar or other tubular element . fig1 illustrates the headlight assembly 50 along with the wide angle lens 150 , forming a clear “ filter ” or “ filter element ,” and various color filters or filter elements 152 , 154 , 156 , and 158 , which are interchangeable or useable in combination with the wide angle lens 150 for use in different environments and under different weather conditions . by way of example , the filter 152 may be green , the filter 154 may be blue , the filter 156 may be yellow , and the filter 158 may be red . each of the filters includes a housing 160 having essentially the same construction as that of the clear filter housing 142 . any of the filter housings is threadedly receivable within the forward end of the first lens housing 140 ( fig4 ) in the same way as the second lens housing 142 . the wide angle lens and various filters can also be attached in series to combine the effects . for example , the clear filter housing 142 can be connected to the first lens housing 140 as shown in fig4 , and the housing 160 of another filter , such as the green filter 152 , can be connected , by cooperating threads , to the forward end of the clear filter housing 142 . of course , it is also possible to reverse this order , so that an appropriate filter housing 160 is directly connected to the first lens housing 140 , and the clear filter housing 142 is connected to the filter housing 160 . the wide angle lens and / or the filters may alternatively be retained in place frictionally or in other appropriate ways , such as by threads or by snap connections , on the appropriate outer circumferential surface . fig1 shows a harness , generally designated 164 , that is designed to extend between the end cap 26 of the power supply unit 20 and the jack 58 of the headlight assembly 50 . although other configurations are conceivable , the harness illustrated includes a first cord 166 exiting the end cap 26 secured to the cylindrical tube 22 of the power supply unit , a second cord 168 detachable from the first cord and extending from a connection with the first cord 166 to a junction 170 , a third cord 172 extending from the junction 170 to a jack connector 174 receivable within the receptacle 144 of the headlight housing 57 so as to electrically interconnect the harness and the power supply unit to the jack 58 , and a fourth cord 176 extending from the junction 170 to a remote control 178 operable by a user . approximate dimensions of the harness 164 are 50 cm total for cords 166 and 168 , 9 . 5 cm for cord 176 , and 17 cm for cord 172 . for a single headlight configuration such as the headlight assembly 50 , a three watt solid state emitter , with high / low intensity , is utilized . the emitter is built as a plug and play module for easy replacement , and the assembly 50 is configured as a miniature headlight structure with minimum diameter and length . an aluminum casing is utilized for high - efficiency heat dissipation , and , although variations are possible , it is contemplated that the interchangeable lenses would include four colored filters , namely yellow , ac red , blue , and green , and one wide angle lens that converts a narrow beam to a wide beam as described above . operation of the remote control 178 , in the single headlight configuration , is off → high → off → low → off . this operation can provide the high / low intensity with an improved , more visual distinction . the quick release bicycle mount preferably has a swivel angle of ± 15 degrees , and the tilt angle is based on the mounting angle . a red led indicator on the remote control unit may be used to signal low battery power . the power supply unit 20 ( the nano - tube assembly ), again , uses four aa batteries , arranged serially . as described below , the power supply unit 20 is intended for installation on a bicycle frame beside s water bottle by way of a quick release bracket that shares the water bottle braze - ons . fig1 shows a dual headlight assembly 180 useable in place of the single headlight assembly 50 described previously and constituting part of a second nano - lux system configuration . the dual headlight assembly 180 ( the nano - pack assembly ) is configured as a pair of single headlight assemblies , each similar to the assembly 50 , mounted together in a unitary housing 182 that is provided with a jack similar to the jack 58 of the assembly 50 . in one preferred configuration , the dual headlight assembly 180 includes a three watt solid state emitter in the left headlight and a one watt solid state emitter in right headlight . all emitters are built as a plug - and - play module for easy replacement . as in the single headlight assembly described previously , the headlight assembly 180 has a miniature structure with minimum diameter and length , the casing is aluminum for high efficiency heat dissipation , and , for each of the pair of headlights , interchangeable lenses , including a multiplicity of colored filters , such as yellow , ac red , blue , and green , and a clear filter , or wide angle lens , that converts a narrow beam to a wide beam , are provided . operation of the remote control is off → right → left → dual → off , and the left headlight is a three watt high beam , while the right headlight is a one watt low beam . when either the single headlight assembly 50 or the dual headlight assembly 180 is to be mounted on a helmet , a one - to - one power cord with an extended length can be used . the headlights in the dual light assembly can have different filters attached to the low and high beam lights . for example , the left , high beam headlight could have a red filter mounted to it , while the right , lower beam headlight could have a clear filter , i . e . a wide angle lens , mounted to it . as described , the power supply unit 20 preferably utilizes four aa batteries , arranged serially . the unit 20 is preferably part of a standard package of components including the single headlight assembly 50 , but is also compatible with the dual headlight assembly 180 . referring to fig1 , in its preferred configuration , the power supply unit 20 is installed on a bicycle frame , beside a water bottle 184 , with a quick release bracket that shares the same water bottle braze - ons , such as a bracket including clips ( such as c - clips ) or clasps 186 . velcro connection elements could additionally or alternatively be used . the jack 40 of the power supply unit 20 ( fig2 ), again , defines a socket adapted to receive a mating plug ( not shown ) of a wire or cable leading to an appropriate tail light . fig1 shows an alternative power supply unit 200 mounted in an alternative position on a bicycle . the power supply unit 200 preferably uses four c batteries , is part of a standard package of components including the dual headlight assembly 180 , and is also compatible with the single headlight assembly 50 . the unit 200 is preferably installed under the bicycle saddle 202 and makes use of a conventional quick release bracket and configuration of a saddlebag . a bracket including clips , such as c - clips , or clasps , for example , could be used . again , velcro connection elements could additionally or alternatively be used . the unit 200 , otherwise , could be contained in a pouch that is securable to the seat post 204 or the top tube of the bicycle frame , for example . fig1 shows a harness , generally designated 206 , that is designed to extend between a jack of the power supply unit 200 and either the jack 58 of the headlight assembly 50 or the analogous jack ( not shown ) of the dual headlight assembly 180 . the harness illustrated in fig1 includes a first cord 210 exiting an end cap 208 of the power supply unit 200 , a second cord 212 detachable from the first cord and extending from a connection with the first gord 210 to a junction 214 , a third cord 216 extending from the junction 214 to a jack connector 218 , receivable either within the receptacle 144 of the headlight housing 57 or within a corresponding receptacle of a housing of the unit 200 , so as to electrically interconnect the harness and the power supply unit to the appropriate headlight assembly jack , and a fourth cord 220 extending from the junction 214 to a remote control 222 operable by a user . approximate dimensions of the harness 206 are 50 cm total for cords 210 and 212 , 9 . 5 cm for cord 220 , and 17 cm for cord 216 . an additional cord 224 , attachable to a rear jack of the power supply unit 200 , is illustrated in fig1 . such an additional cord 224 can be used to interconnect the unit 200 to an appropriate tail light , enabling power to be supplied to the tail light . the various filters as described serve to provide a new cosmetic for both single and dual headlight configurations . as noted , the nano lux series or system includes a first model , which is the single headlight system described , and a second model , which is the dual headlight system described . each headlight can accommodate interchangeable color filters for different weather and environments , as well as an interchangeable wide - angle lens to convert a narrow beam to a wide - angle beam . each configuration described utilizes a miniature headlight structure for an already crowded handlebar that is lightweight , permitting installation on a helmet as well as at locations such as on handlebars . in the dual headlight configuration , a pitched dual beam is provided , with the left and right headlights pitched 5 ° for better road coverage . in a preferred configuration , again , the left headlight is a high beam light with a three watt solid state emitter , and the right headlight is a low beam light with a one watt solid state emitter . the power supply unit 20 ( the nano - tube configuration ), again , is one of a number of standard parts for the single headlight arrangement , but it is to be recognized that the unit 20 is also compatible with the dual headlight arrangement . the unit 20 has a diameter of approximately 15 mm , uses four standard aa batteries as described , and , again , is preferably installed beside the water bottle with a quick release bracket that shares the water bottle braze - ons . the alternative power supply unit 200 ( the nano - pack configuration ) is one of a number of standard parts for the dual headlight arrangement , but the unit 200 is also compatible with the single headlight arrangement . as described , the nano - pack power supply unit 200 uses four standard c - cell batteries . certain functions and features of the single headlight configuration that are to be particularly noted will be reiterated here . the single headlight configuration includes a three watt solid state emitter , with high / low intensity . the emitter is built as a plug and play module for easy replacement , and the headlight has a miniature structure , with minimum diameter and length . an aluminum casing is used in order to provide high - efficiency heat dissipation . the interchangeable lenses include four colored filters , namely yellow , ac red , blue , and green . a wide angle lens that converts a narrow beam to a wide beam is also provided . the off → high → off → low → off sequence by which the remote control 178 is operated assists in providing the high / low intensity with more visual distinction . the quick release bicycle mount provided by the bicycle grip or holder 78 , the bicycle housing element 80 , and the mounting bracket 82 has a tilt or swivel angle of approximately ± 15 degrees based , of course , on the mounting angle . a red led indicator on the remote control unit may be used to signal low battery power . the power supply unit 20 is installed beside the water bottle , by way of clips , for example , that form a quick release bracket sharing water bottle braze - ons . a rear socket defined in the power supply unit 20 permits a tail light power supply . in its preferred configuration , the quick release headlight bike mount has a ± 15 degree swivel angle , as does the quick release helmet mount . in its preferred configuration , the quick release bracket for the nano - tube has two long bolts and one velcro element . in one preferred configuration , the left headlight of the double headlight arrangement is a three watt high beam , while the right headlight is a one watt low beam . the swivel angle of the quick release bicycle mount is ± 15 degrees , and the tilt angle is based on the mounting angle , with the low beam is pitched − 5 degrees with respect to the high beam . two interchangeable filters sets , each having four colors , namely yellow , ac red , blue , and green , are provided for the double headlight arrangement . two interchangeable wide - angled lenses are also provided , and a quick - release battery bracket , which is the same as that for the saddle bag , is installed under the saddle . the foregoing disclosure has been set forth merely to illustrate the invention and is not intended to be limiting . since modifications to the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons of ordinary skill in the art , the invention should be construed to include everything within the scope of the appended claims and equivalents thereof . | 1 |
referring now to fig1 - 3 , a heat exchanger is shown generally at 10 as comprising structural support members 12 , and a plurality of tube circuits 14 . structural supports 12 are usually comprised of galvanized steel or stainless steel , while heat exchanger tubes 14 can be comprised of galvanized steel , stainless steel , or other suitable materials such as copper . ends of heat exchanger tubes 18 are seen to extend through openings 20 in second header section 16 . header section 16 itself is usually comprised of galvanized steel , but can be comprised of stainless steel or other suitable materials such as copper . tubing ends 18 are seen to extend through openings 20 in second header section 16 . second header 16 itself is seen to be comprised of an elongated , generally half cylindrical shaped structure . second header section 16 includes top edge 22 and bottom edge 24 , which extend the length of second header section 16 . further , second header section 16 is seen to have a concave side 26 and a convex side 28 . further , as shown in fig1 , first header section 29 is seen to be assembled against second header section 16 . first header section 29 is similar to second header section 16 , except that it usually does not have openings to receive heat exchanger tubes therein . in all other respects , first header section 29 is similar in shape and material to second header section 16 . in assembling heat exchanger 10 , heat exchanger tubes 14 are spaced and placed within structural supports 12 . the ends 18 of heat exchanger tubes 14 are then placed through openings in second header section 16 . a continuous weld is them formed around the section of tubing end 18 that directly passes through and is adjacent opening 20 . in this manner , by forming the welding of concave side 26 of second header section 16 , a continuous weldment is formed about tubing end 18 to ensure a complete and watertight weld . from an access point of view , it is seen to be difficult to perform welding about the tubing end 18 at convex side 28 of second header section 16 , but it is possible to perform welding at certain of tubing end of convex side 28 . however , it is seen to be preferable to perform welding from an access point of view and a continuity point of view from concave side 26 of second header section 16 . in the last step of assembling heat exchanger 10 , first header section 29 is placed such that its top and bottom edges contact , respectively , top edge 22 and bottom edge 24 of second header edge 16 . then appropriate welding is performed along the junction of such edges again to produce a watertight seal between first header section 29 and second header section 16 . referring now to fig4 - 6 , a heat exchanger is shown generally at 30 as comprising structural support members 32 , and a plurality of tube circuits 34 . structural supports 32 are usually comprised of galvanized steel or stainless steel , while heat exchanger tubes 34 can be comprised of galvanized steel , stainless steel , or other suitable materials such as copper . ends of heat exchanger tubes 38 are seen to extend through openings 40 in first heat and second header section 36 . header section 36 itself is usually comprised of galvanized steel , but can be comprised of stainless steel or other suitable materials such as copper . tubing ends 38 are seen to extend through openings 40 in second header section 36 . second header section 36 itself is seen to be comprised of an elongated , generally half cylindrical shaped structure . second header section 36 includes top edge 42 and bottom edge 44 , which extend the length of second header section 36 . further , second header section 36 is seen to have a concave side 46 and a convex side 48 . further , as shown in fig4 , first header section 49 is seen to be assembled against second header section 36 . first header section 49 is similar to second header section 36 , except that it usually does not have openings to receive heat exchanger tubes therein . in all other respects , first header section 49 is similar in shape and material to second header section 36 . in assembling heat exchanger 30 , heat exchanger tubes 34 are spaced and placed within structural supports 32 . the ends 38 of heat exchanger tubes 34 are then placed through openings 40 in second header section 36 . a continuous weld is them formed around the section of tubing end 38 that directly passes through and is adjacent opening 40 . in this manner , by forming the welding of concave side 46 of second header section 36 , a continuous weldment is formed about tubing end 38 to ensure a complete and watertight weld . from an access point of view , it is seen to be difficult to perform welding about the tubing end 38 at convex side 48 of second header section 36 , but it is possible to perform welding at certain of tubing end of convex side 48 . however , it is seen to be preferable to perform welding from an access point of view and a continuity point of view from concave side 46 of second header section 36 . in the last step of assembling heat exchanger 30 , first header section 49 is placed such that its top and bottom edge contact , respectively , top edge 42 and bottom edge 44 of second header edge 36 . then appropriate welding is performed along the junction of such edges again to produce a watertight seal between first header section 49 and second header section 36 . | 5 |
the present invention concerns a disk braking system 10 having active pad retraction functionality intended and configured to address the afore - mentioned concerns of the prior art , including brake drag , and pad / rotor corrosion . the inventive system 10 may be of the type used in automotive applications that feature a caliper 12 , opposite first and second brake pads 14 , a hydraulic drive 16 drivenly coupled to the caliper 12 and pads 14 , and a rotor ( or “ disk ”) 18 intermediately disposed between and selectively engagable by the pads 14 . preferred embodiments described and illustrated herein present an inventive caliper 12 ; however , it is appreciated that the present invention encompasses the use of active material actuation to effect brake pad retraction in general , such that the active material actuation may be performed or embodied by any component of the braking system 10 . the invention may be utilized with other types of braking systems that benefit from active brake retraction ; and as such , is not limited to the configurations and uses described herein . the system 10 utilizes active material actuation , and thereby includes an active material element 20 that is configured to drive retraction when activated or deactivated . the term “ active material ” shall be afforded its ordinary meaning as understood by those of ordinary skill in the art , and includes any material or composite that exhibits a reversible change in a fundamental ( e . g ., chemical or intrinsic physical ) property , when exposed to an external signal source . suitable active materials for use with the present invention include but are not limited to the class of active materials known as shape memory materials . exemplary shape memory materials include shape memory alloys ( sma ), electroactive polymers ( eap ), ferromagnetic smas , electrorheological ( er ) and magnetorheological ( mr ) elastomers , dielectric elastomers , piezoelectric polymers , piezoelectric ceramics , various combinations of the foregoing materials , and the like . depending on the particular active material , the activation signal can take the form of , without limitation , an electric current , an electric field ( voltage ), a temperature change , and the like . more particularly , shape memory alloys ( sma &# 39 ; s ) generally refer to a group of metallic materials that demonstrate the ability to return to some previously defined shape or size when subjected to an appropriate thermal stimulus . shape memory alloys are capable of undergoing phase transitions in which their yield strength , stiffness , dimension and / or shape are altered as a function of temperature . the term “ yield strength ” refers to the stress at which a material exhibits a specified deviation from proportionality of stress and strain . generally , in the low temperature , or martensite phase , shape memory alloys can be pseudo - plastically deformed and upon exposure to some higher temperature will transform to an austenite phase , or parent phase , returning to their shape prior to the deformation . materials that exhibit this shape memory effect only upon heating are referred to as having one - way shape memory . shape memory alloys exist in several different temperature - dependent phases . the most commonly utilized of these phases are the so - called martensite and austenite phases discussed above . in the following discussion , the martensite phase generally refers to the more deformable , lower temperature phase whereas the austenite phase generally refers to the more rigid , higher temperature phase . when the shape memory alloy is in the martensite phase and is heated , it begins to change into the austenite phase . the temperature at which this phenomenon starts is often referred to as austenite start temperature ( a s ). the temperature at which this phenomenon is complete is called the austenite finish temperature ( a f ). when the shape memory alloy is in the austenite phase and is cooled , it begins to change into the martensite phase , and the temperature at which this phenomenon starts is referred to as the martensite start temperature ( m s ). the temperature at which austenite finishes transforming to martensite is called the martensite finish temperature ( m f ). generally , the shape memory alloys are softer and more easily deformable in their martensitic phase and are harder , stiffer , and / or more rigid in the austenitic phase . in view of the foregoing , a suitable activation signal for use with shape memory alloys is a thermal activation signal having a magnitude to cause transformations between the martensite and austenite phases . shape memory alloys can exhibit a one - way shape memory effect , an intrinsic two - way effect , or an extrinsic two - way shape memory effect depending on the alloy composition and processing history . annealed shape memory alloys typically only exhibit the one - way shape memory effect . sufficient heating subsequent to low - temperature deformation of the shape memory material will induce the martensite to austenite type transition , and the material will recover the original , annealed shape . hence , one - way shape memory effects are only observed upon heating . active materials comprising shape memory alloy compositions that exhibit one - way memory effects do not automatically reform , and will likely require an external mechanical force to reform the shape . intrinsic and extrinsic two - way shape memory materials are characterized by a shape transition both upon heating from the martensite phase to the austenite phase , as well as an additional shape transition upon cooling from the austenite phase back to the martensite phase . intrinsic two - way shape memory behavior must be induced in the shape memory material through processing . such procedures include extreme deformation of the material while in the martensite phase , heating - cooling under constraint or load , or surface modification such as laser annealing , polishing , or shot - peening . once the material has been trained to exhibit the two - way shape memory effect , the shape change between the low and high temperature states is generally reversible and persists through a high number of thermal cycles . in contrast , active materials that exhibit the extrinsic two - way shape memory effects are composite or multi - component materials that combine a shape memory alloy composition that exhibits a one - way effect with another element that provides a restoring force to reform the original shape . the temperature at which the shape memory alloy remembers its high temperature form when heated can be adjusted by slight changes in the composition of the alloy and through heat treatment . in nickel - titanium shape memory alloys , for instance , it can be changed from above about 100 ° c . to below about − 100 ° c . the shape recovery process occurs over a range of just a few degrees and the start or finish of the transformation can be controlled to within a degree or two depending on the desired application and alloy composition . the mechanical properties of the shape memory alloy vary greatly over the temperature range spanning their transformation , typically providing the system 10 with shape memory effects , superelastic effects , and high damping capacity . suitable shape memory alloy materials include , without limitation , nickel - titanium based alloys , indium - titanium based alloys , nickel - aluminum based alloys , nickel - gallium based alloys , copper based alloys ( e . g ., copper - zinc alloys , copper - aluminum alloys , copper - gold , and copper - tin alloys ), gold - cadmium based alloys , silver - cadmium based alloys , indium - cadmium based alloys , manganese - copper based alloys , iron - platinum based alloys , iron - platinum based alloys , iron - palladium based alloys , and the like . the alloys can be binary , ternary , or any higher order so long as the alloy composition exhibits a shape memory effect , e . g ., change in shape orientation , damping capacity , and the like . it is appreciated that sma &# 39 ; s exhibit a modulus increase of 2 . 5 times and a dimensional change ( recovery of pseudo - plastic deformation induced when in the martensitic phase ) of up to 8 % ( depending on the amount of pre - strain ) when heated above their martensite to austenite phase transition temperature . it is appreciated that thermally induced sma phase changes are one - way so that a biasing force return mechanism ( such as a spring ) would be required to return the sma to its starting configuration once the applied field is removed . joule heating can be used to make the entire system electronically controllable . the active material element 20 may also comprise an electroactive polymer such as ionic polymer metal composites , conductive polymers , piezoelectric material and the like . electroactive polymers include those polymeric materials that exhibit piezoelectric , pyroelectric , or electrostrictive properties in response to electrical or mechanical fields . the materials generally employ the use of compliant electrodes that enable polymer films to expand or contract in the in - plane directions in response to applied electric fields or mechanical stresses . an example of an electrostrictive - grafted elastomer with a piezoelectric poly ( vinylidene fluoride - trifluoro - ethylene ) copolymer . this combination has the ability to produce a varied amount of ferroelectric - electrostrictive molecular composite systems . these may be operated as a piezoelectric sensor or even an electrostrictive actuator . materials suitable for use as an electroactive polymer may include any substantially insulating polymer or rubber ( or combination thereof ) that deforms in response to an electrostatic force or whose deformation results in a change in electric field . exemplary materials suitable for use as a pre - strained polymer include silicone elastomers , acrylic elastomers , polyurethanes , thermoplastic elastomers , copolymers comprising pvdf , pressure - sensitive adhesives , fluoroelastomers , polymers comprising silicone and acrylic moieties , and the like . polymers comprising silicone and acrylic moieties may include copolymers comprising silicone and acrylic moieties , polymer blends comprising a silicone elastomer and an acrylic elastomer , for example . materials used as an electroactive polymer may be selected based on one or more material properties such as a high electrical breakdown strength , a low modulus of elasticity ( for large or small deformations ), a high dielectric constant , and the like . in one embodiment , the polymer is selected such that is has an elastic modulus at most about 100 mpa . in another embodiment , the polymer is selected such that is has a maximum actuation pressure between about 0 . 05 mpa and about 10 mpa , and preferably between about 0 . 3 mpa and about 3 mpa . in another embodiment , the polymer is selected such that is has a dielectric constant between about 2 and about 20 , and preferably between about 2 . 5 and about 12 . the present disclosure is not intended to be limited to these ranges . ideally , materials with a higher dielectric constant than the ranges given above would be desirable if the materials had both a high dielectric constant and a high dielectric strength . in many cases , electroactive polymers may be fabricated and implemented as thin films . thicknesses suitable for these thin films may be below 50 micrometers . as electroactive polymers may deflect at high strains , electrodes attached to the polymers should also deflect without compromising mechanical or electrical performance . generally , electrodes suitable for use may be of any shape and material provided that they are able to supply a suitable voltage to , or receive a suitable voltage from , an electroactive polymer . the voltage may be either constant or varying over time . in one embodiment , the electrodes adhere to a surface of the polymer . electrodes adhering to the polymer are preferably compliant and conform to the changing shape of the polymer . correspondingly , the present disclosure may include compliant electrodes that conform to the shape of an electroactive polymer to which they are attached . the electrodes may be only applied to a portion of an electroactive polymer and define an active area according to their geometry . various types of electrodes suitable for use with the present disclosure include structured electrodes comprising metal traces and charge distribution layers , textured electrodes comprising varying out of plane dimensions , conductive greases such as carbon greases or silver greases , colloidal suspensions , high aspect ratio conductive materials such as carbon fibrils and carbon nanotubes , and mixtures of ionically conductive materials . materials used for electrodes of the present disclosure may vary . suitable materials used in an electrode may include graphite , carbon black , colloidal suspensions , thin metals including silver and gold , silver filled and carbon filled gels and polymers , and ionically or electronically conductive polymers . it is understood that certain electrode materials may work well with particular polymers and may not work as well for others . by way of example , carbon fibrils work well with acrylic elastomer polymers while not as well with silicone polymers . the active material may also comprise a piezoelectric material configured as an actuator for providing rapid deployment . as used herein , the term “ piezoelectric ” is used to describe a material that mechanically deforms ( changes shape ) when a voltage potential is applied , or conversely , generates an electrical charge when mechanically deformed . preferably , a piezoelectric material is disposed on strips of a flexible metal or ceramic sheet . the strips can be unimorph or bimorph . preferably , the strips are bimorph , because bimorphs generally exhibit more displacement than unimorphs . finally , electrorheological and magnetorheological compositions , such as er and mr elastomers are “ smart ” materials whose rheological properties rapidly change upon application of an electric potential or magnetic field . mr elastomers , for example are suspensions of micrometer - sized , magnetically polarizable particles in a thermoset elastic polymer or rubber . the stiffness of the elastomer structure is accomplished by changing the shear and compression / tension moduli by varying the strength of the applied magnetic field . the mr elastomers typically develop structure when exposed to a magnetic field in as little as a few milliseconds . discontinuing the exposure of the mr elastomers to the magnetic field reverses the process and the elastomer returns to its lower modulus state . returning to the structural configuration of the invention , preferred embodiments of the inventive caliper 12 are variously shown in fig2 - 9 . in each of the embodiments , the caliper 12 includes a hollow cylinder 22 that is communicatively coupled at one end to the hydraulic drive 16 , and open at the other end . the caliper 12 further includes a reconfigurable piston 24 coaxially aligned with , disposed within , and translatable relative to the cylinder 22 . the piston 24 is fixedly attached to the brake pad 14 , and as such presents an attached end that translates between an applied position spaced from the open end of the cylinder 22 and configured to engage the pad 14 and rotor 18 , and a retracted position preferably flush with the open end of the cylinder 22 , when functioning properly . more particularly , as is conventionally the case , hydraulic fluid 26 is used to convert a force applied to the brake pedal ( not shown ) by a user ( also not shown ) into pressure within the cylinder 22 and against the piston 24 , such that the piston 24 and cylinder 22 are sealingly engaged . alternatively , it is appreciated that pneumatic or otherwise pressure may be utilized . the pressure causes the piston to travel outwards within the cylinder and the pad 14 to engage the rotor 18 . once the force is removed , the pressure is discontinued , allowing the piston to retreat . as previously mentioned , however , it is appreciated that residual fluid pressure after a braking event often causes the pad to remain in the applied position , so as to clean the rotor , but that said residual engagement may result in brake drag , or pad / rotor corrosion when the vehicle is sedentary for an extended period of time . in the present invention , the reconfigurable piston 24 is operable to push off of the rotor 18 , so as to selectively cause translation towards the retracted position , and in this manner , effect brake pad retraction . to that end , the piston 24 further comprises an outer shell 28 , and member 30 translatable relative to the shell 28 . the member 30 is fixedly attached to the pad 14 at a distal end exterior to the open end of the cylinder 22 . in fig2 and 3 , the member 30 presents a plunger concentric with the shell 28 . a sloped plate 32 is concentrically aligned and disposed beneath the plunger 30 . a ball bearing ( or a roller attached to the plunger ) 34 intermediately engages the plunger 30 and plate 32 , and rollingly engages the two . as the plate 32 rotates , the bearing 34 and therefore the plunger 30 is caused to linearly translate towards a deployed or retracted condition . finally , the plate 32 rides upon a thrust bearing or roller pin 36 . as shown in fig2 , the active material element may comprise at least one , and more preferably for redundancy , a plurality of shape memory alloy wires 20 that are wound about the plate 32 and fixedly attached to the shell 28 . more particularly , the sma wires 20 are wrapped counter - clockwise around the ramped actuation plate 32 and attached to the plate 32 . as the wires 20 are heated , they contract , rotating the plate 32 clockwise between a thrust bearing 36 and the plunger 30 . the wires 20 are preferably activated by an electric current through joule heating . as used herein the term “ wire ” shall encompass other equivalent geometric forms suitable for use as a flexible tensile actuator , including but not limited to braids , cables , ropes , etc . the wire 20 is depicted , herein , as being wrapped , however , it is appreciated that a linear wire , a bowstring , or another configuration may be equally employed to effect the intended displacement . finally , it is understood that a wire wrapped in a clockwise configuration and resultant opposite rotation would be equally effective , and that the two directions are interchangeable throughout this disclosure . because the pad 14 already bears against the rotor 12 due , for example , to the residual pressure , it is appreciated that the member ( e . g ., plunger ) 30 is prevented from further outward translation relative to the open end of the cylinder 22 . as such , when the wire 20 is activated , the shell 28 will be caused to translate inwardly into the cylinder 22 , thereby pushing fluid 26 back up the line . once the wire 20 is deactivated , the plunger 30 retracts into the shell 28 thereby pulling the pad 14 away from the rotor 18 . the shape memory alloy is allowed to retract to its non - activated state , by releasing heat to the surrounding environment . more preferably , the shell 28 and cylinder 22 may cooperatively define a detent 37 ( fig1 ), so as to retain the shell in the retracted position , while the member 30 recedes therein . where the element 20 presents one - way actuation , a return mechanism 38 is provided to rotate the plate 32 clockwise and drive the plunger 30 back towards the retracted condition when the element 20 is deactivated . in fig2 , the return 38 presents a disk or wave spring concentrically aligned with the plunger 30 and disposed between the plunger 30 and an upper travel stop 40 defined by the shell 28 . as such , it is appreciated that extending the plunger 30 relative to the shell 28 simultaneously compresses the spring 38 . this stretches the slack sma wires 20 to their original length further causing them to transition back to the deactivated martensitic phase . finally , in case the member ( e . g ., plunger ) 30 is blocked from moving outward , an overload protection mechanism 42 is preferably provided to present a secondary output path . in fig2 , the mechanism 42 comprises an elastomeric disk disposed beneath the thrust bearing 36 . the elastomeric disk 42 allows the plate 32 to still rotate when the sma wires 20 are activated but the plunger 30 and shell 28 are unable to relatively translate , thereby protecting them from damage . that is to say , in this instance , the slope of the ramp exerts a downward force upon the thrust bearing 36 causing the disk 42 to compress . in a second embodiment , the inventive caliper 12 includes an sma screw type actuator , wherein the member 30 is a screw and the plate 32 is replaced by a ball or lead nut 44 ( fig4 - 5 ) threadably engaged with the screw 30 . here , the sma wires 20 are again connected at one end to the inner wall of the shell 28 , wrapped counter - clockwise around the nut 44 and attached to the nut 44 . as the wires 20 are heated , they contract , rotating the nut 44 clockwise between two thrust bearings 36 a , b ; the first 36 a between the shell 28 and the nut 44 , and the second 36 b between the nut 44 and an elastomeric overload protection disk 42 . this extends the screw 30 out of the shell 28 , and towards the brake rotor 18 . a disk or wave return spring 38 is disposed beneath an outbound travel stop 40 and the flanged lower end of the screw 30 . the return spring 38 is simultaneously compressed as the screw 30 is caused to extend . once power is cut to the sma wires 20 , they cool and become slack . the return spring 38 then pushes the screw 30 inward , rotating the nut 44 counter - clockwise and stretching the sma wires 20 to their original length . in case the screw 30 is blocked from moving outward relative to the shell 28 , the overload protection mechanism 42 compresses and allows the nut 44 to still rotate when the sma wires 20 contract , protecting them from damage . in a third embodiment , the piston 24 includes a multi - stage telescoping member 30 , which preferably allows for different magnitudes of retraction ( fig6 - 9 ). more particularly , the member 30 herein comprises a plurality of extensions , exemplarily depicted as two in the illustrated embodiment . the extensions are concentric with the cylinder , and radially disposed relative to each other . preferably , each extension is separately controllable . the first and radially exterior extension 46 is slidably engaged to a thread 48 that mates with the shell 28 ( fig6 - 9 ). the extension 46 includes a first set of shape memory wire bundles 50 , preferably comprising martensitic sma , which are connected at their upper ends to the thread 48 and at their opposite ends to a first set of laterally adjacent rigid rods 52 . when the first bundles 50 are activated they are caused to contract , further causing the rods 52 to move out of the shell 28 . the first set of bundles 50 are also connected to the second extension 54 , and more particularly , to a second set of rigid rods 56 comprising the same . as such , when activated , the first set of bundles 50 also lifts the second extension 54 to the first stage . it is appreciated that , similarly , for a greater plurality of extensions , it is appreciated that each extension is drivenly coupled to the radially interior extension ( s ). the second set of rods 56 are fixedly coupled to a second set of wire bundles 58 , again preferably comprised of sma . when the second set of bundles are activated , they contract causing the second set of rigid rods 56 to move further out of the shell 28 relative to the first set of rigid rods 52 and to a second stage ( fig9 ). in a preferred embodiment , the first and second sets of bundles 50 , 58 can be actuated together or independently depending on the requirement . to effect overload protection , the first and second set of rods 52 , 56 preferably include elastomeric ( or otherwise compressible ) longitudinal sections 42 integrated therein . here , the elastomeric mechanism 42 protects the shape memory bundles 58 from overloading by compressing or buckling when the extensions 46 , 54 are unable to translate relative to the shell 28 . finally , first and second spring steel sets 60 , 62 are configured to engage the first and second extensions 46 , 54 , respectively , so as to act as returns . more particularly , when the bundles 50 , 58 are deactivated , they are caused to retract by the first and second spring steel sets 60 , 62 , which release energy stored during the outward translation of the extensions 46 , 54 . it is appreciated that various other spring configurations ( e . g ., compression , extension , etc .) may alternatively be utilized . in operation , it is appreciated that the anticipatory temperature range to be encountered by the system 10 , during driving conditions , is generally between 150 ° and 300 ° c . and that sudden stop or aggressive driving conditions may approach and / or surpass the upper end of this range . as such , to enable passive actuation , thermally activated elements 20 should preferably present transition temperatures within this range and more preferably retain memory properties up to the maximum range temperature . where temperatures at and above the upper end of the range are abusive to the elements 20 , it is desirable to insulate these elements 20 from the heat generated during aggressive stop conditions . in a preferred embodiment , an activation signal source 64 ( fig1 ) is coupled to the active material element 20 and configured to selectively ( e . g ., manually or in response to sensory input ) generate an activation signal . the source 64 , for example , may be the charging system of the vehicle , that is controllably coupled to the element 20 through conductive leads . the source 64 may be directly or indirectly operable . with respect to the latter , the leads preferably engage the element 20 , for example , by delivering an electric current through the resistance of the element . alternatively , it is appreciated that the signal may be provided by the ambient environment or a contacting fluid , such that the element 20 is passively activated . in a preferred embodiment , the system 10 further includes a sensor 66 operable to determine a condition ( fig1 ) and communicatively coupled to the element 20 . the system 10 is configured such that the element 20 is activated only upon determination of the condition . for example , a sensor 66 communicatively coupled to the rotor 18 or drive axle ( not shown ) may be operable to detect a brake drag condition , such that the element 20 is activated only when brake drag is detected . this written description uses examples to disclose the invention , including the best mode , and also to enable any person skilled in the art to make and use the invention . the patentable scope of the invention is defined by the claims , and may include other examples that occur to those skilled in the art . such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims , or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims . also , as used herein , the terms “ first ”, “ second ”, and the like do not denote any order or importance , but rather are used to distinguish one element from another , and the terms “ the ”, “ a ”, and “ an ” do not denote a limitation of quantity , but rather denote the presence of at least one of the referenced item . all ranges directed to the same quantity of a given component or measurement is inclusive of the endpoints and independently combinable . | 5 |
some content delivery networks ( cdn ) make use of a software application known as dynamic content delivery ( dcd ), which is designed for use in distributing file content . in the dcd application , an upload and replication model is followed , wherein the content is initially uploaded to a depot server repository . an application such as dcd keeps a catalog or record of where specified file content is located in the cdn system . also , the application notifies respective clients when the content becomes available for downloading , and tells them to take such action . then , when a client submits a request to proceed with downloading , the application responds by providing the client with a download plan , which is a list of all sources that have the specified content . thereupon , the client connects to one of those sources to obtain the content . in the environment of a cdn of this type , content that clients will need and will request is known . thus , this environment differs significantly from the environment of the internet , wherein the requests that the client will make are generally not known . however , a process wherein file content is replicated to depot servers in successive , gradual stages , as described above , tends to be very unpredictable . as a result , it can be quite difficult to determine the time at which clients should be notified that particular content has become available for downloading . embodiments of the invention are intended to address this difficulty . referring to fig1 , there is shown a content delivery network ( cdn ) 100 that comprises a number of geographic regions , such as usa , china , and brazil regions 102 - 106 , respectively . region 102 further includes branch office zones 108 and 110 , and region 104 includes a branch office zone 112 . cdn 100 is a distributed network configured to efficiently move data content , including large data files , from one location of the network to another . cdn 100 is further configured , as described hereinafter in further detail , to download the same file content to multiple clients with significantly increased efficiency , in accordance with an embodiment of the invention . to achieve these results in part , depot servers 112 - 132 are strategically located in respective regions or zones , so that each depot server is physically close to groups of clients . fig1 shows exemplary clients and groups of clients , such as clients 134 - 138 proximate to depot server 112 , clients 140 - 142 proximate to depot server 124 , clients 146 - 148 proximate to depot server 114 and client 152 proximate to server 120 . generally , when a client submits a request to download file content , a content distribution application , such as the cdc application described above , notifies the client of the closest depot server or other source for the file content . then , the client can download the content from the closest depot server or other source , and thus avoid any need to download the content over a great distance , such as from one part of the world to another . the content distribution application is located at the management center 150 of cdn 100 . this application usefully comprises a distributed , grid - like service for efficiently moving large files around a network , and allowing such files to be downloaded by multiple clients . it is to be emphasized that a principal goal of embodiments of the invention is to enable files to be downloaded to a branch office or the like once and only once . after one source in the branch starts downloading the file , all clients associated with the branch wait to get the file from that source . in order to use cdn 100 to distribute file content in accordance with an embodiment of the invention , the content is initially uploaded into one of the depot servers , under the direction of the content distribution application . the file content can comprise an entire data file , or may be a specified segment or portion of a file . also , the file content initially may be uploaded or published from a client or other source . for example , if certain file content that is needed elsewhere resides in a client 152 of branch office zone 110 , the content would initially be published from client 152 to depot server 120 , the closest server to client 152 . in typical operation of the content distribution application , an upload of specified file content to depot server 152 would be accompanied by deployment specifications or the like , which identify clients in cdn 100 that need to receive the specified content . the deployment specifications would be processed by the content distribution application , in order to generate a download plan for the content that was published to server 120 . for example , the deployment specifications could indicate that the uploaded content was needed by clients 134 - 138 in the new york branch office zone 108 , and was also needed by clients 140 - 144 in china region 104 . based on these specifications , the distribution application would generate a plan that designated depot servers 116 , 112 , and 124 as respective target depot servers . the plan would also direct replications of the specified file content , initially uploaded to depot server 152 , to take place in successive stages . thus , in the first stage the content would be replicated from initial server 120 to target depot server 116 . then , in the second stage , the content would be replicated from server 116 to depot server 112 in zone 108 , and would also be replicated from server 116 to depot server 124 in region 104 . when the specified file content is initially uploaded to depot server 120 , the distribution application broadcasts a message to clients that need the content , such as clients 134 - 138 and 140 - 144 . the message informs the clients that the content is in the process of being made available for download . upon receiving this message , respective clients seek to download the file content , by submitting requests to the content distribution application at management center 150 . in response , each requesting client is sent the download plan . the download plan notifies each client of the target depot server that is closest to the client , and that the target depot server either has received or will receive the specified file content . referring to fig2 , there are shown each of the clients 140 - 144 of china region 104 , wherein each client has been notified by the content distribution application that specified file content is going to be made available as described above . upon requesting download of such content , each client 140 - 144 receives the download plan , and therefore knows that depot server 124 , the closest server thereto , is a target depot server for the specified content . accordingly , fig2 shows all the clients 140 - 144 disposed to ask server 124 for the file content simultaneously , or within a narrow time window that may be on the order of seconds . in order to establish a more efficient procedure for enabling each of the clients 140 - 142 to download the specified file content from closest depot server 124 , server 124 is configured to operate , in response to a client , in one of a number of optional modes . these modes include the following , but are not necessarily limited thereto : ( 1 ) if depot server 124 has finished replicating the specified file content when a client requests the content from the server , server 124 will immediately start serving the specified file content to the requesting client . ( 2 ) if depot server 124 is in the process of replicating the specified file content when a client requests the content from the server , server 124 will estimate how much time is required to finish the replication . the server will then give the client a value representing this amount of time , whereupon the client places the server on hold . when the amount of time has elapsed , the client again asks the depot server 124 for the specified file content . if a second client requests the specified file content that is still replicating , server 124 will estimate how much time is required to finish the replication and add a specified amount of time since it is the second client requesting . in making estimate for subsequent clients requesting the same file , the depot server keeps track of the number of clients that have asked for the file previously . the depot server then adds time based on this number to its estimate . for example , it could add 5 seconds for each requesting client . in this example , if the first client was told to come back in 30 seconds and 10 seconds later the second client requests the same content , it will be told to come back in 20 sec +( 1 * 5 sec )= 25 seconds . if the third client asks for the same file one second later , it will be told to come back in 19 sec +( 2 * 5 sec )= 29 seconds . this is done to avoid having all clients come back at the exact same time that the depot server finishes downloading the file . ( 3 ) if depot server 124 does not have the specified file content when a client requests the content from the server , server 124 will return a file not found error message to the requesting client . if the download plan the client has indicates that the depot server is in a pending state to get the file , the client understands therefrom that it must wait a predefined amount of time , e . g . 60 seconds , before asking the server again for the specified content . however , if the download plan indicates that the depot server is supposed to have the file already , the client reports the depot server to the management center . the client does not retry that depot server again . when downloading a file using cdn 100 , a client can open connections to multiple servers , and can simultaneously retrieve different segments of a file from the different servers . the above set of modes would be available to each of the multiple servers . clients can also be configured to retrieve a file or file segments from peers , that is , other clients that have previously downloaded the same file or file segments . fig3 is a flow chart setting forth principal steps in operating cdn 100 in accordance with an embodiment of the invention . at step 302 , specified file content is initially uploaded from a source to a particular depot server . as described above , the source can comprise a client that originally contained the specified content . at step 304 , immediately after uploading the specified file content to the particular depot server , certain clients of the cdn 100 are notified that the content is being made available for downloading . these clients could include those known to need the specified file content . a download plan based on content deployment specifications is generated at step 306 by the content distribution application , as described above . the plan provides for replicating the specified file content in stages , at designated target depot servers . at step 308 , the download plan is furnished to each client that submits a request to download the specified content , in order to notify respective clients of the closest target depot server . finally , in accordance with step 310 , when a client asks the target depot server for the specified file content , the server is operated in one of the modes described above . these modes are collectively selected to ensure that any client requesting the specified file content can at some time , either immediately or later , download the file content from the closest target depot server . referring to fig4 , there is shown a flow chart pertaining to operation of a target depot server in different optional modes , as described above . at step 402 , it is determined whether or not the target depot server has finished replicating specified file content . if it has finished , step 404 indicates that the content is downloaded to a client requiring the specified content . however , if the target depot server has not finished replicating the specified file content , it must be determined if the target depot server is currently in the process of replicating the specified file content , as provided by step 406 . as shown by steps 408 and 412 , if the server is currently replicating the file content , the target depot server provides the client with a value indicating the amount of time until replication is finished . the client then puts the target depot server on hold for this amount of time , and thereafter again queries the target depot server to download the specified file content . if step 406 has a negative result , it is necessary to determine at step 412 whether the download plan specifies a pending state for the target depot . if it does , the client waits for a predefined amount of time , such as 60 seconds , and then again queries the target depot server to download the specified file content , as shown by step 414 . otherwise , as shown by step 416 , the client reports to the network management center that the target depot server does not have the specified file . the client does not retry that depot server again . with reference now to fig5 , a block diagram depicts a data processing system 500 that may be implemented as a server , to provide one of the depot servers for cdn 100 of fig1 . data processing system 500 may be a symmetric multiprocessor ( smp ) system including a plurality of processors 502 and 504 connected to system bus 506 . alternatively , a single processor system may be employed . also connected to system bus 506 is memory controller / cache 508 , which provides an interface to local memory 509 . i / o bus bridge 510 is connected to system bus 506 and provides an interface to i / o bus 512 . memory controller / cache 508 and i / o bus bridge 510 may be integrated as depicted . peripheral component interconnect ( pci ) bus bridge 514 connected to i / o bus 512 provides an interface to pci local bus 516 . a number of modems may be connected to pci bus 516 . communication links may be provided through modem 518 and network adapter 520 connected to pci local bus 516 through add - in boards . additional pci bus bridges 522 and 524 provide interfaces for additional pci buses 526 and 528 , from which additional modems or network adapters may be supported . in this manner , data processing system 500 allows connections to multiple network computers . a memory - mapped graphics adapter 530 and hard disk 532 may also be connected to i / o bus 512 as depicted , either directly or indirectly . those of ordinary skill in the art will appreciate that the hardware depicted in fig5 may vary . for example , other peripheral devices , such as optical disk drives and the like , also may be used in addition to or in place of the hardware depicted . the depicted example is not meant to imply architectural limitations with respect to the present invention . the data processing system depicted in fig5 may be , for example , an ibm risc / system 6000 system , a product of international business machines corporation in armonk , n . y ., running the advanced interactive executive ( aix ) operating system . alternatively , the operating system may be another commercially available operating system such as javaos for business ™ or os / 2 ™, which are also available from ibm . referring to fig6 , there is shown a block diagram of a generalized data processing system 600 which may be implemented as a client for cdn 100 . data processing system 600 exemplifies a computer , in which code or instructions for implementing processes associated with the present invention may be located . data processing system 600 usefully employs a peripheral component interconnect ( pci ) local bus architecture , although other bus architectures may alternatively be used . fig6 shows a processor 602 and main memory 604 connected to a pci local bus 606 through a host / pci bridge 608 . pci bridge 608 also may include an integrated memory controller and cache memory for processor 602 . referring further to fig6 , there is shown a local area network ( lan ) adapter 612 , a small computer system interface ( scsi ) host bus adapter 610 , and an expansion bus interface 614 respectively connected to pci local bus 606 by direct component connection . scsi host bus adapter 610 provides a connection for hard disk drive 618 , and also for cd - rom drive 620 . an operating system runs on processor 602 and is used to coordinate and provide control of various components within data processing system 600 shown in fig6 . the operating system may be a commercially available operating system such as windows xp , which is available from microsoft corporation . instructions for the operating system and for applications or programs are located on storage devices , such as hard disk drive 620 , and may be loaded into main memory 604 for execution by processor 602 . 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 , etc . 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 tangible apparatus that can contain , store , communicate , propagate , 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 , infrared , or semiconductor system ( or apparatus or device ) or a propagation medium . 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 . the description of the present invention has been presented for purposes of illustration and description , and is not intended to be exhaustive or limited to the invention in the form disclosed . many modifications and variations will be apparent to those of ordinary skill in the art . the embodiment was chosen and described in order to best explain the principles of the invention , the practical application , and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated . | 6 |
the exhaust emissions , and especially the no x emissions , from a direct injected homogeneous charge compression ignition engine can be controlled and held at a low level or reduced by combusting in the direct injected hcci engine in which fuel is injected during the compression stroke , a fuel having a cetane number or derived cetane number as determined by astm d613 or astm d6890 , respectively , of between about 20 - 50 , preferably about 20 - 40 , and more preferably about 20 - 30 , with the fuel also having a total aromatics content of about 15 wt % or more , preferably 28 wt % or more , more preferably between about 15 to 50 wt %, and most preferably between about 28 to 50 wt %. fuel boiling range can be from 25 ° c . to 380 ° c . for gasoline fuels the average of research and motor octane numbers , (( r + m )/ 2 ), can be 60 to 91 , preferably 60 to 81 , and more preferably 60 to 70 . diesel fuel is defined as a mixture of hydrocarbons which boil at atmospheric pressure over a temperature range within about 150 ° c . to 380 ° c ., whereas gasoline fuels are those which boil at atmospheric pressure over a temperature range within about 25 ° c . to 220 ° c . the fuels used can also contain non - hydrocarbon components , such as oxygenates . they can also contain additives , e . g ., dyes , antioxidants , cetane improvers , cold flow improvers , or lubricity improvers . a study was conducted to explore fuel property effects on hcci engine performance and exhaust emissions , focusing on cetane number , aromatic content and volatility for all fuels , and octane number for gasoline fuels . the properties of diesel fuels used in this study are shown in table 1 . the properties of gasoline test fuels are presented in table 2 . the engine used in this study was a single cylinder caterpillar 3401 engine with specifications given in table 3 . a hydraulically intensified fuel injector was used to provide a uniform spray distribution . intake and exhaust surge tanks were used to provide boost and backpressure levels that are representative of actual multi - cylinder turbocharger operation . no oxidation catalyst was used so the hc and co levels reported are all engine - out values . exhaust gas emissions of co , hc , no x and co 2 were measured with a horiba exsa analyzer . an avl smoke meter was used for smoke measurement . the fuels were tested at engine speeds of 1200 , 1500 and 1800 rpm and engine loads of 25 %, 50 % and 70 +%. the study was focused on engine operating conditions characterized by no x emissions & lt ; 0 . 2 g / hp · h and avl smoke numbers & lt ; 0 . 1 . the former corresponds to us epa 2010 no x emission standard for heavy - duty engines , while the latter is roughly equivalent to the 2010 particulate emission requirement of 0 . 01 g / hp · h . the effect of cetane number on the performance and emissions of the hcci engine was evaluated by comparing low cetane ( 38 . 5 ) diesel fuel d3 with mid - range cetane ( 45 . 5 ) fuel d4 , as well as mid - range cetane number ( 46 . 7 ) diesel fuel d7 with high cetane ( 55 . 4 ) diesel fuel d8 . the fuels in each pair had very similar distillation properties and aromatic content . the effect of cetane number increase achieved through changes in the hydrocarbon composition of the fuel ( natural cetane number ) was also compared to cetane number enhancement achieved through the use of ethylhexyl nitrate ignition improver . this comparison involved testing of natural cetane fuels d3 and d4 alongside the cetane enhanced fuel d1 ( prepared by treating fuel d3 with the ignition improver ). the cetane number of fuel d1 ( 45 . 9 ) was matched to that of fuel d4 ( 45 . 5 ), along with aromatic content and distillation properties . in addition , diesel fuel d2 whose cetane number was 31 . 7 , and three gasolines , g1 , g2 and g3 , whose derived cetane numbers equaled 20 . 4 , 26 . 7 and 31 . 2 , respectively , were tested to determine the effect of further reduction in cetane number on the operating range of the engine . fuels g1 , g2 and g3 also allowed the effect of octane number to be evaluated . the effect of aromatic content was investigated using fuels d4 and d7 which contained 44 . 7 and 28 . 7 wt % of aromatics , respectively . volatility effects were investigated by comparing middle distillate fuels d6 and d7 . fuel d6 was more volatile than fuel d7 , as its distillation range was lower , e . g . the 90 % distillation temperatures of these fuels equaled 257 ° c . and 313 ° c ., respectively . fuel d7 had the volatility of no . 2 diesel fuel , while fuel d6 had the volatility of no . 1 diesel fuel or kerosene . volatility effects were also determined by comparing results for diesel and gasoline fuels . fig1 through 5 show no x , avl smoke , hc , co and thermal efficiency of the test engine operated on fuels d3 and d4 whose cetane numbers were 38 . 5 and 45 . 5 , respectively . the same parameters are plotted in fig6 through 10 for fuels d7 and d8 whose cetane numbers were 46 . 7 and 55 . 4 , respectively . in each case , cetane effects are shown for a single speed / load condition but they did not vary significantly over the conditions tested . no x emissions increased as fuel injection timing was retarded , while smoke , hc and co emissions were reduced or remained unchanged . at early ( advanced ) injection timings , the no x emissions are very low since ample time for fuel to vaporize and mix with air leads to relatively homogeneous distribution of fuel within the combustion chamber at low combustion temperatures . for the late ( retarded ) combustion timings , fuel distribution within combustion chamber becomes less homogeneous leading to higher local combustion temperatures and increased no x emissions , but reduced hc , co and smoke . an intermediate injection timing region is used where low no x and smoke can be realized with moderate levels of hc and co . thermal efficiency tended to improve with retarded injection timing , in line with lower hc and co emissions . overall , the effects of differences in cetane number on engine performance and emissions were small and tended to disappear as injection timing was retarded at all engine operating conditions used in this study . where its effect was detectable , cetane number increase seemed to improve co , hc and smoke emissions at advanced fuel injection settings compared against low cetane number fuel . these small effects of cetane number which were observed may be attributed to increased fuel reactivity and advanced start of combustion timing associated with increased cetane number of the fuel . while the higher cetane number fuel appeared to improve co , hc and smoke emissions at advanced fuel injection settings as compared against lower cetane number fuel , the lower cetane number fuel appeared to hold no x reduction to the same low level or to improve it beyond that demonstrated with the high cetane number fuel over the injection setting range investigated ( see fig1 - 10 and table 4 ). the effects of natural and enhanced cetane number are compared in table 4 which contains results of engine tests performed at 1200 rpm , 25 % load . these results demonstrate roughly equivalent effect of the 45 . 5 cetane unadditized fuel d4 and the 45 . 9 cetane ignition enhanced fuel d1 on nox , avl smoke number , hc , co and thermal efficiency of the hcci engine relative to the 38 . 5 cetane base fuel d3 . as shown in fig1 and 12 , fuels d1 and d4 also advanced the start of combustion timing by about 6 degrees crank angle relative to fuel d3 . this effect of cetane number on soc timing is not desirable in hcci engines . in fact , it is counterproductive from the point of achieving higher load operation on hcci engines . increasing cetane number makes it more difficult to achieve optimum combustion phasing at high loads and maximize thermal efficiency of the engine within the constraints of the cylinder pressure and rate of pressure rise limits . as shown in tables 5 and 6 , diesel fuel d2 and gasoline g3 allowed the hcci engine to operate over the broadest speed and load ranges . fuel d2 enabled engine operation at 72 % at 1200 rpm , and 78 % at 1800 rpm . fuel g3 enabled operation at 75 % load at 1200 rpm , and 83 % load at 1800 rpm . the cetane number of fuel d2 and the derived cetane number of fuel g3 were 31 . 7 and 31 . 2 , respectively . on the other hand , gasolines g1 and g2 proved to be excessively resistant to autoignition and severely restricted the operating range of the engine . fuel g2 ( derived cetane number of 26 . 7 ) allowed the engine to achieve 75 % load at 1200 rpm , but limited its operation at 1800 rpm to a single load of 71 %. at 1200 rpm , engine operation on fuel g1 ( derived cetane number of 20 . 4 ) was limited to the narrow load range of 50 to 75 %. at 1800 rpm , hcci combustion was not achieved on this fuel . the testing results also show that engine operating range increases as fuel octane number is reduced . fuel g3 with ( r + m )/ 2 octane number of 63 . 2 provided a larger operating range than g2 , with r + m / 2 of 81 . 2 , which in turn provided a larger operating range than g1 with r + m / 2 of 91 . 2 . octane number is a measure of ignition resistance for gasoline fuels . unlike a standard gasoline engine , hcci engines do not have a spark plug to initiate ignite the fuel . if the ignition resistance of the fuel is too high then the fuel is too difficult to ignite and engine operation is restricted . the effect of aromatic content of the fuel on exhaust emissions and thermal efficiency is shown in fig1 through 17 for the 1500 rpm , 25 % load operating point . the comparison is based on fuels d4 and d7 whose total aromatic content equaled 44 . 7 and 28 . 7 wt %, respectively . in general , the observed effects were small and followed no clear trends for the engine operating conditions used in this study . these results suggest that this hcci combustion system could be relatively insensitive to the aromatics content of diesel fuel . hcci combustion systems seem to be relatively insensitive to the aromatics content of diesel fuel , whereas conventional diesel combustion systems are sensitive to this parameter . this insensitivity to aromatics along with the ability to run well and with low no x emissions using lower cetane number diesel fuel could significantly increase the size of the pool of useable diesel fuel . as shown in tables 5 and 6 , the engine was able to operate up to 78 % load with diesel fuel d2 and up to 83 % load with gasoline fuel g3 . this demonstrates that a wide range of fuel volatility can be used in the engine . fig1 and 19 compare cylinder pressure and heat release rate for fuels d6 and d7 . these fuels differed in volatility but their aromatic content and cetane number were well matched . increased volatility had no significant effect on start of ignition timing and did not impact cylinder pressure , and rate of heat release . the effect of fuel volatility on exhaust emissions and thermal efficiency is shown in fig2 through 24 for engine loads of 25 and 50 %, by comparing d6 and d7 . increased volatility had a small effect on emissions and efficiency . nox , smoke and hc emissions decreased with the more volatile fuel d6 , while thermal efficiency was not affected . these effects could be caused by the more uniform distribution of the more volatile fuel d6 within the combustion chamber of the engine at the time of ignition . however , co emissions results were mixed . these results indicate that a broad range of fuel volatility types can be utilized in this engine . more volatile fuels like kerosene or gasoline can provide emission benefits due to better fuel vaporization and mixing . there are also benefits to using less volatile fuels like diesel since these fuels have higher energy density and will therefore provide better mileage , which is very important to the trucking industry which is a known large consumer of diesel fuels . | 5 |
the liquefier 10 embodying the invention comprises a container or jar 12 removably mounted coaxially with a conventional power unit 14 having a timer selector 16 to control a universal motor for a selected period of time at any one of a number of fixed speeds or alternatively by a push button 18 ( fig1 ) to start a predetermined period of time . a selected motor speed varies but very little with volume changes involving the same ingredients substantially within the range of load volumes generally involved . cutters 20 rotatably journaled in the base 22 of the assembled container 12 are rotated counterclockwise as viewed from above ( fig4 ) when in place on the power unit 14 and a removable cover 24 is provided at the top to confine mixture in the container 12 and having an axial wall 45 to redirect movement of the ingredients to the center and downwardly of the container . the jar 12 as sectionally illustrated in fig3 is a knock - down assembly of parts for cleaning purposes . it has a transparent central container portion 26 having a handle 27 and is enlarged at the upper end with a lip 28 for pouring . it tapers downwardly towards a cylindrical bottom opening 30 where it is terminally reduced and externally provided with a coarse male thread at 32 . a cutter unit 34 having a retaining flange 40 is received against the lower end with a resilient washer 42 between them as releasably secured in sealed relation by a collar 36 . the collar in turn has a coarse female thread at 38 engaging the thread 32 and the pitch of the coarse threads enables the threads to engage each other and establish a sealed relation in approximately one - half turn . the collar 36 is externally fluted at 41 to be supported against rotation on the base 22 . it is desirable to have the housing 12 removable from the base for cleaning purposes with the cutter supporting pedestal 50 large enough at its base ( fig3 ) to provide minimized clearance space at 44 between it and the reduced bottom end 30 of the removable jar 12 to assist in preventing any collection of food particles there which might burden mixture circulation flow rate in the jar . the direction and speed of cutter - induced flow accelerates the flow that moves small and minutes objects through and out of the space 44 , and carries larger food objects at high velocity past the space 44 and repeatedly through the cutter paths for comminution . more particularly , the cutter unit 20 includes the shaped pedestal element 50 which supports a sleeve bearing 52 that journals the cutter drive shaft 54 . the shaft has a driven spider 56 on the lower end and a cruciform cutter 20 on the upper end , the latter preferably being made of two elements 56 and 58 bevel - sharpened on their lower faces at their leading edges 60 to direct several material radially inwardly as indicated by the broken line arrow in fig3 and then directed back through the blades 20 by the downstream convergence and narrowing clearance between the trailing edge 64 of recess 62 and the path of the cutting blades 58 . for the purposes of understanding the high rate of positive circulation and comminution , each blade is formed with its cutting edge 60 parallel to but ahead of a radial line and also is pitched in the direction of rotation 65 to provide a downward propulsion and a swirling of liquid in the jar . as indicated in phantom line 61 the two upper blades 56 are tilted upwardly at approximately 45 ° to provide central cavitation of the jar and an outward and downward propulsion of liquid therefrom into the flutes 53 of the jar against their bottom end walls 63 for a positively driven upward movement in the flutes to circulate the contents in the jar while bringing fresh material , and particularly solid particles , into proximity to the conical pedestal surface . here the axially pitched lower blades 58 are inclined downwardly and outwardly at approximately 45 ° with an inclination to provide an inward movement of liquid which can be referred to as down - and - in towards and through the lower cutters 58 . the lower edge of the conical surface is disposed below the upper rounded inner edge of the cylindrical inner wall of the flange on the jar when assembled to dispose the tips of the lower cutters 58 at approximately the level of the lower ends of the four vertical flutes 53 in the side walls of the jar . the conical wall on the pedestal is horizontally recessed at 62 at circumferentially spaced points to provide horizontally disposed approximately cylindrical surface portions of revolution of 90 ° which are substantially vertical at their top edges 70 and horizontal at their lower edges 72 . the agitated liquid has a circular and a down - and - in movement from the cutters 58 that is smoothly redirected by the recesses 62 in an outwardly direction at their radially shallow downstream edges 64 . this provides agitation in the narrow small area 44 between the pedestal and cylindrical jar surface at the bottom of the jar to keep it flowing with the redirected flowing liquid as propelled to enter the vertical flutes 53 of the jar and circulate larger solid portions in the jar quickly up the sides of the jar and back through the cutter blades for a nondelaying repeated action that is substantially independent of the initial sizes of the solids being comminuted in the liquefied and aerated mixture at different selected speeds . the down - and - out blades 56 operate initially to reduce large particles rapidly while the down - and - in blades 58 comminute solids with a rapid radial flow of mixture that is substantially uninterrupted with respect to a timed cycle . the tapered wall portions 63 between the recesses 62 greatly dampen any circulatory movement of mixture induced by the cutters and thereby augment the radial movement . compositely , the cutters 56 and 58 also aspirate downwardly liquid from the center of the jar to develop a column of air extending to the cutters . in doing this , the cutters develop a vortex and drive the aspirated liquid up the flutes 53 of the jar to carry liquid circulation to the top of the jar and establish a determined liquid flow path down the center and up the sides of the jars . preferably , the cover 24 for the container has a downwardly opening annular space 46 at the top of the jar and an axial flange 48 with circular radial sealing flanges 50 which receive or are engaged by the mix rising on the side walls . they redirect a swirling mix inwardly where it engages a central flange 45 carrying a detachable ingredient measuring cup 51 and direct flow downwardly for return by gravity to the cutters 20 for further comminution of solid particles in the mixture as described . also , where solids are hydraulically and pneumatically forced to pass in and out of recesses 62 across the path of cutter movement as at trailing stationary edges 64 , the constancy of cutter action is related to the constancy of mixture flow . accordingly , where everything must pass through the cutters 56 and 58 each time around , the dominant variable factor is the excursion distance from the cutters up the wall of the jar and back down its center , with the effect of gravity being a constant and the cutter speed being substantially the same under load variations within this range . the cutters in the present invention propel and cavitate all volumes of liquid that are one cup or greater , in a jar capable of handling five cups where the depth of two cups is approximately the mean inside diameter of the fluted jar , and , the cutter diameter closely approaches the minimum diameter at the bottom of the jar . therefore , solids that may be present in the mixture in both instances circulate approximately the same distance and number of times to and from the cutters 56 and 58 in a timed cycle . the measuring cup 51 is mounted in the cap 24 with a bayonet joint having two teeth 70 received through grooves 72 to lock under inclined cam edges on the inner circular track of the sleeve portion 74 . this measuring cup 51 can be removed during a timed liquefying operation to add measured ingredients when desired without permitting any liquid mix to escape during a mixing operation . the sleeve portion 74 redirects centrally and downwardly the mixture driven upwardly on the side walls in its flow path of movement . | 0 |
the following description references fig1 through 11 of present application in an indistinct manner , in which the modular system of niches or crypts 10 can be seen , which are formed by different assembly modules 20 for the depositing of ashes and / or dry remains . the modular system 10 can be mounted in open and / or enclosed areas in a very easy , fast way and without the need of requiring anyone with a prior high skilled level for its installation . examples of open areas where the modular system 10 could be installed include cemeteries , church yards or any area in the open air suitable for said purposes . the modular system 10 can also be installed in appropriate enclosed areas . the modular system for niches or crypts 10 is made up of at least two assembly modules 20 . the assembly modules 20 are formed by horizontal plates 21 and by vertical plates 22 which are interconnected by means of connector elements 23 ′, 23 ″ and / or 23 ′″. said connector elements have at least two arms ( 36 ). the horizontal plates and / or vertical plates may be manufactured of various materials which do not bend easily but which in turn do have a certain amount of flexibility such as plastics , woods , metals which tend to have certain flexibility such as aluminum , cardboard , corrugated cardboard , etc . the laminate plates 21 , 22 can be recoated with an aesthetically pleasing material , such as ceramic or marble or even yet a light layer of cement as for example cellular concrete with the end goal that the modular systems have both an adequate support as well as a visually pleasing aesthetic . additionally , given that the sheets are made of materials such as aluminum or stainless steel they can be highly resistant to environmental conditions such as , for example oxidation . additionally , given that the sheets can be recoated with some of the above mentioned materials , the sheet which is still made of a material which can become oxidized would be maintained in optimal conditions thanks to the recoating with any adequate material which additionally grants it a visually acceptable aesthetic . the assembly modules 20 can be of a width and a height which by way of example , but not limited to , approximately between 25 cm by 40 cm to approximately between 35 cm by 40 cm and a depth of approximately between 20 cm to approximately 60 cm . however , the modular system for niches and crypts 10 can contain assembly modules 20 of various sizes , that is , the connector elements 23 ′, 23 ″ or 23 ′″ in conjunction with the horizontal plate 21 and the vertical plate 22 allow for a variety of sizes of the width and the height of the assembly modules 20 , in this way allowing a design for the modular system 10 according to the client &# 39 ; s specifications . the assembly modules 20 are constructed by means of horizontal plates 21 and vertical plates 22 connected by means of connector elements 23 ′, 23 ″ and / or 23 ″′ through its arms . as can be seen from the figures , all the plates 21 and 22 have two cavities 24 which are near to a first end and two recesses 25 on a second end opposite to the first end , into which any of the connector elements 23 ′, 23 ″ and / or 23 ′″ could be introduced into , such as is shown in fig1 and 11 . each cavity 24 is found near the lateral parts of the first end , while each recess 24 is found on the lateral parts of the second end . at the second end of the plates 21 and 22 , flanges are found 26 and 26 ′ such as can be seen starting in fig9 . it should be mentioned that said flanges 26 and 26 ′ are constructed in such a way that the connector elements 23 ′, 23 ″ and / or 23 ″′ can be introduced in an easy way ; specifically , the connector elements can be slideable along the length of the recess 24 encircling said flange 26 , such as will be described . the connector elements 23 ′, 23 ″ and / or 23 ″′ have on their back part a horizontal aperture 27 and a vertical aperture 28 , both in the shape of a “ c ”. more preferably , the connectors 23 ′, 23 ″ and / or 23 ″′ are constituted by at least five different walls . a first wall with a first length has a first direction . a second wall with a second length has a second direction substantially perpendicular to the first wall . a third wall with a third length has a third direction which is vectorially opposite to the first direction and consequently substantially perpendicular to the second wall . a fourth wall with a fourth length has a fourth direction which is vectorially opposite to the second direction and consequently substantially perpendicular to the third wall . finally a fifth wall with a fifth length , similar to the first length , has a fifth direction which is vectorially opposite to the first direction and consequently substantially perpendicular to the fourth wall . between the first and fifth wall , same which are opposite , an aperture 27 is formed . the length of the third wall is equivalent to the sum of the first wall , the fifth wall and the aperture . in this way , between the walls of the connectors 23 ′, 23 ″ and / or 23 ″′ an inner space is formed . the inner space of the connectors is configures to receive the flanges of the plates 21 and / or 22 within the same , in such a way that upon sliding the connectors in the inner space , said connectors , by means of their walls encircle the flanges 26 , 26 ′ of the plates and wherein the first and fifth wall of the connectors , upon the connectors with the plates being in a mounted position , they are in near proximity to the corresponding cavity 24 and / or the recess 25 . similarly , the plates 21 and 22 have a central rim ledge 31 , a first lateral rim ledge 33 and a second lateral rim ledge 32 , wherein the second lateral rim ledge is opposite to the first lateral rim ledge . as can be seen , starting from fig1 , the upper part of the connectors 23 ′, 23 ″ and / or 23 ″′ has a horizontal aperture 27 which begins at an end 29 and ends at an end 30 opposite to the end 29 , that is , the aperture 27 is continuous along the length of the horizontal axis of the connector element 23 ′, 23 ″ and / or 23 ″′. the aperture is introduced into the flanges 26 of the plate 21 and the connector slides horizontally up until the central rim ledge allows it to , such as is shown in fig1 . in this way the cavities 24 of the plate 21 remain occupied by the connector elements 23 ′, 23 ″ and / or 23 ′″. similarly , the flanges 26 ′ of the plate 21 are introduced into the apertures 27 of the connectors 23 ″′, wherein the connectors 23 ″′ slide horizontally until they come into contact with a central rim ledge , which limits the horizontal movement of the connectors such as is shown in fig1 . in this way the horizontal plate 21 is assembled with the connectors 23 ′, 23 ″ and / or 23 ″′ through its arms , in such a way that the back part of the connectors 23 ′ or 23 ″ is oriented with the back part of the connectors 23 ″′. as can be seen starting from fig1 , the rim ledge 34 , 35 of the connectors 23 ′ or 23 ″ remains exposed in view such that the arms of the connector elements 23 ″′ remain hidden from view . the connector elements 23 ′, 23 ″ and / or 23 ″′ allow connecting different sizes of horizontal plates and / or vertical plates by means of connector arms , in this way allowing for variation in the size of the vertical plates and / or horizontal plates , that is to say , assembly modules 20 can be constructed in different sizes by varying the length of the horizontal or vertical plates , whether it is the width , the height or both to achieve a modular system 10 in different sizes of the assembly module 20 . for example , the client or clients can request a niche or crypt in a smaller size , while other desire one of a larger size , which is possible thanks to the connector elements 23 ′, 23 ″ and / or 23 ″′ which are being described in present invention , given that they would allow to construct a modular system 20 according to the different needs of the clients . the connector elements 23 ′, 23 ″ and / or 23 ″′ have similar connection structural features , the difference being the intermediate element 34 , 35 which is found in the same . the connector element 23 ′ has an intermediate element 34 which is beveled and which rests over a vertical plate and / or supports a vertical plate , as can be seen for example starting from fig1 . the intermediate element 34 in a preferred embodiment can have an intermediate element which is longer than that which is shown in fig6 ( not shown ). the intermediate element in another preferred embodiment can have a more rectangular shape , in this way forming an intermediate element 35 , which itself also provides support to the modular system 20 in its assembled position . in yet another preferred embodiment , the connector element does not possess any beveled element , as can be seen for example starting from fig8 . however , said connector element is found oriented in such a way that it remains hidden from human view , that is , it is found at the back part of the modular system . as can be seen starting from fig4 and 5 , the lateral rim ledges 32 and 33 of the plate 22 and the lateral rim ledges 32 and 33 of the plate 21 have distant lengths , that is , the length of the lateral rim ledges 32 and 33 of the plate 21 are longitudinally smaller than the lateral rim ledges 32 and 33 of the plate 22 . the lateral rim ledges 32 and 33 of the plate 21 are smaller with the end goal that any of the connectors 23 ( 23 ′, 23 ″ and / or 23 ″′) can correctly couple the plates 21 and 22 in a firm and secure manner . as was mentioned previously , the connectors 23 ′, 23 ″ and / or 23 ″′ have an inner space into which the flanges 26 and 26 ′ of the plates 22 are introduced into , where the connectors slide in a vertical manner and wherein the rim ledge 31 , 32 and 33 limit the vertical movement such as is shown , for example in fig3 . it should be mentioned that the rim ledges 32 and 33 of the plates 21 and 22 remain exposed in full view , in so far as the rim ledges 31 of the plates 21 and 22 are found at the back part , that is , they remain hidden from view . a horizontal plate 21 and a vertical plate 22 once assembled , as is shown in fig3 , the procedure is repeated with the end goal of assembling an assembly module 20 as is shown in fig2 and the connector elements 23 ′, 23 ″ and / or 23 ″′ will allow the addition of however many more assembly modules 20 will be necessary . the vertical plates have four orifices uniformly distributed towards the center ( not shown ) which have the objective of providing ventilation to the dry remains . the arms of the connector elements 23 ′, 23 ″ and / or 23 ″′ may be of different lengths with the end goal of achieving niches or crypts of various sizes , and also to be able to meet different design requirements according to the specifications of the clients , dimensions of the places where they will be placed , among other considerations . persons skilled in the art will easily understand how changes to the present invention can be accomplished without deviating from the summarized concepts of the above description . it is considered that these changes are included to lie within the claimed scope of present model . consequently , the particular embodiments previously described in detail are merely illustrative and not limitative in terms of the scope of present model , to which full extension of the attached claims should be granted , in addition to all and any equivalent of the same . | 0 |
with reference first to fig1 a building wiring system interface utilizing the present invention is shown generally at 2 . this building wiring system consists of a cable 4 having multiple signal conductors 6 in the form of twisted wires 8 that are surrounded by individual shielding 10 , which could take on the form of a foil . the conductors 6 are terminated by an electrical connector 12 incorporating the present invention . the electrical connector 12 includes a main housing 14 having an edge - card receiving slot 16 and a rear cover 18 . the connector 12 further includes a latch 20 for retaining the connector 12 in an access box 22 . while the connector 12 utilizes an integrally molded latch 20 , for snapping the connector 12 into the box 22 , other mounting techniques may be used , such as a screw or other fastener . the box 22 is a rectangular shell having a forward opening 24 , a rear end 26 and a cable exit 28 . the forward end includes latches 30 for retaining an insert 32 therein . the insert 32 includes a pcb 34 having a rear end 36 formed as a card edge with multiple conductors 38 thereupon . a connector 40 is incorporated onto the pcb 34 . in particular , this connector 40 is a modular jack receptacle and provides an interface 42 for receiving a modular jack plug ( not shown ). the interface 42 is surrounded by a bezel 44 that includes latch arms 46 to engage latches 30 in box 22 when the insert 32 is placed within the box 22 . a rear cover 48 is provided to close the rear end 26 of the box 22 once the connector 12 is mounted therein . the rear cover 48 includes a tab 50 that is received within the slot 28 of box 22 when the cover 48 is affixed thereto . the tab 50 , in cooperation with the edges of the slot 28 , engages the cable 4 to provide strain relief and possibly grounding of any general shielding of the cable 4 to the box 22 . with reference now to fig2 the electrical connector 12 according to the present invention is shown mounted within the box 22 . the box 22 includes a mounting wall 52 which is engaged by the latch 20 for retaining the connector 12 therein . if the connector box 22 is conductive , either by having been formed from a conductive material or a metallized plastic , and the connector 12 is also advantageously formed of conductive material , such as metallized plastic , by placing the connector 12 within the box 22 , the connector 12 will be electrically commoned thereto . this will have further advantageous effects . with reference now to fig3 the electrical connector 12 will now be described in greater detail . the electrical connector 12 incorporates a main housing 14 . the main housing 14 has a mating side 54 which in this example includes the card receiving slot 16 ( fig1 ). it is important to note that while the present invention can be advantageously used in a card - edge connector style , that the invention should not be limited . the main housing 14 also includes an open cable side 56 that is divided into a plurality of compartments 58 by partitions 60 . advantageously , the main housing 14 will be formed from a conductive material or metallized plastic . a plurality of contact carrying modules 62 are constructed to be received within compartments 58 . the contact carrying modules 62 include opposing latches 64 so that they can be snapped in place within the main housing 14 . the contact carrying module 62 is advantageously formed of insulative material although selective metallization could be used if desired . each contact carrying module 62 includes two contacts 66 that are best seen and described in fig4 and 5 . these contacts 66 include a mating end and a wire termination end 70 . the connector 12 further includes a rear cover 18 that is fittable to the main housing 14 by a pair of latch arms 72 designed to engage corresponding catches 74 upon the main housing 14 . the cover 18 further includes multiple u - shaped cable tabs 76 . it is also envisioned that tabs 76 may be omitted . the rear cover 18 will also be manufactured from a conductive material or advantageously a metallized plastic . with reference now to fig4 and 5 , the contact 66 will be described in greater detail . the contact 66 includes a mating end 68 that , in this embodiment , is a resilient tongue for engaging the conductive pads 38 of the card edge 36 . various configurations of this mating end 68 may be realized depending on the interface desired . the contact 66 further includes a cable termination end 70 that is formed as an insulation displacement contact ( idc ). the idc includes a wire receiving slot 78 for receiving an insulated wire and making connection thereto , as is well known in the industry . the wire termination end 70 could take on various other configurations , such as a crimp connection or a solder termination . a body section 80 is located between the mating end 68 and the wire termination end 70 . the body portion 80 includes a retention lance 82 for incorporating the contact 66 into the contact carrying module 62 . various materials may be used for the contact 66 as desired and it may be advantageous to include a precious metal contact patch 84 for engaging the conductive pads 38 of the card edge 36 . with reference now to fig6 a body 84 that substantially makes up the contact carrying module 66 will be described in detail . the body 84 carries the two latches 64 extending from a front surface 86 thereof . the latches 64 retain a contact carrying module 62 within the main housing 14 in a manner best seen in fig1 . the body 84 includes a rear idc portion 88 having a pair of contact passageways 90 that extend through the body 84 and open at the front surface 86 so that a contact 66 may be disposed therein ( best seen in fig1 ). a wire receiving slot 92 extends across the idc termination portion 88 and the associated contact passageways 90 and is constructed for receiving the individual wires 8 of the twisted - pair conductors 6 therein . additionally , on either side of the contact carrying passageway 90 are guide slots 94 that extend into the module 84 basically parallel to the contact receiving passageways 90 . these guide slots 94 , along with large chamfers 96 on both sides of the wire receiving slots 92 , are useful for stabilizing a wire termination tool ( not shown ) that would be used to stuff the insulated wires into the idc contact slot 70 of the contact 66 in a manner well known in industry . with reference now to fig7 the main housing 14 will be described in greater detail . the open cable side 56 of the main housing 14 is shell - like and defined by a lower wall 98 , opposing side walls 100 , 102 and upper wall 103 . this shell - like open cable side 56 is further divided into a row of compartments 58 by partitions 60 that extend between the lower wall 98 and the upper wall 103 . advantageously , in this embodiment , the partitions 60 are formed as tongues having a chamfered surface 104 extending on a side thereof to an end 106 of the tongue 60 . the end 106 of tongue 60 is slightly recessed from the open cable side 56 of the connector 14 . each compartment 58 further includes a table 108 having an inverted , u - shaped , end 110 defining a passageway 112 thereunder and a passageway 114 thereover . the passageway 114 extends through the housing 14 to the mating side 54 while the passageway 112 exposes a latch 116 for retaining the contact carrying module 62 . the table 108 is used to position the contact module 62 within the main housing 14 . the upper wall 103 is considerably thicker than the lower wall 98 or the side walls 100 , 102 in this embodiment . the reason for this is that the upper wall 103 carries at least a first portion of a wire exit saddle 118 . the first portion of this wire exit saddle 118 includes a pair of scalloped saddle surfaces 120 that are separated by a tab receiving trough 122 that extends into the wall 103 for receiving the u - shaped tabs 76 of the cover 18 , as will be described below . as mentioned above , the main housing 14 would either be manufactured from a conductive material or molded from plastic and metallized such that the main housing 14 would provide shielding or anything received therein . with reference now to fig8 the end cover 18 that is constructed to close the open cable side 56 of the main housing 14 will be described in greater detail . the end cover 18 includes latches 72 to engage the catches 30 of the main housing in order to fix the cover 18 to the main housing 14 . the cover 18 includes a body portion 124 having a rearward side 126 and a connector side 128 . an interior surface 130 of the rearward side 126 faces the connector side 128 . combined with side walls 132 , 134 , lower wall 136 and upper wall 140 , a trough - like structure is formed . the trough - like structure is further divided into compartments 58 a by second partitions 60 a that correspond to the partitions 60 of the main housing 14 , as will be described below with reference to fig1 and 12 . the second partition 60 a also include chamfers 104 a that extend along sides of the partition 60 a to ends 142 . it is important to note that at least a portion of the chamfer 104 a of the partition 60 a extends beyond the connector surface 128 in order to provide the ends 142 of the partition 60 with some flexibility . in this particular embodiment , the second partition 60 a itself extends a small distance 144 beyond the connector edge 128 . further , the end 142 of the partitions extends upwards to a ledge 146 such that the second partitions 60 a would be received between the lower wall 98 and the upper wall 103 of the main housing 14 when the cover 18 is fitted thereto . advantageously , the cover 18 would be manufactured from a conductive material or a metallized plastic mold . a portion 148 of the partition 60 a extends above the ledge 146 to be received within slots 150 formed in the upper wall 103 of the main housing 14 that correspond to the partition 60 therein . in addition , located along the upper wall 140 of the cover 18 are a plurality of u - shaped tabs 76 constructed to be received within the troughs 122 of the main housing 14 . these legs of the u - shaped tabs 76 may take on various lengths as desired and provide some strain relief for the twisted - pair wire 6 and discontinuity in any pathway . as mentioned above , these tabs 76 are optional . at the base of the u - shaped tab 76 is a second saddle portion 152 that will be disposed opposite the first saddle portion 118 in the main housing 14 . with reference now to fig9 the electrical connector 12 is shown in partially assembled form . the contact carrying modules 62 , with the contacts 66 therein , are shown received within the main housing 14 . the cover 18 is positioned to be mounted upon the main housing 14 . as can be seen , the partition 60 a will be received between adjacent contact carrying modules 62 and the upper portions 148 of the partition 60 a will be received in the slots 150 . additionally , if desired to improve the flexibility of the cover 18 , reliefs 154 may be provided in the rear surface 126 . with reference now to fig1 , the electrical connector 12 is shown in assembled form . the contact carrying module 62 with the contact 66 is fitted to the housing 14 by the latch members 64 engaging corresponding latches 116 formed in the main housing 14 . the contact 66 extends through the contact carrying passageway 90 such that the mating end 68 is disposed in the card edge receiving slot 16 on the mating end 54 of the main housing 14 . the contact 66 is retained therein by the locking lance 82 that is received in a recess 156 of the body 84 in order to further retain the contact 66 . a staking operation can be performed that utilizes the recess 158 above the contact lance 82 prior to assembling of the module 62 with the main housing 14 to further assure contact retention . at this point , the main housing has been assembled to the extent shown in fig9 . with the cover 18 attached to the main housing 14 as shown in fig1 , the open cable side 56 of the main housing 14 has been closed . a wire exit 160 is defined by the two saddle portions 120 , 152 of the main housing 14 and cover 18 respectively for each of the compartments 58 . this wire exit 160 is configured to be slightly smaller than that of the wires exiting such that an interference will exist . this interference is advantageously taken advantage of by allowing the shielding 10 that surrounds the wires 8 to extend into the compartment and be terminated only slightly above the rear idc portion 88 of the contact module 62 when the various conductors 6 are being terminated . once the cover 18 is attached to the main housing 14 , it is easily recognized that the saddle portions 120 , 152 will come into engagement with the shielding 10 . as both the main housing 14 and the cover 18 are manufactured from either conductive material or metallized plastic , the saddle surfaces 120 , 152 are electrically commoned to the shielding 10 . returning to fig1 and fig2 it can be seen that as a result of closing of the rear cover 18 upon the main housing 14 with the conductors 6 extending therefrom , the shielding 10 of the individual conductors is slightly compressed in the region 161 indicating engagement with the housing 14 and cover 18 . with reference now to fig1 and 12 , in addition to providing for the commoning of the conductive main housing 14 and rear cover 18 to the shielding 10 of the individual conductors 6 by way of the saddle portions 120 , 152 , it is necessary to also assure that the termination and contacts within adjacent compartments 58 are completely isolated from one another . this is reliably achieved by the first partitions 60 of the main housing 14 and the second partition 60 a of the cover 18 being provided with respective chamfers 104 , 104 a and configured such that the respective ends 106 , 142 also overlap and result in a slight interference 162 within the space 164 between adjacent modules 84 contained within their respective compartments 58 . as can be imagined , this space 164 and the associated partition walls are extremely thin and , hence , some flexibility of the partitions 60 , 60 a is realized . furthermore , it is this space requirement that prevents easily manufacturing these partitions as a single piece extending outward from either the cover 18 or the housing 14 exclusively . as each of the partitions 60 , 60 a are conductive , a shielding partition is formed between adjacent compartments 58 . advantageously then , what is realized from the present invention is a structure that continues the shielding 10 provided to the twisted pair of wires 8 to a compartment 58 within a connector 12 such that a fully shielded twisted - pair interconnection is provided , thereby greatly reducing the effect of cross - talk from adjacent signal conductors 6 and any spurious electromagnetic fields . | 7 |
turning to fig1 a latch needle 1 which serves as a knitting tool has a head or hook 2 adjoined by a throat 3 which , in turn , is adjoined by a needle cheek 4 . in the needle cheek 4 a longitudinal sawslot 6 is provided in which a needle latch 7 is arranged for pivotal motion about a latch bearing 8 . the needle cheek 4 is adjoined , with the intermediary of a groove 9 , by a blade 11 which , during operation , is received in a needle channel of the knitting machine . the blade 11 which is provided with a plurality of recesses 12 giving the blade a meandering configuration , has a butt 14 at its end 13 opposite the hook 2 . the butt 14 is formed as a one - piece member with the blade 11 and extends perpendicularly to the longitudinal direction 16 of the latch needle 1 . the periphery of the butt 14 passes over to the blade 11 at arcuate transitional zones 17 , 18 . the latch needle 1 has two opposite , parallel , relatively wide side faces 21 , 22 between which relatively narrow , opposite edge faces , that is , the upper needle face 23 and the needle back 24 are located . also referring to fig3 between the upper needle face 23 and the side faces 21 , 22 transitional regions 26 and 27 are provided which are slightly rounded and thus form a transition which is void of sharp edges . corresponding transitional regions 28 , 29 are provided between the needle back 24 and the side faces 21 , 22 . the opening of the sawslot 6 at the upper needle face 23 is bordered by oblique flanks 31 , 32 which form , without sharp edges , zones of transition to the upper needle face 23 . similar oblique flanks 54 , 55 ( fig8 ) may be provided at the bottom opening of the sawslot 6 , that is , at the region of transition to the needle back 24 . the initial , starting component in making the latch needle 1 is a needle blank 33 which is shown in fig2 and which has been stamped out of a thin steel ribbon ( stock material ). the contour 34 of the needle blank 33 is essentially determined by the stamping tool and includes the side faces 21 , 22 ( also shown in fig4 ) as well as the upper needle face 23 and the needle back 24 . the needle blank 33 , in its state after stamping from the steel ribbon , is asymmetrical relative to the longitudinal central plane 36 which extends parallel to the side faces 21 , 22 . while along the contour 34 at the upper face as shown in fig4 the needle blank 33 has burrs 34 , the side 38 is rounded . the fractured surfaces 39 lying therebetween are not planar and in most cases are not exactly perpendicular to the side faces 21 , 22 . also referring to fig4 to remove at least the burr 37 which projects by a burr height g beyond the side face 21 an embossing tool 41 is used which is composed of an upper tool 41a and a lower tool 41b and by means of which the stamped blank 33 is converted into an embossed blank 33a . a die 42 which has an engraved pattern is formed in the embossing tool 41 and corresponds in shape to the embossed blank 33a from which the base body of the latch needle 1 is formed . in the closed position of the embossing tool 41 the inner clearance w of the die 42 of the embossing tool 41 corresponds to or is slightly less than the thickness d of the stamped blank 33 . to obtain a desired edge deformation of the stamped blank 33 , rounded edge portions 44 , 45 , 46 and 47 are provided in the upper tool 41a and the lower tool 41b along the border of the engraved pattern of the die 42 . otherwise the die 42 is bounded by planar faces . a stamped blank 33 positioned in the die 42 is therefore , when the embossing tool 41 is closed , deformed particularly in the region of its outer edges whereby its thickness d remains essentially unchanged . the stamped blank 33 is transformed into a configuration ( that is , into the embossed blank 33a having an outer contour 34a ) which is essentially symmetrical relative to its longitudinal central plane 36 as shown in fig5 . both the burrs 37 and the side 38 of the stamped blank 33 are deformed in the course of the embossing step by means of the embossing tool 41 , whereby the transitional regions 26 , 27 , 28 , 29 are formed with radii which are determined by the edge regions 44 to 47 of the die 42 . the direction of material flow is , related to the cross - sectional surface shown in fig4 and 5 , approximately diagonal to the middle of the cross section . a more pronounced deformation of the stamped blank 33 is possible where the fractured faces 39 are smoothened by virtue of the flow of material . independently therefrom , burr - free , positively rounded or chamfered , strengthened edge regions are obtained by the embossing operation . this applies for the edges in the yarn gliding region of the throat 3 , the cheek 4 and the groove 9 as well as to the edges of the blade 11 . the edge - rounding in the thread gliding region improves the properties of the latch needle 1 as far as handling of the yarn during the knitting operation is concerned . the rounding of the edges of the blade 11 improves the gliding properties of the latch needle 1 in the needle channel . the obtained surface strengthening is of advantage in either case . the embossing operation positively affects particularly the dynamic strength of the butt 14 . this is achieved by embossing particularly the arcuate transitional zones 17 and 18 between the blade 11 and the butt 14 . the respective surfaces and edges are throughout smoothened or rounded and , as result , the butt 14 is capable of withstanding higher continuous dynamic loads . during the embossing operation microscopic surface irregularities are eliminated and the surface is smoothened particularly in the regions of the transitions 17 , 18 . during the subsequent operation the sawslot 6 is formed in the embossed blank 33a . for rounding or blunting the edges bounding the sawslot 6 , an embossing step performed on the needle cheek is included in the manufacturing sequence for making the latch needle 1 . in its mid zone , the sawslot 6 shown in fig8 is bounded by two mutually parallel sawslot flanks 51 , 52 adjoined at the upper needle face 23 of the latch needle 1 by the oblique faces ( flanks ) 31 , 32 . likewise , at the needle back 24 oblique flanks 54 , 55 are formed which , similarly to the oblique flanks 31 , 32 , form an acute angle α of , for example , 60 ° with one another . the oblique flanks 31 , 32 ; 54 , 55 shown as planar , may be rounded or may be arranged at another angle to one another . turning to fig7 and 9 , the embossing punches 57 and 58 serve for forming the oblique flanks 31 , 32 ; 54 , 55 . the upper embossing punch 57 which is conformed in its longitudinal direction to the curvature of the embossed blank 33a in the region of the throat 3 and the cheek 4 , has a trapezoidal cross section with a narrow end face 59 whose width is slightly less than the distance of the sawslot flanks 51 and 52 from one another . the cooperating lower embossing punch 58 has a trapezoidal cross section as well , but is of straight configuration corresponding to the needle back 24 . the embossing punches 57 and 58 are moved towards the embossed blank 33a held therebetween and press a cross - sectionally trapezoidal longitudinal groove 61 , 62 in the upper needle face 23 and the needle back 24 , respectively . the edges 63 and 64 provided during this step in the transitional zone to the upper needle face 23 and the needle back 24 are not sharp but rounded . the outer contour 34a , together with the external transitional regions 26 , 27 , 28 and 29 and the edges 63 and 64 , is defined exclusively by means of shaping steps which do not involve material removal ( cutting ). after completion of the embossing process , one half of the sawslot 6 is milled , starting from the longitudinal groove 61 , to the vicinity of the longitudinal groove 62 , as a result of which first a thin sawslot bottom remains . in a consecutive stamping operation the sawslot bottom is broken through to obtain a throughgoing passage 60 . the sawslot 6 obtained in this manner has a contour such as shown at 65 in fig9 . by pre - forming the longitudinal grooves 61 , 62 before providing the sawslot 6 with the cutting operation proper , not only the sawslot edges are broken off or rounded but also the material at the sawslot rim is strengthened . in this manner the edges of the sawslot 6 designed to receive and support the needle latch 7 are less prone to wear under the effect of the blows delivered by the back - and - forth snapping needle latch 7 . furthermore , knitting machine needles are known which have no throughgoing aperture 60 and thus in their manufacture the last - named stamping operation and the embossing of the longitudinal slot 62 are omitted . turning to fig1 , instead of the embossing punches 57 , 58 rollers 71 , 72 may be used which have a trapezoidal pattern on their cylindrical surface . for forming the longitudinal grooves 61 , 62 , the blank 33 , 33a is guided between the rollers 71 and 72 in such a manner that the rollers press into the upper needle face 23 and the needle back 24 or the rollers 71 , 72 are guided along the blank 33 , 33a . during such an operation the roller 72 moves on a linear track 73 while the roller 71 is guided along a curvilinear path 74 corresponding to the needle contour . after forming the grooves 61 , 62 the subsequent shaping is performed as described above . independently of whether the grooves 61 , 62 are made by the embossing punches 57 , 58 or by the rollers 71 , 72 , they run out in a gradual manner at their ends ; this may be achieved by the oblique surfaces 76 , 77 at the frontal faces of the embossing punches 57 , 58 or by a corresponding positioning of the rollers 71 , 72 . thus , according to the invention , as part of the manufacturing process , the knitting tools 1 are stamped out from stock material , such as a steel ribbon . the stamped needle blanks 33 obtained in this manner are submitted to an embossing operation in which sharp edges , particularly burrs 37 , obtained as a result of the stamping operation , are eliminated by a plastic deformation of the stamped blank 33 . for example , in the manufacture of needle sawslots 6 , the embossing operation precedes a cutting operation ( such as milling ) in the shaping sequence . in some instances , however , it is advantageous to first perform the milling operation and then submit the knitting tool to an embossing step . in such a case first a depression 61 is embossed in the blank , and the bottom of the depression 61 is subsequently removed by a cutting operation until the desired configuration of the depression is obtained . the rim of the depression appearing first by an embossing step is free from sharp edges without the need for subsequent machining , and also , a deburring is not required . the strengthening of the material achieved as a result of the embossing operation yields additional advantages . it will be understood that the above description of the present invention is susceptible to various modifications , changes and adaptations , and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims . | 3 |
referring to fig3 to 4 , there is illustrated a method of making a dram according to an embodiment of the present invention . fig3 is provided to show a layout diagram of a dram in accordance with an embodiment of the present invention . fig4 a to 4k are cross - sectional views showing a method of making a dram in accordance with an embodiment of the present invention . first , two field insulation films 22 for defining an active region are formed with a constant interval on a semiconductor substrate 21 , using a local oxidation of silicon ( locos ) method , as shown in fig4 a . subsequently , a first thermal insulation film is thermally formed on the whole surface of the semiconductor substrate 21 , including the field insulation films 22 and then a first conductor and a second cvd insulation film are formed , in this order , on the surface of the first thermal insulation film , using a chemical vapour deposition ( cvd ) method . subsequently , the first thermal insulation film , the first conductor and the second cvd insulation film are subjected to a patterning process including a photolithography process and an etch process , using a gate mask . as a result , word lines are formed uniformly spaced from each other respectively on the active region and the two field insulation films 22 . as shown in fig4 a each word line includes a gate insulation film 23 formed on the semiconductor substrate 21 , a gate electrode 24 formed on the gate insulation film 23 and a gate cap insulation film 25 formed on the gate electrode 24 . subsequently , a conductivity type of impurity ions are implanted on the semiconductor substrate 21 using each of the word lines as masks for impurity implantation , thereby forming impurity regions 26 serving as source regions and drain regions in the surface of the semiconductor substrate 21 corresponding to the area between the word lines . subsequently , a third insulation film is deposited on the whole surface of the semiconductor substrate 21 including the word lines and the field insulation films 22 using a cvd method and then etched - back by a reactive ion etching rie method to form side wall insulation films 27 at the side walls of the word lines . thereafter , a fourth cvd insulation film 28 is deposited on the exposed whole surface of the semiconductor substrate 21 including the side wall insulation films 27 and the word lines , using a cvd method . here , silicon can be used as a material of the semiconductor substrate 21 . an oxide or a nitride can be used as a material of the first thermal insulation film to the fourth cvd insulation film . also , a metal or a polysilicon doped with an impurity can be used as a material of the first conductor . subsequently , the fourth cvd insulation film 28 is selectively etched to merely remove a portion located between the word lines formed on the field insulation films 22 and the word lines formed on the active region , thereby forming capacitor contact holes between the word lines formed on the field insulation films 22 and the word lines formed on the active region , as shown in fig4 b . at this time , there merely remains portions of the fourth cvd insulation film 28 which are located between the word lines formed on the field insulation films 22 and between the word lines formed on the active region . storage nodes of the capacitor will thereafter be formed in the capacitor contact holes . here , an oxide or a nitride can be used as a material of the fourth cvd insulation film 28 . as shown in fig . 4c , thereafter , a second conductor is deposited on the exposed whole surface using a cvd method and then etched - back uniformly until the surface of the fourth cvd insulation film 28 is exposed , thereby forming conductor plugs 29 in the capacitor contact holes and on the surface of the remaining fourth cvd insulation film 28 which are located between the word lines formed on the field insulation films 22 . here , a metal or a polysilicon doped with an impurity can be used as a material of the second conductor . subsequently , a fifth cvd insulation film 30 for a buffer layer is thickly deposited on the exposed whole surface as shown in fig4 d and then patterned to remove a portion between two word lines of the active region . upon patterning the fifth cvd insulation film 30 , a dry etch process is used . thereafter , a wet etch is performed using the fifth insulation film 30 for a buffer layer as an etch mask , to remove a portion of the conductor plug 29 and a portion of the remaining fourth cvd insulation film 28 formed between two word lines of the active region . thus , a bit line contact hole is formed between two word lines of the active region . as shown in fig4 f , subsequently , a third conductor having a planarizing surface is deposited using a cvd method on the exposed whole surface including the remaining fifth insulation film 30 for a buffer layer and the bit line contact hole so that the bit line contact hole is filled completely . a sixth cvd insulation film 31 for bit line definition is deposited on the third conductor using a cvd method . subsequently , an etch mask 32 for bit line definition having a width wider than that of the bit line contact hole is formed on a portion corresponding to the upper side of the bit line contact hole , of the surface of the sixth cvd insulation film 31 , and then the sixth cvd insulation film 31 , the third cvd conductor and the fifth cvd insulation film 30 for a buffer layer are etched together , thereby forming a bit line 33 in the bit line contact hole . at this time , on the surface of the bit line 33 , a portion of the sixth cvd insulation film 31 remains and at the side walls of the bit line 33 , a portion of the fifth cvd insulation film 30 for a buffer layer remains . as shown in fig4 g , subsequently , the etch mask 32 is removed and then a seventh cvd insulation film 34 for bit line insulation is deposited on the exposed whole surface using a cvd method . thereafter , a fourth conductor 35 for a capacitor plate node having a planarization surface is formed on the seventh cvd insulation film 34 using a cvd method and then a eight cvd insulation film 36 for capacitor definition is deposited on the fourth cvd conductor 35 using a cvd method . here , a metal or a polysilicon doped with an impurity can be used as a material of the third conductor and the fourth conductor . an oxide or a nitride can be used as a material of the fifth thermal insulation film 30 to the eighth cvd insulation film 36 . as shown in fig4 h , subsequently , an etch mask 37 is formed at a portion between two word lines formed on the field insulation films 22 and a portion corresponding to the upper side of the bit line 33 , of the surface of the eighth cvd insulation film 36 , and then the fourth cvd conductor 35 and the eighth cvd insulation film 36 are etched , thereby a portion formed in the upper side of the bit line 33 and portions formed between two word lines of the field insulation film 22 merely remains . the remaining fourth cvd conductor 35 serves as the plate node . as shown in fig4 i , subsequently , the etch mask 37 is removed and then a first cvd dielectric film 38 and a fifth cvd conductor 39 for the storage node are deposited , in this order , using a cvd method . thereafter , the first cvd dielectric film 38 , the fifth cvd conductor 39 and the seventh cvd insulation film 34 are etched by a reactive ion etching ( rie ) method , thereby portions formed at the side walls of the remaining fourth cvd conductor 35 , the eighth cvd insulation film 36 and the seventh cvd insulation film 34 merely remain . in a similar manner to the above case , a metal or a polysilicon doped with an impurity can be used as a material of the fifth cvd conductor 39 and an oxide or a nitride can be used as a material of the cvd insulation films . as shown in fig4 j , subsequently , a sixth conductor 40 for a storage node is deposited on the exposed whole surface and then patterned with a photolithography process and an etch process , thereby merely removing portions formed on the remaining eighth cvd insulation film 36 . at this time , the remaining sixth conductors 40 for the storage node are connected to the conductor plugs 29 formed in the capacitor contact holes and the remaining fifth cvd conductors 39 are connected to the remaining sixth cvd conductors 40 . the connected conductors 29 , 39 , 40 serve as the storage node of the capacitor . as shown in fig4 k , subsequently , a second dielectric film 41 is formed and then the remaining eighth cvd insulation film 36 and a portion of the second dielectric film 41 formed on the remaining eighth cvd insulation film 36 are removed . subsequently , a seventh conductor 42 is deposited on the exposed whole surface , using a cvd method . at this time , the remaining second cvd dielectric film 41 is connected to the remaining first cvd dielectric film 38 and the connected dielectric films 38 , 41 serve as the dielectric film of the capacitor . also , the seventh cvd conductor 42 is connected to the remaining fourth cvd conductor 35 and the connected conductors 35 , 42 serve as the plate node of the capacitor . as mentioned above , the storage node of the capacitor includes the remaining first and second conductors 39 , 39 , 40 , the dielectric film of the capacitor includes the remaining first and second dielectric films 38 , 41 and the plate node of the capacitor includes the remaining fourth and seventh conductors 35 , 42 . as above mentioned , also , all of the above conductors can be made of a polysilicon doped with an impurity or a metal and all of the above insulation films can be made of an oxide or a nitride . also , the first and second dielectric films 38 , 41 can be made of a stack structure of thin insulation films such as oxide - nitride ( o - n ), nitride - oxide ( n - o ) and oxide - nitride - oxide ( o - n - o ). according to the embodiments of present invention , it is possible to obtain the following advantages . first , since the bit line contact is formed after planarizing the exposed whole surface by forming the conductor plug 29 , it is possible to stably form the bit line contact . second , since the fourth cvd insulation film 28 , the conductor plug 29 and the fifth cvd insulation film 30 for a buffer layer are made of materials having an etch selectivity different from each other , it is possible to reduce surface defects of the semiconductor substrate 21 upon the formation of the bit line contact . third , since the fifth insulation film 30 for a buffer layer remains between the word line and the bit line , it is possible to reduce the parasitic capacitance occurring between the word line and the bit line and also to prevent shorts of between the bit line and the word line . fourth , since the area of the capacitor is increased as compared with the conventional art , it is possible to increase the capacitance of the capacitor . | 7 |
a hesitation free roller is disclosed . in the following description , numerous specific details are set forth such as specific materials , configurations , dimensions , 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 need not be employed to practice the present invention . in other instances , well known materials or methods have not been described in detail in order to avoid unnecessarily obscuring the present invention . fig3 illustrates the cleaning process of a wafer in a double sided scrubber which incorporates a preferred embodiment of the present invention . although the present invention is described in conjunction with the scrubbing of a wafer , it will be appreciated that any similarly shaped , i . e . generally flat substrate , may be processed by the methods and apparatuses of the present invention . further , it will appreciated that reference to a wafer or substrate may include a bare or pure semiconductor substrate , with or without doping , a semiconductor substrate with epitaxial layers , a semiconductor substrate incorporating one or more device layers at any stage of processing , other types of substrates incorporating one or more semiconductor layers such as substrates having semiconductor on insulator ( soi ) devices , or substrates for processing other apparatuses and devices such as flat panel displays , multichip modules , etc . the wafer 310 is placed between the brushes 320 of the double sided scrubber . stepper motor 340 rotates the roller 330 of the present invention . when the roller 330 is in contact with the wafer 310 friction is created between their edges . thus , the rotating motion of the roller 330 and the friction that is created causes the wafer 310 to rotate . the rotation of the wafer 310 between the brushes 320 allows the entire surface of the wafer to be cleaned . as can be seen , in a preferred embodiment , two rollers 330 contact the wafer at two locations to rotate the wafer and to hold it in place ( i . e ., prevent forward motion ) as it is scrubbed . fig4 illustrates a roller 330 in a preferred embodiment of the present invention . the roller 330 comprises a somewhat flexible material . in general , the material of the roller should have a sufficient softness such that the roller pinches the wafer &# 39 ; s edge as described herein . additionally , the material is preferably machinable , as it is desirable to avoid the high cost of tooling for molded rollers , and to avoid the particle generation of parting lines . the material should not , however , generate excessive particles in use . further , the material should have a sufficient memory to retain its shape . in a preferred embodiment , a urethane , for example , 70 durometer natural urethane is utilized . this material has been found to have sufficient softness , machinability , memory and low particle generation to meet the needs of the present invention . as shown , the top and bottom surfaces of roller 330 are generally flat . in a currently preferred embodiment , roller 330 has flat portions 401 and 402 , slightly indented portions 404 and 403 , and also an inner groove ( groove ) 410 . when a wet wafer is being cleaned between the brushes , it is pushed forward and inserted into the groove 410 of roller 330 , such that groove 410 pinches the wafer 450 causing increased contact , and therefore , increased friction on roller 330 and the edge of wafer 450 . thus , when the roller 330 is rotated the friction causes wafer 450 to rotate . when cleaning solutions such as ammonium hydroxide ( nh 4 oh ) are used , the pinching of the wafer creates enough friction that the wafer 250 does not slip . additionally , the pinching of the wafer squeezes the cleaning solution off of the edge , so that there is not an excessive amount of solution in the contact area between the roller and the wafer &# 39 ; s edge . also , when the hesitation free roller reaches the point p of the flat ( as illustrated in fig2 ) the pinching of the wafer creates enough friction on the edge of the wafer allowing the roller to regain the radius without stalling . in other words , the roller pinches the wafer enough that it grips the edge of the wafer allowing the roller to reach the curved portion of the wafer without hesitating . fig5 illustrates a wafer 550 in groove 410 of roller 330 . as can be seen from the figure , the edge profile of the wafer 550 is substantially more square than that of wafer 450 . because the roller 330 is made of a flexible material , groove 410 deforms slightly to fit the edge of wafer 550 , providing improved contact with it , as with wafer 450 . fig6 illustrates the dimensions of a preferred embodiment of the present invention for use with a 6 . 0 inch ( 150 mm ) wafer . it will be obvious to one of skill in the art that any of the dimensions may vary depending upon the wafer diameter and thickness and may be adjusted to serve the purpose of the present invention . the dimensions given below for roller 330 are merely an example of a preferred embodiment of the present example and are meant simply to illustrate , and not limit the scope of the present invention . as described herein , it is desired for the groove to pinch the wafer or to some extent conform to the edge of the wafer . it is further desired that the pinching action does not occur on the upper or lower surface of the wafer . therefore , the groove should have a shape and dimension such that the wafer may not be inserted into and gripped by contact between the groove wall and the upper and lower surfaces of the wafer . in this regard , the &# 34 ; v &# 34 ; shape disclosed is advantageous since as the edge enters the groove , it contacts the groove at a narrow location of the groove while the surfaces of the wafer are near or within a wider portion of the groove , thus avoiding contact . further , the groove should not be too shallow such that the leading edge of the wafer contacts the apex of the groove , prior to the walls of the groove pinching the edges , thereby resulting in single point contact . in a currently preferred embodiment , groove thickness 630 at the outer opening of the groove ranges from approximately 0 . 005 - 0 . 040 inch in a currently preferred embodiment and , in general , is approximately equal to ( e . g ., within 25 % of ) the thickness of the wafer . for example , in one embodiment groove thickness 630 is preferably tailored to be approximately 0 . 005 inch greater than the thickness of the wafer . the distance between outer edge 640 and inner edge 650 is , in a preferred embodiment , approximately 0 . 067 inches . the distance 655 from the outer edge 640 to the center of curvature of the groove 410 is approximately 0 . 620 inch a currently preferred embodiment . the maximum radius of curvature from this point is approximately 0 . 005 inch . in the manufacture of the roller 330 , the roller is machined in a frozen state , as it is too flexible for machining otherwise . since the portion of the bit which carves the groove 410 is relatively small , it will wear over time . therefore , initially the radius of curvature may be less than the 0 . 005 inch specified above , as virtually all wafer edges will be gripped without penetrating any further . however , once the bit is worn down such that its radius of curvature is any greater than 0 . 005 inch , the bit should be replaced so that subsequent rollers manufactured with a bit continue to grip all wafers . groove angle 560 , in a preferred embodiment , is approximately 24 °. also in a currently preferred embodiment , roller thickness 610 is approximately 0 . 433 inch . roller length 620 is approximately 1 . 625 inches . it should be noted that since the roller material is somewhat flexible the greater the surface thickness 670 the more rigid roller 330 becomes . the surface thickness 670 may be varied to give desired degree of flexibility in the groove and tightness of the pinch . a greater surface thickness 670 leads to less flexibility , and therefore a tighter pinch . conversely , a thinner surface thickness 670 leads to more flexibility and a less tight pinch . various thicknesses may be used to achieve the desired flexibility , for allowing the wafer to slip into the groove 410 , while still giving sufficient pinch . in a preferred embodiment the surface thickness 670 is approximately 0 . 062 inch . it will be appreciated that many modifications of roller 330 may be made within the spirit and scope of the present invention . referring to fig4 and 5 , note that the presence of the groove 410 provides for contact at at least two points , compared with the single point contact of the prior art roller 100 . in this regard , it will be appreciated that the &# 34 ; point &# 34 ; of the contact is in reality a small area . it will further be appreciated that due to the pinching of the groove 410 , each of the two points of contact of the present invention are generally larger areas than the prior art single point contact . thus , any shaped groove which provides this increased contact will achieve the objects of the present invention . for example , although a &# 34 ; v &# 34 ; shaped groove has been illustrated , it will be appreciated that other shapes such as a &# 34 ; u &# 34 ; shaped groove , a substantially square groove , a groove with curved walls , etc ., may be used . further , it will be appreciated that the groove need not be uniform . for example , the groove may have a wide angle at the opening , and a narrower angle farther in . in this regard , the roller may not have a discrete groove as such , but rather may have a pinched &# 34 ; v &# 34 ; shape e . g ., a gradual and continuous transition from the substantially straight sidewall of the roller at the top and bottom to the gripping , groove shape section in the middle . therefore , reference herein to a groove is not meant to limit the invention to rollers having a discrete , discernible groove but rather encompasses any roller having a portion which pinches the edge of the wafer or conforms , at least to some extent , to the edge of the wafer as described herein . if desired , the groove can be tailored to the edge profile of a specific type of substrate . for example , the groove may have a portion which essentially mates with the edge of the wafer . typically , the portion which mates with the edge is slightly smaller than the edge to provide better contact . however , wafer specific grooves have not been found to be necessary since , as described in conjunction with fig4 and 5 , the same groove 410 has been successful in rotating wafers having different edge profiles . in general , the groove 410 has a thickness ( dimension 630 of fig6 ) greater than the leading portion of the edge of the wafer , so that the wafer edge readily fits into the groove 410 . additionally , the groove narrows sufficiently ( e . g ., by having a maximum radius of curvature from a specified point , as in the embodiment described in relation to fig6 ) to pinch the wafer within the groove , without contacting the top or bottom surfaces of the wafer . thus , a hesitation free roller has been described . although specific embodiments , including specific equipment , parameters , methods , and materials have been described , various modifications to the disclosed embodiments will be apparent to one of ordinary skill in the art upon reading this disclosure . therefore , it is to be understood that such embodiments are merely illustrative of and not restrictive on the broad invention and that this invention is not limited to the specific embodiments shown and described . | 7 |
fig1 is a schematic illustration of a representative network environment in which embodiments of the disclosure may be advantageously employed . in fig1 , an exemplary network 10 may include a plurality of sub - networks 12 , 14 , 16 , 18 . sub - networks 14 , 16 , 18 may be coupled with a web server 20 . sub - network 12 may be coupled with web server 20 via an internet service provider ( isp ) 26 and the internet 22 . internet 22 may also be coupled with sub - networks 14 , 16 , 18 . web server 20 may be served by a web server cache 24 . internet 22 may be coupled with other networks ( not shown in fig1 ). sub - network 12 may include a plurality of client units 30 , 40 , 50 coupled with an internet service provider ( isp ) 26 . isp 26 may be served by an isp proxy cache 28 . client unit 30 may include a client 32 coupled with a browser 34 and a browser cache 36 . browser 34 may be served by browser cache 36 . client 32 may access web server 20 via browser 32 , isp 26 and internet 22 . client unit 40 may include a client 42 coupled with a browser 44 and a browser cache 46 . browser 44 may be served by browser cache 46 . client 42 may access web server 20 via browser 42 , isp 26 and internet 22 . client unit 50 may include a client 52 coupled with a browser 54 and a browser cache 56 . browser 54 may be served by browser cache 56 . client 52 may access web server 20 via browser 52 , isp 26 and internet 22 . clients 32 , 42 , 52 are respectively labeled client 1 , client 2 , clientn in fig1 . the indicator “ n ” is employed to signify that there can be any number of clients in sub - network 12 . the inclusion of three clients 32 , 42 , 52 in fig1 is illustrative only and does not constitute any limitation regarding the number of clients that may be included in a sub - network of exemplary network 10 . sub - network 14 may be configured as a local area network ( lan ) 60 . sub - network 16 , 18 may each also be configured as a local area network similar to lan 60 . details of lan configurations in sub - networks 16 , 18 will not be included in this description because describing sub - networks 16 , 18 may be repetitive and prolix , and may clutter fig1 . sub - networks 14 , 16 , 18 are respectively labeled lan 1 , lan 2 , lanm in fig1 . the indicator “ m ” is employed to signify that there can be any number of local area networks ( lans ) in exemplary network 10 . the inclusion of three lans ( lan 1 , lan 2 , lanm ) in sub - networks 14 , 16 , 18 in fig1 is illustrative only and does not constitute any limitation regarding the number of lans that may be included in exemplary network 10 . lan 60 may include a plurality of clients 62 , 64 , 66 . client 62 may be coupled with a browser 63 . browser 63 may be served by a browser cache 80 . client 64 may be coupled with a browser 65 . browser 65 may be served by a browser cache 82 . client 66 may be coupled with a browser 67 . browser 67 may be served by a browser cache 84 . browsers 80 , 82 , 84 may be coupled with a lan control unit 70 . lan control unit 70 may be coupled with a lan proxy server 72 . lan proxy server 72 may also be known as a lan gateway . lan proxy server 72 may be served by a reverse lan proxy cache 74 . reverse lan proxy cache 74 may also be known as a lan gateway cache . lan proxy server 72 may be coupled with a lan firewall 76 . lan firewall 76 may be served by a lan proxy cache 78 . lan firewall 76 may be coupled with web server 20 . clients 62 , 64 , 66 are respectively labeled client 11 , client 12 , client 1 p in fig1 to indicate clients 1 , 2 and p in lan 1 . the indicator “ p ” is employed to signify that there can be any number of clients in lan 60 . the inclusion of three clients 62 , 64 , 66 in fig1 is illustrative only and does not constitute any limitation regarding the number of clients that may be included in lan 60 . one skilled in the art of system design may recognize that fig1 may be a simplistic representation of a network . each respective lanm may itself contain more than one local area network , and there may be more than one local area network protected behind a respective firewall 76 . alternatively , a firewall may be provided between web server 20 and the internet 22 for protecting all lans , web server 20 and web server cache . lan proxy cache 78 may sometimes be identified as a forward proxy cache . client 62 may access internet 22 or web server 20 via browser 63 , lan control unit 70 , lan proxy server 72 and lan firewall 76 . client 64 may access internet 22 or web server 20 via browser 65 , lan control unit 70 , lan proxy server 72 and lan firewall 76 . client 66 may access internet 22 or web server 20 via browser 67 , lan control unit 70 , lan proxy server 72 and lan firewall 76 . sub - networks 16 , 18 ( lan 2 , lanm ) may provide connection with internet 22 for respective clients ( not shown in fig1 ) substantially as described in connection with lan 60 . fig2 is a flow chart illustrating operation of a method according to an embodiment of the present invention . in fig2 , a method 100 for obtaining a result for a query formulated using information contained in an on - line form 102 ( e . g ., a post - query ) may begin by preparing the form 102 , as indicated by a block 104 . method 100 may continue with treating information in form 102 with a predetermined algorithm to present an algorithmically - treated content , as indicated by a block 106 . as further exemplified in block 106 , the algorithmic treating may be effected using a hash function such as , by way of example and not by way of limitation , a message digest md 5 hash function known by those skilled in the art of secure data communication and identified as internet engineering task force ( ietf ) request for comments ( rfc ) 1321 , commonly abbreviated as ietf - rfc1321 . the algorithmically - treated content may be employed in a form of a substantially unique pseudo - get phrase . by way of example and not by way of limitation , such a pseudo - get phrase may include a recognizable get phrase such as “ getfile . asp ?” with a signature phrase , such as “ hashsignature = 123abc . . . ” appended to the get phrase to create a web identifier [ getfile . asp ? hashsignature = 123abc . . . ]. such a getfile identifier may be used to compose a universal resource locator ( url ) such as , by way of example and not by way of limitation , http :// www . company . com / getfile . asp ? hashsignature = 123abc . . . as indicated by block 106 . use of the symbols “?” and “=” appearing in this exemplary url represent syntax requirements that may be employed to satisfy standard requirements for http communications . by way of further example and not by way of limitation , the “. asp ” suffix on the “ getfile . asp ” phrase may indicate that the web server is using “ active server pages ” from microsoft to serve dynamically composed html content . one could employ other suffixes indicating other web server features including , by way of example and not by way of limitation , “. php ”, “. cgi ”, “. aspx ” and “. jsp ”. such other suffixes and the parameters following them in a “ get ” query may all adhere to the parameter syntax phraseology : “? hashsignature = 123abc . . . ”. method 100 may continue with a requester submitting or sending the query via a network from a requesting station to a responding station requesting the result , as indicated by a block 108 . the responding station may be identified by a web identifier . the web identifier may include the pseudo - get phrase . the network may include a plurality of cache units situated between the requesting station and the responding station . by way of example and not by way of limitation , cache stations involved with communications between client 32 and web server 20 ( fig1 ) may involve browser cache 36 , isp proxy cache 28 and web server cache 24 . the plurality of cache units may include a distal cache unit nearer the responding station than the requesting station , such as web server cache 24 ( fig1 ) when a subscriber receives a response from web server 20 responding to a query submitted pursuant to block 108 . actions effected to carry out method steps indicated by blocks 104 , 106 , 108 may be performed by a requester , as indicated by an encompassing block 101 surrounding blocks 104 , 106 , 108 . method 100 may continue with determining whether the query is a get - type query or a post - type query , as indicated by a query block 110 . if the query is a get - type query , method 100 may proceed from query block 110 via a get response line 120 and method 100 may inquire of at least one selected cache unit in the network the result or response to the query is contained in at least one selected cache unit in a manner identified with the web identifier , such as by indexing the response with respect to the web identifier . by way of example and not by way of limitation , if client 62 ( fig1 ) is acting as requester 101 in fig2 , this inquiry may involve interrogating browser cache 80 , reverse lan proxy cache 74 , lan proxy cache 78 and web server cache 24 to ascertain whether a result or response is stored in at least one of caches 80 , 74 , 78 , 24 in a manner identifiable or indexed to the web identifier [ getfile . asp ? hashsignature = 123abc . . . ] ( composed pursuant to block 106 ). if the result is contained in a cache unit in a manner associated with the web identifier , method 100 may operate the cache unit containing the result as a providing cache unit to effect providing the result to the requesting station ( i . e ., requester 101 ), as indicated by a block 146 . it may be preferred that the result obtained also be stored in downstream caches — i . e ., caches between the responding cache and requester 101 — as indicated by a block 142 . surrounding block 144 enclosing block 142 ( in fig2 ) is intended to indicate that method 100 may store the found result in all downstream caches between the cache from which the response was obtained to the cache nearest to requester 101 . making web form post - query responses cacheable may significantly reduce network bandwidth usage and may reduce web server and database processing activity . these results may be achieved by reducing duplicate requests to a web server within a given page freshness period . there is a need for a method for obtaining a response for a post - query that may be cacheable . fig2 represents this multi - cache inquiry by a block 122 ( labeled “ cache ”) followed by a query whether the information sought is available , indicated by a query block 124 . if the information is available in the then - addressed cache ( block 122 ) in a manner associated with the web identifier , method 100 may proceed from query block 124 via a yes response line 140 , store the response or result in downstream caches ( block 144 ) and provide the information to requester 101 , as indicated by block 146 . if the information is not available in the then - addressed cache ( block 122 ) in a manner associated with the web identifier , method 100 may proceed from query block 124 via a no response line 126 and a next cache may be selected for interrogation , as indicated by a block 128 . method 100 may then inquire whether the next - to - be - interrogated cache is the web server cache ( or another cache closest to the responder and distal from requester 101 ), as indicated by a query block 130 . if the next - to - be - interrogated cache is not the web server cache , method 100 may proceed from query block 130 via a no response line 132 to a locus 133 and steps associated with blocks 122 , 124 , 128 , 130 may be repeated . if the next - to - be - interrogated cache is the web server cache , method 100 may proceed from query block 130 via a yes response line 134 and a query may be posed whether the requested information is contained in the web server cache in a manner associated with the web identifier , as indicated by a query block 136 . if the requested information is contained in the web server cache in a manner associated with the web identifier , method 100 may proceed from query block 136 via a yes response line 138 , store the response or result in downstream caches ( block 144 ) and provide the information to requester 101 , as indicated by block 146 . if the requested information is not contained in the web server cache in a manner associated with the web identifier , method 100 may proceed from query block 136 via a no response line 148 and instruct requester 101 to resubmit the query as a post - query using the pseudo - get phrase in the url of the request , as indicated by a block 150 . regarding the query posed by query block 110 , if the query is a post - type query , method 100 may proceed from query block 110 via a post response line 112 and the web server ( or other distal server ) may be contacted for inquiry and obtaining the response or result of the query posed ( block 108 ), as indicated by a block 114 . method 100 may continue with caching the result obtained pursuant to block 114 in the web server cache in a manner associated with the web identifier , such as by indexing the response with respect to the web identifier , as indicated by a block 116 . actions effected to carry out method steps indicated by blocks 114 , 116 may be performed by a responder via a web server or other distal server , as indicated by an encompassing block 103 surrounding blocks 114 , 116 . method 100 may continue with instructing requester 101 to resubmit the request as a cacheable get - query using the pseudo - get phrase in the url of the request , as indicated by a block 118 . method 100 may continue with repeating steps indicated by blocks 108 , 110 , 122 , 124 , 128 , 130 , 136 , 144 , 146 until at least one cache may be operated as a providing cache unit to effect providing the result to requester 101 , as indicated by block 146 . method 100 may reduce traffic to any of various caches in a system , and likely may reduce traffic with a web server . employing method steps represented by blocks 122 - 130 , method 100 may retrieve information stored in a cache anywhere “ en route ” from a client to a web server if that information is within its respective freshness period . a freshness period may be established by a system when information is stored in a cache , and an indication of the freshness period may be stored with the information . there may be more than one opportunity to avoid inquiring for information from a web server . by way of example and not by way of limitation , referring to fig1 ., client 62 may find information requested has been earlier requested and is stored ( within the freshness period for the information ) in any of browser cache 80 , reverse lan 1 proxy cache 74 and lan proxy cache 78 . response to a query by client 62 may be satisfied from the earliest - encountered opportunity to obtain the requested information . thus , a query from client 62 may be responded to by reverse lan 1 proxy cache 74 if , for example , client 64 had earlier requested the same information . in such an exemplary situation , the query posed by client 62 may not proceed further within the system , thereby avoiding traffic to other system components , such as by way of example and not by way of limitation , 1 lan 1 firewall 76 , lan 1 proxy cache 78 and web server 20 . making web form post - queries cacheable may also make network and web server usage predictable for web forms that contain fields with predefined possible selections . the maximum number of hits on a given web server in a given page freshness cycle may be calculated as the number of choices per field raised to the power of the number of form fields . by way of example and not by way of limitation , a web form ( e . g ., form 102 ; fig2 ) with 10 fields , each field having 3 drop down choices , may have a maximum of 3 to the 10th ( 3 10 ) possible cacheable query requests . this may amount to a maximum of 59 , 049 possible hits to a web server using the exemplary web form . the actual upper bound for a given freshness period may be smaller because it may be unlikely that users would exercise the entire extent of form field value combinations . it is to be understood that , while the detailed drawings and specific examples given describe preferred embodiments of the disclosure , they are for the purpose of illustration only , that the apparatus and method of the disclosure are not limited to the precise details and conditions disclosed and that various changes may be made therein without departing from the spirit of the disclosure which is defined by the following clams : | 6 |
in fig1 and 2 there is shown a pair of cast mould parts 12 , 14 each of which comprises a relatively rigid body 16 . each part 12 , 14 includes an abutment face 17 which are in mutual contact when the mould parts made and each abutment face 17 is provided with a recess 18 which is filled with a mouldable material 20 which is curable to form a resilient heat stable material . a rubber composition based upon rubber reclaimed from tyres has been found suitable for moulding thermoplastics such as polypropylene . the out surface of the mouldable material 20 is arranged to be substantially contiguous with the abutment face 17 and prior to creating an impression is preferably coated with a release agent such as talcum powder . an original sculpture or article 30 from which replicas are to be made is positioned between the mould parts 12 , 14 and these are then closed by , for instance , a press ( not shown ). closing of the cast mould parts causes the article 30 to be pressed into the opposed faces of the mouldable materials and causes an impression to be made therein . due to the flow characteristics of the mouldable material a natural separation line around the periphery of the article is achieved between the opposed surfaces of the mouldable materials . the closed cast mould parts are now heated to cause the rubber compound to vulcanise and thereby form a heat stable resilient material . the mould parts are now separated and the article is removed to leave a mould casting 50 ( see fig3 and 4 ). the bodies of resilient material 28 may now be removed from the cast mould parts 12 , 14 , thereby defining a pair of mould inserts 100 , in block form , formed from the resilient material . the pair of mould inserts 100 can be directly mounted into opposed mould platens 40 ( only one of which is shown in fig3 ) of an injection moulding machine . attachment means , for example bolts 101 ( fig4 ) or a rigid backing plate 110 ( fig5 ) may be received to the resilient material prior to insertion of the mould insert into the mould platens 40 . the backing plate 110 may include one or more bolts 111 . advantageously the attachment means are located with the cast mould parts so that the attachment means become secured to the resilient material during the curing process . it is envisaged that the backing plate 110 may be attached to the resilient material after casting , for instance by bonding . preferably , as schematically illustrated in fig6 the resilient mould inserts 100 when located within the opposed platens 40 are positioned such that the separation surfaces 120 of the mould inserts 100 are located slightly above the abutment faces 41 of the platens 40 . accordingly when the mould platens 40 close , the opposed surfaces 120 of the mould inserts initially contact one another and then are placed under a resilient loading caused by compression of the resilient material as the platens reach their fully closed position . the resilient loading on the opposed surfaces 120 resists flashing occuring during the injection moulding process . as illustrated in fig2 it is envisaged that location formations , such as pegs 25 , may be spaced about the mould cavity such that when the mould inserts 100 are closed the location formations co - operate to resist relative slidable movement of the opposed surfaces 120 . as illustrated in fig3 it is envisaged that the cast mould parts can be used as attachment means . in this case the opposed surfaces 120 of the resilient material are substantially contiguous with the abutment faces 17 of the mould parts . the body 16 of each mould part has an outer shape complementary to that of a location recess formed in a platen 40 of an injection moulding machine . accordingly the body 16 can be accurately located in the platen 40 whilst being easily removable to facilitate replacement of the mould inserts . the platen 40 shown in fig3 includes radially extending channels 41 along which plastics is injected . each body 16 has a channel 42 formed therein for communication with a respective channel 41 . after curing and separation of the mould parts 12 , 14 a channel ( not shown ) is cut into the resilient material for feeding plastics material from the channel 42 of the body to the mould cavity portion formed therein . when casting the resilient inserts the size of each recess 18 of the cast mould parts and the amount of mouldable material contained therein is chosen to provide sufficient mouldable material to provide an adequate impression . preferably in order to assist heat dissipation during the moulding process the amount of mouldable material is chosen to be minimum to obtain the above criteria . in addition it is envisaged that the bodies 16 may be provided with ducts for coolant fluid which communicate with coolant ducts formed in the supporting platen 40 . in addition , the resilient material at least in the vicinity of the mould cavity is preferably arranged to be of a minimum thickness so as to resist distortion of the mould cavity arising from fluid pressure of the moulten plastics during the injection moulding process . in order to assist heat dissipation the mouldable material may be adapted to improve its heat conductivity . for instance the chemical composition of the mouldable material may be adjusted to maximise its heat conductivity and / or the mouldable material may include particles of a good heat conductor such as metallic particles dispersed therein . in addition , or as an alternative , coolant conduits , such as metallic pipes , carrying a coolant may extend into the recess 18 so as to be partly or wholly surrounded by the mouldable material . furthermore , blocks of suitable metals may be located within the mouldable material to act as heat sinks . these blocks may be in direct contact with the body 16 to thereby provide a good path of heat conduction from the mouldable material and into the body 16 . | 8 |
the microporous aluminophosphate , having ato type framework disclosed in the present invention is produced by microwave - hydrothermal crystallization from a reaction mixture containing reactive sources of phosphorus and aluminum and an organic structure directing agent ( diquat - hydroxide ), and , optionally , additional divalent metals or sources of silica . the preparative process typically comprises forming a reaction mixture which in terms of mole ratios is : the reaction mixture is placed in a teflon vessel inert towards the reaction mixture and heated under microwave - hydrothermal conditions ( mars - 5 , cem corp , usa ) until crystallized , under static conditions at a temperature of at least about 100 ° c ., preferably between 150 ° c . and 200 ° c . for a period of 5 to 360 mins . the solid crystalline reaction product is then recovered by any convenient method , such as filtration or centrifugation , washed with water and dried in air at a temperature between ambient and about 120 ° c . in a preferred crystallization method , the source of phosphorus is phosphoric acid , and the source of aluminum is a hydrated aluminum oxide of the trade name catapal ( sasol ), the temperature is 150 ° c . to 180 ° c ., the crystallization time is from 15 to 180 mins , and the ratio of compounds in the reaction mixture is 1 . 0 al 2 o 3 : 1 . 0 - 1 . 2 p 2 o 5 : 0 . 5 - 1 . 0r : 40 - 75 h 2 o . the templating agent is diquat - hydroxide and is present in the reaction mixture in an amount ranging from about 0 . 5 to 1 . 0 moles per mole of alumina . additionally silica may also be introduced into the reaction . the preferred source of silica is either ludox as - 30 or tetraethyl orthosilicate . the structure directing agent used is known as diquat compounds . the organic cation r + , also designated herein as diquat - 6 / 7 , is derived from the diquat - 6 / 7 hydroxide or organic or inorganic salt of diquat - 6 / 7 . the salts of diquat - 6 / 7 are obtained by reacting a suitable precursor salt containing the functional group r 1 , e . g ., a hexyl / heptyl derivative , containing two anions at the terminal carbon atoms , such as , 1 , 7 - dibromoheptane / 1 , 6 - dibromohexane , with a stoichiometrically required amount of trimethylamine to form a diquaternary salt of the organic cation . the synthesis of the original salt of diquat - 6 / 7 can be carried out with an organic or inorganic precursor salt containing the functional group r 1 . the r 1 group of the organic cation may be heptyl / hexyl or it may have one or more double or triple unsaturated bonds . thus , for example , r 1 may have one double unsaturated bond , or two or three consecutive or non - consecutive double unsaturated bonds . alternatively , the r 1 group may contain at least one triple unsaturated bond . however , in the most preferred embodiment , the r 1 group is heptyl / hexyl . the precursor salt contains two anions at the terminal carbon atoms of the functional group r 1 . thus , the precursor salt has a formula a - r 1 - a , wherein r 1 is as defined above and a is an organic or inorganic anion . suitable inorganic anions are phosphate , halogens , e . g ., fluoride , chloride , bromide or iodide , sulfate , bisulfate , bisulfite , carbonate , bicarbonate , hexafluorophosphate , nitrate , oxyhalogen , such as chlorate , clo 3 − or perchlorate , clo 4 − . representative suitable organic anions are carboxylate , r — coo − , amide , rcon − , alkoxide , r 3 co − , or etherate , ro − . the synthesis of the diquat - 6 / 7 salt is conducted with a continuous stirring at a temperature of about 50 to about 80 ° c ., preferably about 60 ° c . to about 80 ° c ., at autogenous pressure in a suitable non - aqueous solvent , such as alcohol , e . g ., ethanol , toluene or tetrahydrofuran , until crystals of the diquat - 6 / 7 salt are formed , usually for about 4 to about 24 hours . the crystals of the product settle to the bottom , the reaction mixture is cooled e . g ., in a water - ice bath , and the product is separated from the reaction mixture by any suitable means , e . g ., by filtration or centrifugaton . the crystals are then washed with a suitable solvent , e . g ., absolute ethanol , followed by a wash with an anhydrous diethyl ether . the diquat - 6 / 7 salt crystals are then dried . the hydroxide form of diquat - 7 is obtained in any conventional manner from the salt of diquat - 6 / 7 , such as by ion exchanging the salt of diquat - 7 with a suitable hydroxide in any conventional manner , e . g ., in an ion - exchange column . any of the conventional ion - exchange techniques is used to replace the original anions with the hydroxide anion , as will be obvious to those skilled in the art . representative of such ion exchange techniques are those disclosed in a wide variety of patents , e . g ., u . s . pat . nos . 3 , 140 , 249 , 3 , 140 , 251 and 3 , 140 , 253 . the diquat - 6 / 7 hydroxide , when used as per the present invention leads to crystallization of alpo - 31 / sapo - 31 phase having a characteristic x - ray diffraction pattern , set forth below in table 1 . the crystallized ato phase is subjected to post synthesis treatment namely calcination in the temperature range of 200 - 800 ° c ., more preferably in the range of 300 - 600 ° c . to remove the entrapped organic moieties for the period of 2 - 24 h in air . thus obtained calcined form is also found to have similar x - ray diffraction pattern as set forth in table 1 . the calcined form of the ato phase is subjected to nitrogen uptake measurement at − 196 ° c . to estimate its surface area and micropore volume as per astm method 4365 applicable for microporous solids . furthermore , the uptake of various probe molecules such as m - xylene , p - xylene , n - hexane , n - octane , n - heptane , cyclohexane is measured over the calcined phase at 20 ° c . to judge the adsorption crystallinity of the phase crystallized as per the art disclosed in the present invention . as noted above , sapo - 31 functions well as a molecular sieve adsorbent . additionally , catalysts containing sapo - 31 in admixture with at least one hydrogenation component , such as platinum , palladium , tungsten , vanadium , molybdenum , nickel , cobalt , chromium , and manganese , are excellent dewaxing catalysts ( sometimes referred to as “ catalysts ”). combinations of these metals such as cobalt - molybdenum , cobalt - nickel , nickel - tungsten or cobalt - nickel - tungsten , are also useful with such catalysts . such catalysts generally comprise sapo - 31 and from about 0 . 01 % to 10 %, preferably from about 0 . 1 % to about 5 % of the hydrogenation component by weight of sapo - 31 . preferred hydrogenation components are platinum and palladium and , when employed , are preferably employed between about 0 . 1 percent and 1 . 5 percent by weight of sapo - 31 . the physical form of sapo - 31 depends on the type of catalytic reactor being employed and may be in the form of a granule or powder , and is desirably compacted into a more readily usable form ( e . g ., larger agglomerates ), with a silica or alumina binder for fluidized bed reaction , or pills , prills , spheres , extrudates , or other shapes of controlled size to accord adequate catalyst - reactant contact . the present invention is further illustrated and supported by the following examples . these are merely representative examples and optimization details and are not intended to restrict the scope of the present invention in any way . the diquat - 6 / 7 dihydroxide salt used to crystallize molecular sieve alpo - 31 and / or sapo - 31 is prepared by reacting 1 , 7 - dibromoheptane / 1 , 6 - dibromohexane and trimethylamine in accordance with the following stoichiometric equation : 50 grams of 1 , 7 - dibromoheptane ( sigma - aldrich chemical company ) is weighed out and transferred directly to a two - liter , three - necked reaction flask equipped with a stirrer . 100 ml absolute ethanol is added to the reaction flask while the contents of the flask are stirred continuously . then , 100 grams ( excess ) of trimethylamine solution ( 25 % in methanol , sigma - aldrich chemical company ) is transferred directly to the two - liter reaction flask . the two - liter reaction flask is fitted with a dry - ice condenser to minimize ( ch 3 ) 3 n loss during reflux . the reaction mixture is refluxed for about 14 hours . white crystals of diquat - 7 dibromide are formed and separated from the reaction solution at the end of the reflux period . the reaction flask is cooled by immersion in water - ice bath . the product is then filtered on a buchner funnel . product crystals are washed on the funnel several times with absolute ethanol , then several times with anhydrous diethyl ether . the diquat - 7 dibromine product crystals are dried by air stream on the buchner funnel after the ether wash . thus obtained dibromide salt of diquat - 7 is subjected to ion exchange procedure to convert it to dihydroxide form using anion exchange resion dowex 8x . typically , aqueous solution of 50 wt % of dibromide salt of diquat - 6 / 7 is slurried in 1 l water containing 20 g of resin for 20 h to obtain dihydroxide salt of diquat - 6 / 7 . alpo - 31 is crystallized from a reaction mixture prepared by combining 2 . 3 grams of psedoboehmite ( catapal vista b , sasol ) with 3 . 7 grams of 85 wt .% orthophosphoric acid ( h 3 po 4 ) and 5 . 0 grams of water and stirred until homogeneous . to this mixture is added 8 grams of diquat - 7 hydroxide solution ( 22 % in water ) and the mixture further stirred . the composition of the final reaction mixture in molar oxide ratios is : 0 . 5 diquat - 7 ( oh ) 2 : 1al 2 o 3 : 1 p 2 o 5 : 45 h 2 o this homogenised reaction mixture is placed in a stainless steel pressure vessel lined with an inert plastic material and heated in under microwave - hydrothermal conditions by employing mars - 5 ( cem , usa ) unit at 180 ° c . at autogenous pressure for 3 hours . the solid reaction product is recovered by filtration , washed with water , and dried in air at 120 ° c . thus obtained product is subjected physicochemical characterization . x - ray diffraction pattern of as - synthesized form displaying the characteristic peaks of ato phase as listed in table 1 . the morphology of the sample is investigated by means of scanning electron microscope ( sem , leica , cambridge , model 440 , fig3 ). alpo - 31 is crystallized from a reaction mixture prepared by combining 2 . 3 grams of psedoboehmite ( catapal vista b , sasol ) with 3 . 7 grams of 85 wt . % orthophosphoric acid ( h 3 po 4 ) and 5 . 0 grams of water and stirred until homogeneous . to this mixture is added 8 grams of diquat - 6 hydroxide solution ( 22 % in water ) and the mixture further stirred . the composition of the final reaction mixture in molar oxide ratios is : 0 . 5 diquat - 6 ( oh ) 2 : 1 al 2 o 3 : 1 p 2 o 5 : 45 h 2 o this homogenised reaction mixture is placed in a stainless steel pressure vessel lined with an inert plastic material and heated in under microwave - hydrothermal conditions by employing mars - 5 ( cem , usa ) unit at 180 ° c . at autogenous pressure for 3 hours . the solid reaction product is recovered by filtration , washed with water , and dried in air at 120 ° c . thus obtained product is subjected physicochemical characterization . x - ray diffraction pattern of as - synthesized form displaying the characteristic peaks of ato phase as listed in table 1 . sapo - 31 is crystallized from a reaction mixture prepared by combining 2 . 0 grams of psedoboehmite ( catapal vista b , sasol ) with 3 . 2 grams of 85 wt . % orthophosphoric acid ( h 3 po 4 ) and 4 . 0 grams of water and stirred until homogeneous . to this mixture is added 1 . 12 grams of an aqueous sol of 30 wt . % sio 2 and the mixture is further stirred until homogeneous . to this mixture is added 7 grams of diquat - 7 hydroxide solution and the mixture is stirred until homogeneous . the composition of the final reaction mixture in molar oxide ratios is : 0 . 5 diquat - 7 ( oh ) 2 : 1 al 2 o 3 : 1 p 2 o 5 : 0 . 4 sio 2 : 45 h 2 o a portion of this reaction mixture is placed in a stainless steel pressure vessel lined with an inert plastic material and heated in under microwave - hydrothermal conditions by employing mars - 5 ( cem , usa ) unit at 160 ° c . at autogenous pressure for 4 hours . the solid reaction product is recovered by filtration , washed with water , and dried in air at 120 ° c . thus obtained product is subjected physicochemical characterization . x - ray diffraction pattern of as - synthesized form displaying the characteristic peaks of ato phase as listed in table 1 . the material from example 1 is calcined in air in the following manner . a thin bed of material is heated in a tubular quartz reactor from room temperature to 120 ° c . at a rate of 1 ° c . per minute and held at 120 ° c . for two hours . the temperature is then ramped up to 540 ° c . at the same rate and held at this temperature for 10 hours . the calcined form of alpo - 31 as prepared in example - 5 has a micropore volume ( t - plot ) of about 0 . 20 cc / gm with surface area of about 275 m 2 / g based on adsorption isotherm at 77 k recorded on as - 1c unit from quantachrome . the nitrogen adsorption isotherm is analyzed using the non linear density function theory ( nldft ) approach ( j . phys . chem . b . ; 2001 105 ( 29 ); 6817 ) and the conventional t - plot method ( j . catalysis , 1965 , 4 , 319 ). the dft analysis also shows that calcined form alpo - 31 has a pore size of about 0 . 53 nm . the acidity for the alumino / silicoaluminophosphate ato framework is measured using ammonia - tpd technique . typically , 50 mg of samples prepared as per examples 2 and 4 and treated as per example 5 are exposed to 6 % ammonia / helium mixture and ammonia desorption is recorded as a function of temperature using alta - mira ami200 unit . the measured tpd curves ( fig2 ) demonstrate increased acidity level for silicoaluminophosphate framework ( 0 . 332 mmol / g ) as against aluminophosphate framework ( which is found to be negligible ). adsorption capacities are measured on this calcined product using a standard mcbain - bakr gravimetric adsorption apparatus . the following data ( table 2 ) is obtained on a sample activated at 300 ° c . thus , the pore size of the calcined product is & gt ; 4 . 3 å and & lt ; 6 . 2 å , as shown by adsorption of n - hexane , kinetic diameter of 4 . 3 a and nil adsorption of m - xylene . 1 . the specific structure directing agent or templating agent disclosed in the present invention favors crystallization of ato framework from a reaction medium having a ph below 4 . 5 . 2 . the present invention discloses a very fast and rapid synthesis approach using such templating agent for preparing crystalline ato type molecular sieve framework . 3 . the crystalline ato type molecular sieve framework obtained by the process of the present invention is very pure and completely free from commonly observed major impurity phase , namely ael framework . | 2 |
by way of overview , the present invention provides an improved head support sleep aid . the improved head support sleep aid maintains correct alignment of the user &# 39 ; s neck and spine . the improved head support sleep aid supports the user &# 39 ; s head in a manner which avoids undue wrinkling of the user &# 39 ; s face particularly in the skin areas proximate the user &# 39 ; s eye . the improved head support sleep aid maintains the appropriate head support during movement as the user sleeps . more specifically , fig1 sets forth a perspective view of a head support and sleep aid constructed in accordance with the present invention and generally referenced by numeral 10 . head support and sleep aid 10 is shown being utilized by a sleeping person generally referenced by numeral 15 in a typical anticipated use of the invention . head support sleep aid 10 includes a generally rectangular segment 11 preferably fabricated of a resilient foam material such as rubber or plastic . head support sleep aid 10 further includes a head and neck support 12 having a generally rectangular resilient foam body 20 . as is described below in greater detail , head and neck support 12 further includes a flexible mesh ear coupling 24 which , in the manner described below , is secured to foam body 20 . in further accordance with the fabrication of ear coupling 24 , sleeping person 15 is resting upon foam body 20 and has a lower ear extending into and received within ear coupling 24 . an elongated cylindrical preferably resilient foam material neck support 13 is positioned upon pillow segment 11 beneath the neck portion of sleeping person 15 . in accordance with the anticipated use of the present invention head support sleep aid , sleeping person 15 is resting upon the combined structures provided by pillow segment 11 and head and neck support 12 . both of these structures are preferably formed of a resilient foam material and thus provide a cushioning support . in further accordance with the anticipated use of the present invention head support and sleep aid , sleeping person 15 is resting the side portion of the users head upon ear coupling 24 and head resting surface 21 of foam body 20 . thus , the weight of the head and neck portion of sleeping person 15 is resting upon and “ crumples ” ear coupling 24 . with temporary reference to fig4 , it will be noted that foam body 20 of head and neck support 12 defines an ear clearance cavity 22 which extends downwardly from head resting surface 21 . thus , the user in the posture shown in fig1 has inserted the user &# 39 ; s ear through ear aperture 26 of ear coupling 24 . as a result , the user in resting the user &# 39 ; s head upon surface 21 of foam body 20 collapses or crumples ear coupling 24 allowing the user &# 39 ; s ear to extend downwardly into ear clearance cavity 22 . in this manner , the surrounding portion of head resting surface 21 supports the head of sleeping person 15 without imposing stress or pressure or wrinkling upon the facial portions of sleeping person 15 in the eye and surrounding regions . as a result , person 15 is able to sleep resting upon head support and sleep aid 10 while ear coupling 24 maintains the correct position between the sleeping persons head and foam body 20 . neck support 13 provides additional foam support for the neck portion of the user . as a result , as sleeping person 15 shifts and moves during the sleep cycle , the captivity of user &# 39 ; s ear within ear coupling 24 is maintained which in turn maintains the correct position of head and neck support 12 . fig2 sets forth a perspective assembly of head support sleep aid 10 in its entirety . in accordance with the preferred fabrication of the present invention , head support sleep aid 10 includes a plurality of interlocking stackable pillow segments 11 , 16 and 17 . in further accordance with the preferred fabrication of the present invention , pillow segments 11 , 16 and 17 form generally rectangular resilient foam plastic or rubber bodies which define different thicknesses or heights . thus , in the illustration of the present invention shown in fig2 , pillow segment 11 is the thickest pillow segment while pillow segment 17 forms the thinnest pillow segment and pillow segment 16 defines an intermediate or medium thickness or height . pillow segment 11 defines a top surface 18 and further defines an interlock receptacle 31 . pillow segment 16 defines an interlock receptacle 33 together with an upwardly extending interlock 30 . finally , pillow segment 17 defines an interlock receptacle 35 and an interlock 32 . in the stack configuration shown in fig2 , pillow segment 11 is resting upon pillow segment 16 and is maintained in attachment by the insertion of interlock 30 of pillow segment 16 into interlock receptacle 31 . similarly , pillow segment 16 is resting upon pillow segment 17 and is maintained in position by the insertion of interlock 32 of pillow segment 17 into interlock receptacle 33 of pillow segment 16 . it will be apparent to those skilled in the art that different pillow thickness may be obtained by utilizing different combinations of pillow segments . for example , it will be apparent to those skilled in the art that the combined thickness of head support sleep aid 10 may be altered by removing pillow segment 16 and securing pillow segment 17 directly to pillow segment 11 . similarly , as set forth above in fig1 , the thickness of the resulting pillow may be further altered by simply using pillow segment 11 alone . finally , pillow segments 16 and 11 may be utilized while omitting pillow segment 17 and so on . it will be equally apparent to those skilled in the art that while three pillow segments are shown in the embodiment illustrated in fig2 , a different number of pillow segments with different thickness relationships may be utilized without departing from the spirit and scope of the present invention . the important aspect of the illustration shown in fig2 is the provision of a selected pillow thickness which is maintained despite movement on the part of the user by the interlocking feature . as described above , head support and sleep aid 10 also includes head and neck support 12 which includes a generally rectangular foam body 20 having a head resting surface 21 . as is also described above , head and neck support 12 includes a flexible mesh material ear coupling 24 secured to surface 21 and having an elastically constricted ear - receiving aperture 26 . while the embodiment show utilizes an elastic constricture , such as an elastic band , for aperture 26 , other closures may be used . for example , aperture 26 may be closed using a sliding bead drawstring , a rubber band , a snap attachment , a button attachment or a hook and loop fabric attachment . it will also be apparent to those skilled in the art that foam body 20 may be formed of other materials such as cotton , pressed fabric or the like without departing from the spirit and scope of the present invention . similarly , the shape of foam body 20 may be formed in a variety of different shapes , including but not limited to circular , oval , pear , horse shoe , kidney bean or heart - shaped . by way of further variation , ear coupler 24 may be formed of various materials , such as cotton , molded plastic or woven fabric without departing from the spirit and scope of the present invention . fig3 sets forth a perspective assembly view of the interlocking pillow segments utilized in the present invention head support sleep aid . as described above , pillow segment 11 defines an interlock receptacle 31 and an upper surface 18 . as is also described , pillow segment 16 defines an interlock receptacle 33 and an upwardly extending interlock 30 . finally , pillow segment 17 defines an interlock receptacle 35 and an upwardly extending interlock 32 . it will be apparent to those skilled in the art that the configurations of interlocks 30 and 32 as well as interlock receptacles 31 , 33 and 35 facilitate mutual intercoupling and attachment . thus , it will be apparent that interlock 30 may be received within interlock receptacle 31 while interlock 32 may be received within either interlock receptacle 31 or interlock receptacle 33 . in this manner , the combined height may be selectively determined by utilizing either a single pillow segment or a plurality of pillow segments which have been stacked and interlocked . the interlock feature facilitates the use of multiple pillow segments in a fixed stacked arrangement despite movement of the user during sleep . in the preferred fabrication of the present invention , pillow segments 11 , 16 and 17 are fabricated of a resilient somewhat firm material such as foam plastic or foam rubber or the like . fig4 sets forth a perspective assembly view of head and neck support 12 which , as is described above , includes a generally rectangular foam body 20 defining a head resting surface 21 and a pillow resting surface 28 . as can be seen in fig1 and 2 above , pillow resting surface 28 generally conforms to the planar upper surface of pillow segments such as pillow segment 11 allowing foam body 20 to rest upon the underlying pillow segment . head resting surface 21 further defines a downwardly extending ear clearance cavity 22 together with a further downwardly extending clearance aperture 23 . head and neck support 12 further includes a flexible mesh material ear coupling 24 . ear coupling 24 defines a bottom edge 25 which is positioned upon head resting surface 21 of foam body 20 so as to enclose ear clearance cavity 22 and as is indicated by dashed line 27 . edge 25 may be joined to head resting surface 21 using virtually any conventional fabrication technique such as adhesive attachment or chemical or sonic welding as desired . ear coupling 24 further includes an ear receiving aperture 26 which is sufficient in size to allow a typical users ear to be passed there through . in the preferred fabrication of the present invention , ear - receiving aperture 26 is elastically constricted by an elastic material which draws ear - receiving aperture 26 to a semi - closed configuration . in this manner , an ear passed through aperture 26 is gripped loosely within the interior of ear coupling 24 and maintained by the constrictor of aperture 26 . this maintains the position of head and neck support against the user &# 39 ; s face and avoids resting the user &# 39 ; s facial skin against foam body 20 in the portions thereof surrounding the user &# 39 ; s eye . the constricting character of aperture 26 maintains the user &# 39 ; s ear in a loose attachment to ear coupling 24 and thus maintains the appropriate head positioning for the user . fig5 sets forth a top view of foam body 20 utilized in head and neck support 12 . foam body 20 defines a head resting surface 21 and an ear clearance cavity 22 . within cavity 22 , a clearance aperture 23 extends downwardly through the remainder of foam body 20 . fig6 sets forth a section view of foam body 20 taken along section lines 6 - 6 in fig5 . as described above , foam body 20 defines a head rest surface 21 together with a clearance cavity 22 and a clearance aperture 23 . foam body 20 further defines a surface 28 which , in the anticipated use of the present invention , is rested upon an underlying pillow segment in the manner shown in fig1 . fig7 sets forth a side elevation view of head and neck support 12 . as described above , head and neck support 12 includes a generally rectangular foam body 20 defining a head rest surface 21 and a pillow rest surface 28 . as is also described above , a flexible mesh material ear coupling 24 extends upwardly from surface 21 and terminates an elastically constricted aperture 26 . in accordance with the preferred fabrication of the present invention , the generally rectangular shape of foam body 20 is altered slightly by a front to back taper of surface 28 . thus , surface 28 is angled slightly with respect to surface 21 producing a dimensional difference 29 at the rear portion of foam body 20 . this front - to - back taper aids in maintaining the correct position of head and neck support 12 . fig8 sets forth a top view of an alternate embodiment earpiece of the present invention head support sleep aid generally referenced by numeral 50 . earpiece 50 is formed of a resilient soft material such as foam plastic or foam rubber . as can be seen in fig8 , earpiece 50 defines a generally round shaped body 51 which , in turn , defines an aperture 52 . aperture 52 also defines an edge 53 along its frontal end . in accordance with the present invention , earpiece 50 is show in position upon a typical ear 55 . in operation , the user places earpiece 50 upon ear 55 as shown to couple the earpiece to the user &# 39 ; s hear ( not shown ). during sleep , earpiece 50 bears a portion of the user &# 39 ; s weight and avoids wrinkling of the user &# 39 ; s facial skin . fig9 sets forth a top view of a further alternate embodiment earpiece of the present invention head support sleep aid generally referenced by numeral 60 . earpiece 60 is similar to earpiece 50 , described above in that it includes a soft resilient body 61 defining an aperture 62 and an edge 63 . earpiece 60 operates in the same manner as earpiece 50 . fig1 sets forth a top view of a still further alternate embodiment earpiece of the present invention head support sleep aid generally referenced by numeral 70 . earpiece 70 is similar to earpiece 50 , described above in that it includes a soft resilient body 71 defining an aperture 72 and an edge 73 . earpiece 70 operates in the same manner as earpiece 50 . earpieces 50 , 60 and 70 are shown to provide alternative earpiece shapes , all functioning in the same manner . thus , it will be apparent to those skilled in the art that earpieces having further alternate shapes may be used without departing from the spirit and scope of the present invention . it will be further apparent that a plurality of soft flexible ties ( not shown ) may be added to the above earpieces to tie them to the user &# 39 ; s head as desired . fig1 sets forth a perspective view of a still further alternate embodiment earpiece of the present invention head support sleep aid generally referenced by numeral 80 . earpiece 80 is preferably formed of a soft resilient material , such as molded foam rubber or molded foam plastic . earpiece 80 includes an elongated , generally planar frontal pad 81 joined to a curved bridge 82 , bridge 82 curves downwardly to an end 84 . bridge 82 also fines an edge 85 and an edge 86 together with a concave curved surface 87 . frontal pad 81 further defines a flexible tie 88 extending from end 83 to end 84 . a clasp , such as a hook and loop fabric attachment pad 89 allows tie 88 to be separatable . in operation , the user places earpiece 80 upon the user &# 39 ; s ear 55 as shown below in fig1 . to couple the earpiece to the user &# 39 ; s hear ( not shown ), clasp 89 is released and earpiece 80 is placed upon user &# 39 ; s ear 55 ( shown in fig1 ). thereafter , tie 88 is drawn and clasp 89 secures earpiece 80 in place . a malleable reinforcing wire 95 is molded into earpiece 80 to aid in forming the earpiece to the user &# 39 ; s ear and head for greater comfort . during sleep , earpiece 80 bears a portion of the user &# 39 ; s weight and avoids wrinkling of the user &# 39 ; s facial skin . fig1 a sets forth a section view of the alternate embodiment earpiece of the present invention head support sleep aid set forth in fig1 taken along section line 12 a - 12 a therein . fig1 b sets forth a section view of the alternate embodiment earpiece of the present invention head support sleep aid set forth in fig1 taken along section line 12 b - 12 b therein . fig1 c sets forth a section view of the alternate embodiment earpiece of the present invention head support sleep aid set forth in fig1 taken along section line 12 c - 12 c therein . fig1 d sets forth a section view of the alternate embodiment earpiece of the present invention head support sleep aid set forth in fig1 taken along section line 12 d - 12 d therein . fig1 e sets forth a section view of the alternate embodiment earpiece of the present invention head support sleep aid set forth in fig1 taken along section line 12 e - 12 e therein ; fig1 sets forth a top view of earpiece 80 fitted to a user &# 39 ; s ear 55 . as described above , earpiece 80 is preferably formed of a soft resilient material , such as molded foam rubber or molded foam plastic . earpiece 80 includes an elongated , generally planar frontal pad 81 joined to a curved bridge 82 , bridge 82 curves downwardly to an end 84 . bridge 82 also fines an edge 85 and an edge 86 together with a concave curved surface 87 . frontal pad 81 further defines a flexible tie 88 extending from end 83 to end 84 . a clasp , such as a hook and loop fabric attachment pad 89 allows tie 88 to be separatable . in operation , the user places earpiece 80 upon the user &# 39 ; s ear 55 . to couple the earpiece to the user &# 39 ; s head ( not shown ), clasp 89 ( seen in fig1 ) is released and earpiece 80 is placed upon user &# 39 ; s ear 55 as is shown in fig1 . thereafter , tie 88 is drawn and clasp 89 secures earpiece 80 in place . during sleep , earpiece 80 bears a portion of the user &# 39 ; s weight and avoids wrinkling of the user &# 39 ; s facial skin . in phantom like depiction , the adjustable position of end 84 to be either closer to end 83 or farther from end 83 is also shown in the figure . fig1 sets forth a side view of earpiece 80 . as described above , earpiece 80 is preferably formed of a soft resilient material , such as molded foam rubber or molded foam plastic . earpiece 80 includes an elongated , generally planar frontal pad 81 joined to a curved bridge 82 , bridge 82 curves downwardly to an end 84 . bridge 82 also fines an edge 86 together with a concave curved surface 87 . frontal pad 81 further defines a flexible tie 88 extending from end 83 to end 84 . a clasp , such as a hook and loop fabric attachment pad 89 allows tie 88 to be separatable . earpiece 80 also defines a bottom surface 90 which is tapered to define a reduced thickness away from frontal pad 81 . thus a small taper angle 91 is formed to aid in positioning the user &# 39 ; s head during sleep . what has been shown is a head support sleep aid which provides a plurality of interlocking pillow segments together with a head and neck support which couples to the user &# 39 ; s ear . the resulting head support sleep aid avoids applying wrinkles and stress to the facial skin area of the user in an about the user &# 39 ; s eye . while particular embodiments of the invention have been shown and described , it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects . therefore , the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention . | 0 |
as shown in fig1 , a communication and documentation system 10 useful in providing care to persons includes a server 12 containing an application portion 14 and a database portion 16 . the server 12 , for example , may comprise one or more computers . for example , the application portion 14 can reside on one or more computers or servers , and the database portion 16 can reside on one or more computers or servers . the server 12 provides both database and web server capabilities . a host computer 18 , which may be a standard desktop personal computer , provides an interface which can be used , for example , by a supervisor or nurse ( a ) to enter and update patient care plans and associated data , ( b ) to enter patient care requirements that are linked to speech segments that can be retrieved when needed by staff members at any time , ( c ) to enter staff member assignments such as which patients are assigned to which staff members on a given shift , ( d ) to schedule patient tasks that result in the server 12 calling the staff members at scheduled times ( e . g ., to communicate appointment reminders ), and ( e ) to enter other information that is linked to the server 12 . this other information can include , for example , the names of new staff members and / or new patients . this information is then integrated by the server 12 into dialogues ( e . g ., james jones gets dressing ; or hello mary smith ). the host computer 18 can also be used ( a ) to generate reports based on patient data ( e . g ., vital signs , falls ) entered either by voice or by use of a screen display on the host computer 18 , ( b ) to display text in a screen display ( e . g ., that indicates that a note is available for a patient and that includes a link that can be clicked on in order to listen to the note through a headset where the note is archived in the form of a sound file , and ( c ) to generate reports on staff performance ( e . g ., productivity reports indicating the number of tasks recorded per hour and exception reports that indicate activities not completed by staff members for each resident . moreover , the host computer can further be used to set system parameters , to conduct training sessions , to provide immediate advice on the care of patients , and to perform additional or alternative functions . the host computer 18 , for example , may include a standard web browser in order to support communications between the host computer 18 and the server 12 . however , alternative apparatus may be used to support communications between the host computer 18 and the server 12 . the server 12 contains host media processing software 20 . this software , for example , is obtainable from intel corporation and can support bi - directional voice communication with the users of mobile terminals 22 1 , 22 2 , . . . , 22 n . the database portion 16 of the server 12 supports database connectivity for the communication and documentation system 10 . the database portion 16 provides a central repository for all communication and documentation system data and , thus , acts as a bridge between the mobile terminals 22 1 , 22 2 , . . . , 22 n and the host computer 18 . the mobile terminals 22 1 , 22 2 , . . . , 22 n can be any type of suitable devices such as cordless telephones , portable data assistants ( pdas ), notebook pcs , tablet pcs , and / or other mobile devices equipped to wirelessly communicate with the server 12 . a computerized device that is not mobile , such as a landline telephone , may also be used to communicate with the server 12 in the same manner as a mobile user device . in one embodiment of the present invention , the mobile terminals 22 1 , 22 2 , . . . , 22 n can be spectralink netlink cordless telephones that operate using 802 . 11 b wireless voice - over - internet - protocol , and thus communicate directly with telephony hardware of the server 12 . the h . 323 protocol may be used for call control . also , the mobile terminals 22 1 , 22 2 , . . . , 22 n may be arranged to communicate with the server 12 and with each other using any desired network such as a wireless internet protocol network 24 . accordingly , examples of communications in the communication and documentation system 10 comprise the following : ( i ) voice - over - internet - protocol ( voip ) calls ; ( ii ) calls that retrieve selected sound files stored on the server 12 and that play the sound files to the staff members over the mobile terminals 22 1 , 22 2 , . . . , 22 n ; ( iii ) interactive calls that interpret the staff members &# 39 ; key presses on the mobile terminals 22 1 , 22 2 , . . . , 22 n ; ( iv ) interactive calls that process the staff members &# 39 ; speech by sending it to a speech recognition engine 26 in the application portion 14 for interpretation and for storing of the interpretation results as text files on an application logic 28 of the database portion 16 ; and , ( v ) interactive calls that process the staff members &# 39 ; speech by recording it as a file stored on the application logic 28 . as described above , the mobile terminals 22 1 , 22 2 , . . . , 22 n are located on the same wireless internet protocol network 24 as the server 12 . appropriate routes can be established in the wireless internet protocol network 24 by software settings so that calls are directed to the server 12 . the server 12 uses the speech recognition engine 26 , which executes speech recognition software , such as from scansoft , inc ., to interpret spoken responses from the users of the mobile terminals 22 1 , 22 2 , . . . , 22 n and to convert them into text that can be processed by application logic 28 of the telephony system . based on the interpretation results , the server 12 executes software in the application logic 28 that matches the text equivalent of the voice message ( for example , requesting a patient &# 39 ; s bathing schedule ) received from the user of the mobile terminal 22 to corresponding text stored in the database portion 16 in order to select the appropriate responses from the database portion 16 . for example , the text equivalent of the voice messages can be used as pointers into the database portion 16 to retrieve the appropriate responses . alternatively , the voice messages can be used a pointers into the database portion 16 without first converting the voice messages to text . the application logic 28 assembles speech segments selected from a speech segment database 29 based on the responses into complete voice messages . these complete voice messages are then transmitted as voice signals to the mobile terminal 22 using the host media processing software 20 . the server 12 and the mobile terminals 22 1 , 22 2 , . . . , 22 n may be located , for example , in the same local area as the staff members that use them . in an alternative embodiment , the server 12 and the mobile terminals 22 1 , 22 2 , . . . , 22 n may be connected to the public internet and the server 12 can be located at a different site from the mobile terminals 22 1 , 22 2 , . . . , 22 n . the host computer 18 and the server 12 communicate through a data network 30 . the supervisor enters , updates , or corrects patient care information data using a mouse or other data entry device . furthermore , data may be exported to and imported from an external database 32 by way of translation logic 34 included in the software of the communication and documentation system 10 . the supervisor can use the host computer 18 to review data collected via the communication and documentation system 10 on patient care and staff member performance in the form of real time host interface reports . for this purpose , the host computer 18 includes a report generator that generates reports based on data stored in the database portion 16 . in addition , selected reports from the host interface provided by the host computer 18 can be made available to physicians and family members on their computers 36 through a secure web site or web connection . the application software of the communication and documentation system 10 is comprised of dialogue scripts that control the “ conversation ” between the staff members and the server 12 . these scripts can follow rules that establish how messages in the communication and documentation system 10 are linked to each other in a database 38 of the database portion 16 . sample scripts are shown in appendix a . accordingly , the database 38 of the communication and documentation system 10 includes a speech file database that stores a set of prerecorded responses , the text of all of the elements of patient care information , the patient data entered by the users of the mobile terminals 22 1 , 22 2 , . . . , 22 n and the host computer 18 , and the voice messages recorded by the users via the mobile terminals 22 1 , 22 2 , . . . , 22 n . based on the responses stored in the database 38 , the application logic concatenates the speech segments stored in the speech segment database 29 to assemble all possible voice responses of the communication and documentation system 10 to staff member commands . the software of the communication and documentation system 10 converts the patient care messages selected on the host computer 18 to speech messages and establishes relationships between the patient care activities . the selected patient care messages are then made available to be heard on the mobile terminals 22 1 , 22 2 , . . . , 22 n at scheduled times or time intervals or otherwise . every message is characterized as either ( i ) a scheduled message ( s ), ( ii ) a message ( t ) that is tied into , and to be played in conjunction with , a scheduled message ( s ), or ( iii ) an information message ( i ) that is for information only and does not , therefore , require a specific activity to be completed . “ s - messages ” can be heard by the staff members over the mobile terminals 22 1 , 22 2 , . . . , 22 n any time during the prescribed time interval . the prescribed time interval , for example , may be the time of a staff member &# 39 ; s shift or some other time interval entered by use of the host interface of the host computer 18 . “ s - messages ” stay active during the prescribed time interval until the staff member reports the activity as completed , at which point they are removed from the list of active messages and are reported as completed in the database portion 16 of the communication and documentation system 10 . when the activity is reported to be completed , the “ s - messages ” are also removed from the list of uncompleted activities displayed by the host interface provided by the host computer 18 . “ t - messages ” are active during the same time period as the associated “ s - messages ”. “ i - messages ” are active and available for the user to hear at all times . all patient care activities tracked by the communication and documentation system 10 may be scheduled at specific times of the day for each patient . this scheduling allows the staff member to hear only relevant activities over the mobile terminals 22 1 , 22 2 , . . . , 22 n in the order in which they need to be completed for the current shift time period . for example , the day shift staff will hear that they must complete breakfast and lunch , in that order . they will not hear that they must complete dinner , because that occurs on the evening shift . the staff members can enter patient data by speaking a number such as temperature . the software of the communication and documentation system 10 establishes an acceptable range for each parameter and each entry must be within this range to be accepted . if the entry is not within the acceptable range , the communication and documentation system 10 asks the staff member to try again . the communication and documentation system 10 provides scheduled outbound calls with messages for the users ( staff members ) of the mobile terminals 22 1 , 22 2 , . . . , 22 n at specific times based on scheduling provided through use of the host interface provided by the host computer 18 . each scheduled call may be simultaneously directed to specified one ( s ) of the mobile terminals 22 1 , 22 2 , . . . , 22 n without a user request . the user ( s ) of the specified one ( s ) of the mobile terminals 22 1 , 22 2 , . . . , 22 n may either accept the call or ask the communication and documentation system 10 to call back later . the communication and documentation system 10 can also provide unscheduled outbound calls when a staff member says a specified word option into the mobile terminal 22 . for example , saying “ emergency ” will result in all logged in staff members receiving an emergency call . other such outbound calls can be triggered by a staff member &# 39 ; s voice command or by a set of specified system conditions . in one embodiment of the invention , each staff member wears a headset that is connected to the corresponding mobile terminal 22 . this headset enables the staff member to “ converse ” hands free with the communication and documentation system 10 from any place within the area covered area by the wireless system antennas and at any time . thus , the staff members can obtain their latest assignments , ask for patient care information , hear patient care messages , input patient data , record the completion of a patient care activity , talk directly to other staff members wearing headsets and logged into the communication and documentation system 10 , and / or record spoken messages that can be accessed by other staff member on the same shift or later shifts . a schematic that provides an example of the overall process is shown in fig2 . the flexible design of the communication and documentation system 10 is not strictly hierarchical and , thus , the sequence of events can vary to meet the user &# 39 ; s needs . as shown by the process of fig2 , the supervisor , using the host computer 18 , enters or modifies the individualized care plan for each patient and assigns each patient to a staff member . this data is imported to the server 12 from an administrative database stored , for example , on the host computer 18 . the staff member turns on his or her mobile terminal 22 and logs in with the appropriate password . thereafter , the process of fig2 follows one of two paths . along one of these two paths , the staff member speaks into the corresponding mobile terminal 22 to record a clinical note or to record a reminder to send a message to the server 12 . the supervisor using the host computer 18 sees a message on the host computer interface that a clinical note is available for retrieval and listens to the note through a voice interface or reads the note that has been converted to text and displayed on the host computer interface . along the other path , the staff member uses one of the mobile terminals 22 1 , 22 2 , . . . , 22 n to access assignments and / or up - to - date patient care information of interest . the staff member then documents the care provided to , and the health data of , the patient using one of the mobile terminals 22 1 , 22 2 , . . . , 22 n . the care and health data are automatically exported to the database portion 16 for storage as described herein . also , the supervisor reviews such stored care and health data on the host computer 18 . moreover , the staff members use the mobile terminals 22 1 , 22 2 , . . . , 22 n to communicate with other staff members as needed . the users must log in to start using and to be recognized by the communication and documentation system 10 and must log out when finished using the system . the dialogues of the communication and documentation system 10 are designed for primarily non - hierarchical navigation , allowing the user to rapidly move from one dialogue section to another when hearing a response message . in an alternative embodiment , a hierarchical dialogue structure may be used . appendix a illustrates typical dialogues in a nursing home environment , consistent with fig2 . the following list includes additional features that can be incorporated into the communication and documentation system 10 : triggering a call to a supervisor and posting an alert note on the host interface provided by the host computer 18 when patient data , such as blood pressure , is out of a predefined “ clinically acceptable range ”; allowing a user to enter and correct data using either one of the mobile terminals 22 1 , 22 2 , . . . , 22 n or the host interface of the host computer 18 , and retaining an audit trail of changes ; recognizing unavailability of staff ( e . g ., staff on lunch break ) to receive an outbound call and redirecting such call to another person logged into the system ; reading data inputs from written or printed data sheets that are scanned and storing such data in the database portion 16 ; automatically inactivating a message for a specified time period when a patient is designated to not receive such message for such specified time period ; notifying staff members when a patient is designated to not receive a message for a specified time period ; reading data from a bar code or radio frequency identification ( rfid ) scanner or other scanning device and storing such data in the database portion 16 ; allowing a free - form spoken message to be recorded , converted to text by commercially available speech - to - text software , displayed by the host interface , and stored in the database portion 16 as a text message ; scheduling reminder messages to the mobile terminals in advance of the reminded activity , where the amount of advance notice may vary by message type ; sending an alert message to a mobile terminal that a change in patient care has been entered on the host interface ; sending an alert message to a mobile terminal when a parameter in a patient &# 39 ; s record has changed ; automatically reviewing and analyzing patterns of data in the database portion 16 and sending an alert message to a mobile terminal when the data analysis indicates that a critical value or range was exceeded ; sending a reminder or educational message to the mobile terminal when a patient is to receive a specified type of care by the user ; sending a reminder or educational message to the mobile terminal when specified types of data are entered by the user ; sending a reminder to the mobile terminal about the patient &# 39 ; s personal information , such as a birthday ; sending an outbound message to all mobile terminals simultaneously ; causing the mobile terminals 22 1 , 22 2 , . . . , 22 n to automatically log out at the end of a shift after notification of the users ; causing the host interface provided by the host computer 18 to automatically log out at the end of a shift after notifying the users ; interfacing the communication and documentation system 10 to third party wireless systems such as nurse call systems via interface software such as that provided by spectralink and converting the alerts produced by the wireless system into a text or speech message on the mobile terminal ; interfacing the communication and documentation system 10 with a telephone system so the mobile terminals 22 1 , 22 2 , . . . , 22 n can make calls via a public telephone network ; interfacing the communication and documentation system 10 with third party software in a way that allows review of data on the host interface before the data are exported to the third party software ; capturing a telephone message from an authorized caller from outside the facility and recording such message as a voice or text note in the database portion 16 ; and , a word option on the mobile terminal that retrieves previously recorded data such as vital signs and that communicates such data to the user in a voice message . the application logic 28 executes a program 300 to perform the functions as described herein . fig3 is a high level flow chart which illustrates the program 300 of the application logic 28 . when a voice message is received by the server 12 from one of the mobile terminals 22 as indicated by a block 302 , a check is made at a block 304 to determine whether the message is a page in which a staff member using the mobile terminal 22 is paging an individual staff member or is paging a group of other staff members . if the received message is a page , a channel is opened and the page is transmitted at a block 306 . if the individual being paged acknowledges the page as determined at a block 308 , the individual staff member and the page originator use the mobile terminals as telephones to conduct a conversation , and program flow returns to the block 302 . if a group of staff members being paged acknowledge the page as determined at a block 308 , the staff members in the group hear a message recorded by the group page originator by speaking into the mobile terminal when the group page is placed , and program flow returns to the block 302 . however , if all staff members being paged do not acknowledge the page , the identities of those staff members not acknowledging the page are stored at a block 310 so that those staff members can be paged at a later time , the staff members acknowledging the page hears a message recorded by the originator of the group page by speaking into the mobile device when the group page is placed , and program flow returns to the block 302 . if the received message is not a page , a determination is made at a block 312 as to whether the received message is information , such as a response to a question previously asked by the server 12 of the user of the mobile terminal 22 , or a word option that engages the server in a continued dialogue . if the message is a response containing information to be stored , a determination is made at a block 314 as to whether the user has verified the information ( this verification step may be skipped in some cases as with many yes / no responses ). if the information has not been verified , then a request is made of the user at a block 316 to verify the information and program flow returns to the block 302 . if the received information is verified , a determination is made at a block 318 as to whether the information has a range check associated with it and whether the information is within the valid range . if so , the information is stored at a block 320 , a next message in the dialogue , if any , is transmitted to the mobile terminal , and program flow returns to the block 302 . if the received information is not in the valid range , or if the received information is not verified , the server 12 transmits a request for retransmission of the information at a block 322 and program flow returns to the block 302 . if the received message is not information , the received message is compared to the dialogue stored in the database portion 16 . a determination is then made at a block 326 to determine if the received message matches any of the dialogue stored in the database portion 16 . if not , the received message must contain an invalid word option and the system cannot act on the received information and thus communicates its inability to proceed to the staff member with a tone or message at a block 328 . program flow then returns to the block 302 . if the received message matches the dialogue stored in the database portion 16 , the matching response stored in the database portion 16 is retrieved from the database portion 16 at a block 330 and is transmitted at a block 332 . program flow then returns to the block 302 . fig4 is a flow chart of a program that can be executed by the block 330 when a request for information is received by the server 12 . specifically , when the part of the dialogue initiated by the staff member through use of a mobile terminal 22 is a request for information as indicated at a block 402 , a check is made at a block 404 to determine if the information requested relates to a current activity , i . e ., whether the request relates to an activity to occur during a scheduled time period , for example the current shift . the blocks 402 and 404 can be arranged to cover different types of scheduled activities . for example , some scheduled messages may occur only once during the scheduled time period such that , if the activity has already been performed , the message is not played . some scheduled messages may occur a fixed number of times greater than one during the scheduled time period such that , if the activity has been performed less than the prescribed number of times , the scheduled message is played . some scheduled messages may have a start and stop time and must be performed every x hours such that , if current time is between the specified start and stop times , the scheduled message is played along with a message stating the timeframe and stating that the last time activity was performed , regardless of how many times it has been performed . if the requested information relates to a current activity , the requested information is played at a block 406 . that is , the requested information is assembled from speech segments into a complete voice message and the voice message is transmitted at the block 332 . this message is referred to above as a scheduled message ( s ). thereafter , a check is made at a block 408 to determine if there is a tied message ( t ) tied into , and to be played in conjunction with , the scheduled message ( s ). if there is a tied message ( t ) tied into the scheduled message ( s ), the tied message is played at a block 410 . if the requested information does not relate to a current activity as determined at the block 404 , or if there is no tied message ( t ) tied into the scheduled message ( s ) as determined at the block 408 , of after the tied message is played at the block 410 , a check is made at a block 412 to determine if there is an information message ( i ) to be played . if there is an information message ( i ) to be played , the information message ( i ) is played at a block 414 . after the information message ( i ) is played at the block 414 , or if there is no information message ( i ) to be played as determined at the block 412 , the routine of fig4 is ended and program flow returns to the block 302 of fig3 . the communication and documentation system 10 can be used in a variety of care giving settings including nursing homes , assisted living facilities , hospitals , home healthcare facilities , and rehabilitation centers . therefore , the terms “ supervisor ” and “ staff member ” as used herein are meant to be generic to cover any person capable of using the communication and documentation system 10 for its intended purpose . similarly , the term “ patient ” as used herein is meant to be generic to cover other people , such as assisted care and / or nursing home residents , who receive care by the users of the communication and documentation system 10 . login process — at the beginning of the shift , each user ( staff member and / or supervisor ) logs in to the communication and documentation system 10 . the login process allows the communication and documentation system 10 to link the user with the user &# 39 ; s patient assignments . here is an example with a fictitious healthcare professional using the communication and documentation system 10 . the material not in brackets represent verbal dialogue . definitions : sm : staff member cds : communication and documentation system sm : [ press the specified button on the mobile terminal ] cds : please log in sm : [ keys in correct passcode on mobile terminal ] cds : donald smith . is this correct ? sm : yes . cds : & lt ; ending tone & gt ; the ending tone signals to the user that the communication and documentation system 10 is finished speaking and it is now the user &# 39 ; s turn . assignment option — the assignment option allows the staff member to review his or her patient assignment list . resident option — the resident option allows the staff member to access a care plan and database associated with a specific patient to either hear or record information about such patient . in the option , the staff member speaks the resident &# 39 ; s room number , and the communication and documentation system 10 then allows the staff member to get or record patient related information . for example , the communication and documentation system 10 can retrieve many types of information that is sent to the mobile terminal as voice messages including : ( i ) background when spoken elicits background information that is individualized to the patient , ( ii ) task list when spoken elicits information that includes activities of daily living in the care plan during a particular shift , ( iii ) & lt ; a specific task name & gt ; when spoken elicits messages with details for a specific task ( e . g ., the task name grooming when spoken may elicit a message at the mobile terminal such as “ provide wig care ”, and ( iv ) & lt ; a specific data name & gt ; when spoken elicits a message with the most recently recorded data for the patient ( e . g ., the data name weight when spoken may elicit a message at the mobile terminal such as “ the patient &# 39 ; s weight is 150 pounds ”). following are some examples : sm : task list cds : james jackson room 292 needs vital signs , bathing , mouth care , dressing , grooming , meals , toilet , positioning , transfers , and ambulation . cds : & lt ; ending tone & gt ; similarly , after a staff member has spoken a patient &# 39 ; s room , the staff member can tell information to the communication and documentation system 10 information about a patient at the point of care . this information will be automatically recorded in the patient &# 39 ; s database . the kinds of patient information that the nursing assistant can tell include : ( i ) & lt ; specific task name & gt ; done when spoken allows the staff member to document the completion of a specific task ( e . g ., the words “ grooming done ” when spoken may elicit at the mobile terminal a question such as “ has the patient had breakfast ?”; and , ( ii ) & lt ; specific data name & gt ; when spoken allows the staff member to speak patient data to be recorded into the mobile terminal ( e . g ., the word option “ pulse ” when spoken may elicit in the mobile terminal a question such as “ what is the pulse ?”). following are some examples : sm : pulse cds : what is the pulse ? sm : 86 . cds : 86 . is this correct ? sm : yes . cds : & lt ; ending tone & gt ; other options can also be provided using similar dialogues . for example , note when spoken allows the nurse to record a note or to listen to one or more previously recorded notes . note in the resident allows the staff member to record a note or to listen to a note about a specific patient . after recording , the staff member may be offered the options of saving , adding to , deleting and listen to the note . a skip option can also be used to allow the user to skip to the next note by saying the option word skip . page when spoken enables a user to talk with one or more other staff members as discussed above . report when spoken enables the staff member to hear the end - of - shift report from the previous shift at any time . certain modifications of the present invention have been described above . other modifications of the present invention will occur to those practicing in the art of the present invention . for example , although as described above staff members are the users of the mobile terminals 22 , the supervisor of the staff members can also use a mobile terminal to communication with the server 12 and / or with the staff members . accordingly , the description of the present invention is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the best mode of carrying out the invention . the details may be varied substantially without departing from the spirit of the invention , and the exclusive use of all modifications which are within the scope of the appended claims is reserved . | 6 |
investment casting is used to produce difficult - to - cast parts in a variety of materials . fig1 depicts a typical turbocharger cast inconel ® turbine wheel . fig2 depicts a typical cast titanium compressor wheel . the turbine wheel ( 3 ) consists of a hub with a detailed backface and detailed nose ( 2 ), incorporating the nut detail , supporting a plurality of blades ( 1 ). the features of the nose are formed by the coming together of the set of die inserts , the features of the backface are often formed by a separate disc which is fitted to the sacrificial pattern tooling plate assembly . thus the accuracy and veracity of the nose features and the concentricity of the backface features are a function of the condition of the tool producing the sacrificial pattern . the compressor wheel hub ( 4 ) supports a plurality of full blades ( 5 ) and partial or splitter blades ( 6 ). in either case the generation of the consumable pattern requires a complex , expensive , finely machined tool . in order to be able to generate a mold cavity which mimics the shape of the part to be cast , the master pattern of the part must first be produced as shown in fig3 which depicts a male consumable pattern of a turbine wheel with a plurality of blades ( 8 ), which have the same shape , size and thickness as the blade to be cast , with consideration given for process shrinkage . the blade in the drawing is seen to have a height ( 9 ). the part to be cast is attached , in this case molded , to a male sprue , or runner ( 7 ), which is required by the casting process to flow molten metal to the cast part . fig4 depicts a shell , which is hollow inside . the inside surface ( 10 ) of the shell represents the negative , or female of the shape , size and thickness as the part to be cast , again , with a mold part ( 11 ) for casting the sprue or runner , the mold part ( 11 ) already molded , or attached to the shell . in this case the blade shell ( 12 ) is much thicker and rougher , and longer ( 13 ), than the male blade ( 8 ), as it represents the blade with a refractory ceramic shell built up over the blade such that the inside surfaces mimic the blade and the outside of the shell is simply in existence to support the inner surfaces . once the shell is filled with molten material and it solidifies , the shell is broken away to reveal a metal version of what is seen in fig3 , albeit corrected by the shrinkage factors so that this piece is the correct size , shape and thickness . a first embodiment of the invention , embodiment ( a ), will be explained by reference to fig5 , illustrating the methodology of a typical well - known rapid prototyping procedure used in a production environment , but in this case , to create a complete tree of a sacrificial material consisting of multiple “ positive ” male patterns ( 52 ), representing the shape , size and thickness of the parts to be cast . the procedures by which the solid forms are produced are variously known as , e . g ., rapid prototyping ( rp ), three - dimensional printing ( 3 - d printing ), selective laser sintering ( sls ), solid ground curing ( sgc ), fused deposition modeling ( fdm ), ink jet printing , solid freeform fabrication (“ sff ”), stereo - lithography ( or stereolithography apparatus , sla ), and cubital &# 39 ; s solider system . the fabrication techniques usually depend on the use of computers to generate cross - sectional patterns representing the layers of the object being formed , and generally require the associated use of a computer and computer - aided design and manufacture ( cad / cam ) software . in general , these techniques rely on the provision of a 3 - d digital representation of the object to be formed . the 3 - d digital representation of the object is reduced or “ sliced ” to a series of 2 - d cross - sectional layers which can be overlaid to describe the object as a whole . the apparatus for carrying out the fabrication of the object then utilizes the cross - sectional representations of the object for building the layers of the object by , for example , determining the path of the laser beam in an sla or the configuration of the mask to be used to selectively expose uv light to photosensitive liquids . the properties required of a good pattern wax are described by j . h . w . booth , foundry trade journal , december 1962 and by d . mills , b . i . c . t . a . 11th annual conference , may 1971 . these include melting point , ash content , shrinkage / expansion characteristics , strength , plasticity , viscosity , thermal stability , oxidative stability and surface appearance . other properties such as resistance to or solubility in acids and bases may be important in certain instances . suitable sacrificial materials are disclosed in u . s . pat . no . 3 , 854 , 962 ( composition for use in the manufacture of precision investment casting molds including combinations of various types of waxes , usually combined with resins such as wood rosin or synthetic resins and a combustible polyhydric alcohol having a melting point above the melting point of the wax to act as a filler for the pattern composition ); gb 1 , 378 , 526a ( investment casting waxes with addition of carbon microspheres to reduce contraction on cooling ); u . s . pat . no . 3 , 880 , 790 ( investment casting wax composition containing substituted polystyrenes — esp . vinyl toluene - alpha - methyl styrene copolymer waxes . pattern waxes in common use may contain natural or synthetic resins , natural or synthetic waxes and a variety of other materials such as stearic acid . resins that may be used include rosin , rosin esters , gum damar , modified phenolics , alkyds of low molecular weight , terpene resins , petroleum resins , chlorinated naphthalene , chlorinated biphenyl , etc . waxes that may be used include beeswax , vegetable waxes such as carnauba and candelilla , mineral waxes such as paraffin wax , microcrystalline wax and montan , and synthetic waxes such as amide waxes , ester waxes , fisher - tropsch waxes , castor oil derived waxes , etc . ); u . s . pat . no . 3 , 717 , 485 ( pattern wax compositions containing aromatic polycarboxylic acid imide as filler for use in investment casting by the lost wax process . the pattern wax composition materials contain base waxes such as petroleum waxes , natural vegetable or mineral waxes , synthetic waxes and various resinous materials derived from the refining of petroleum and wood rosin , and mixtures of the above and solid filler particles such as phthalic acid ); u . s . pat . no . 3 , 704 , 145 ( investment casting wax composition consisting essentially of refined petroleum wax , solid chlorinated biphenyl , ester type montan waxes , fischer - tropsch wax , and a metal soap ); u . s . pat . no . 3 , 655 , 414 ( pattern materials for use in investment casting by the lost wax process consisting essentially of waxes such as petroleum waxes , natural vegetable or mineral waxes , synthetic waxes and various resinous materials derived from the refining of petroleum and wood resin , and mixtures of the above . the base wax generally has a melting point of between about 120 ° to 180 ° f . the base wax composition is improved by the inclusion of up to about 75 percent by weight , preferably a minor amount , of solid filler particles of a phthalic acid . isophthalic acid is the preferred filler ); and u . s . pat . no . 5 , 975 , 188 ( casting by investment casting of a metal or alloy , especially titanium and its alloys , in a ceramic investment shell mold . the ceramic facecoat slurry typically is applied as one or more coatings to a fugitive pattern , such as a wax pattern , having a configuration corresponding to that of the casting to be made pursuant to the well known lost wax process . for example , a pattern made of wax , plastic , or other suitable removable material having the desired configuration is formed by conventional wax or plastic die injection techniques and then is dipped in the aforementioned ceramic mold facecoat slurry . the slurry also may be applied to the pattern by flow coating , spraying or pouring . in the event that the mold facecoat will comprise two dipcoats or layers , the pattern may again be dipped in the ceramic facecoat slurry and partially dried and / or cured ). referring now to fig5 , the initial or bottom plane ( 54 ) is the first plane upon which fine particles of fusible material is deposited . then , layer , by layer , the fusible material is spread on the platen , and selectively fused to the already fused material deposited on the prior layer , until a full tree “ positive ” sacrificial pattern is built . when plane ( 55 ) has been offered and no material is deposited onto this level , the procedure advances to the next step wherein unfused particles are separated from the fused form . the sacrificial patterns ( 52 ) are linked to the vertical sprues ( 7 ) and the connecting runners ( 56 ). the runners , sprues and patterns are printed with the male patterns . the filling funnel ( 58 ) may be printed with the patterns , sprues and runners , or it may be added later . fig6 a illustrates only one turbine wheel of the “ tree ” of fig5 , showing in greater detail the sacrificial pattern ( 52 ), of fig6 a which is repeatedly dipped in a refractory slurry until the thin blade sections ( 8 ) become thick ceramic shells ( 12 ) as shown in fig6 b . during this process , the sprue ( 7 ) also acquires a ceramic shell with an outer surface ( 11 ) as well as an inner surface ( 10 ) surrounding the sacrificial core which will be removed to form the channel through which the molten material will travel to the wheel casting . this process produces the part depicted in fig6 b . this last operation , translating the image of fig . a to the image of fig6 b is typical of the investment casting process . the end result of the above process becomes the end result of the second embodiment of the invention , which is generated in a different and innovative manner . a second embodiment of the invention , embodiment ( b ), will be explained by reference to fig7 . the methodology of a typical rapid prototyping procedure is again used in a production procedure , but this time , instead of fusing particles in order to create a male “ positive ” pattern , the method creates a “ negative ” female mold about a complete tree defining multiple shells ( 62 ) of the parts to be cast . in the second embodiment of the invention , the initial plane ( 64 ) is the first plane upon which material is deposited . then , layer , by layer , the deposition material is placed on the platen , and fused to the material deposited on the prior layer , until a full mold is built defining within it a tree . when plane ( 65 ) has been offered and no material is deposed onto this level , the process is complete . the mold shells ( 62 ) are linked to the mold of the vertical sprue ( 11 ) and the mold of the connecting runners ( 66 ). unsolidified particles exterior to the mold fall away as the mold is removed from the rapid prototyping “ box ”. interior non - fused particles are then removed by shaking or blowing , or are melted or burned out , producing a mold ready for casting . interior particles can also be blown away intermittently during mold forming . alternatively , the particles can be of a composition that changes from soluble to insoluble when fusing or cross - linking , such that interior non - fused particles can be dissolved following mold forming . further yet , the mold can be formed in , e . g ., stages of 20 layers , each stage can be rendered free of unfused particles , and stages can be stacked to form the final mold . the desired metal is melted and molten material enters the runners , sprues and patterns through the funnel ( 68 ). suitable mold forming particle materials and rapid prototyping processes are disclosed for example in u . s . pat . no . 5 , 382 , 308 ; u . s . pat . no . 6 , 335 , 052 ; u . s . pat . no . 6 , 350 , 495 ; u . s . pat . no . 5 , 902 , 441 ; u . s . pat . no . 5 , 940 , 674 ; ep 0731743 b1 ; and wo / 2001 / 029103 . in a variation of the second embodiment of the invention , as seen in fig8 b , instead of a thick ceramic shell ( 41 ), as seen in fig8 a , the shell ( 42 ) in the zone of the blades ( 1 ) is much thinner and is supported by a less dense structure . in the exemplary first variation of the second embodiment of the invention , the thinner ceramic shell is supported by struts ( 43 ) which are generated during the deposition stage of the process . the result is that the shell has less mass , which means that less material is used in generating the shell , the thermal inertia of the shell is reduced and the shrinkage deformation generated in the historic process ( with the thick shell ( 41 ) around the critical shapes and areas of the part being cast ) is minimized . the shell is constrained in a much more defined manner as the supporting structure can be placed to constrain the shell in the planes desired . the placement and orientation of the support structure can be ascertained by modeling rather than experience . in the above variation of the second embodiment of the invention , the support structure is shown as struts between shell walls . it could be a honeycomb - like structure , it could be any shape shown as desirable by finite element analysis or a computer driven modeling program . advances in the state of the art can be found in both forms of the invention : in case ( a ), the first embodiment of the invention : the present invention completely eliminates the capital cost of tooling , which can range from $ 20 , 000 to $ 150 , 000 . in case ( a ), the patterns are made using technology which was formerly used only for rapid prototyping and these are merged with the historical process , in place of tooling . this reduces what was a 6 basic step process down to 5 basic steps . in case ( b ), the second embodiment of the invention : the tooling , positive patterns and dipping and drying process are totally removed and replaced by a process in which the shell is produced as the first step in the foundry process . this takes what was a 6 basic step process down to 3 basic steps . the remaining 3 steps are eliminated . the short term gains will be lowered capital costs , the longer terms gains will be lower capital tooling cost and no drying rooms being required . taking at least 4 days out of the 5 formerly required for drying . because the layers are printed rapidly , and are , by design , thin steps , they dry quickly , with resultant minimal distortion . no hard tooling to manage . hard tooling simply no longer exists . each shell is produced , raw , from digital data , so the quality system required simply reverts to design control . no hard tooling to wear out . each tree made is made “ fresh ” directly from digital data . parts with complex geometry , which were not possible to manufacture using the traditional investment casting process , such as compressor wheels and turbine wheels with complex blade geometry ( twist , undercut , backsweep , warp , etc .) can be made with the same effort as those normally made using the investment casting process . negative rakes , or “ catches ”, which would have prevented retraction of the insert in the usual process , present no hindrance to this new process as there are no inserts which require retraction . cast titanium compressor wheels with a high degree of wrap and backsweep , which were limited to those which were pullable as disclosed for example in u . s . pat . no . 6 , 663 , 347 roby , decker need no longer be pullable , so that they can be cost - effectively cast using the investment process . this is true for any part using this invention . changeover from part to part is seamless as it will be simply a matter of loading software . from global perspective this means that not only can the “ printing ” device make turbine wheels of different sizes and designs , it could make turbine wheel shells one day and cast titanium compressor wheels the next , all tasks performed “ lights out ”, 24 / 7 . no wax machines to load the wax into the tools . in case “ b ”, no wax , or the machines in which the wax is injected into the voids , are a requirement . this reduces capital costs and space requirements . similarly with plastic sacrificial patterns , neither the devices to produce them , nor the material in which they are made , are required . in case “ a ” there will still be a requirement for some material from which to build the sacrificial male trees . no hand labor to build trees from patterns and flow runners . since , in case “ a ”, the entire tree will be produced lights - out , this will reduce head count . in case “ b ” this step simply does not exist . there will be less chance of damage to components of the wax trees as the wax handling requirement is either diminished or eradicated . since the mass , shape and volume of the shell are critical to the drying and shrinkage elements of the process , these parts of the shell can be modified so that the design of the areas is related to the function of each area . for example the shell must be capable of handling molten material . the backup to the shell can be made in a honeycomb pattern , rather than solid . this provides sufficient support to the shell but using less material and with the material placed where function requires for it to be placed . this will assist in both drying and shrinkage , at a reduced cost as there will be less material used . approximately 65 % of the cost of an investment cast turbocharger wheel is in the total shell manufacturing process . by taking the shell building segment of the process from 5871 minutes to 499 minutes , the cost of the wheel is reduced by 43 . 5 %. that is the 65 % shell process component of the part cost becomes only 5 . 5 % of the part cost . the total time for the entire process is 5871 minutes in 2007 . for case a , where the process prints the male consumable patterns as a tree , the process time using this invention rises by 418 minutes , an increase of 7 . 08 %, which is offset by no tooling to pay for or manage . although using case ( a ) increases the cost by 7 . 08 %, it makes it possible to manufacture a non - pullable wheel , or part , using the investment process , with the added incentive of no tooling cost . for case ( b ), where the process prints the female refractory shells as a tree , the process time is reduced by 5 , 372 minutes ( 89 . 5 hours ), a decrease of 91 . 5 %. this produces a massive reduction in cost , for a turbocharger wheel casting , normally costing $ 50 , the casting cost goes to around $ 22 , a savings in the region of 56 %. the material cost stays the same and the shell process cost goes from $ 32 . 50 to $ 4 . 25 . for either process it should be noted that in the case of a turbocharger with a cast titanium compressor wheel , and a standard turbine wheel , the cost savings will double . there will be the capital cost of the printing machine ( s ), but they run “ lights out ” so labor costs are greatly reduced and the automated assets are utilized to the maximum per day . since the asset can print any number of parts , the total asset cost of all the machines will be greatly reduced . parts are preferably arranged for uniform , even cooling of the mold . the following provides one example of cost savings on an industrial scale : step process time 2007 step 1 make wax pattern 2 step 1a make 30 wax patterns 60 step 2 build tree 2 step 3 build shell 5760 step 4 remove wax 30 step 5 pour metal 15 step 6 remove shell 4 total time ( minutes ) 5871 case a : step 1a make tree 480 step 2 0 step 3 build shell 5760 step 4 remove wax 30 step 5 pour metal 15 step 6 remove shell 4 total time ( minutes ) 6289 case b : step 3 build shell of tree 480 step 5 pour metal 15 step 6 remove shell 4 total time 499 ( minutes ) differences time change 2007 5871 case b 499 5372 91 . 5 % 2007 5871 case a 6289 − 418 − 7 . 1 % % cost in process minutes shell wheel cost shell cost matl 5871 65 . 00 % $ 50 . 00 $ 32 . 50 $ 17 . 50 499 5 . 52 % $ 21 . 75 $ 4 . 25 $ 17 . 50 56 . 50 % 86 . 92 % 0 . 00 % | 1 |
referring first more particularly to fig1 the electronic weighing apparatus 1 includes a housing 3 containing a weighing cell 5 , which housing also includes a weighing chamber 9 containing a weighing pan 11 . the housing includes a base 15 supported by three support feet 13 , which base also includes an off - set vertically displaced bottom wall 27 . the weighing pan 11 is connected for vertical movement relative to the housing 3 by means of a horizontal support arm 17 , and a vertically displaceable load receiver member 19 that is guided for vertical movement by resilient parallel horizontal upper and lower guide members 20 , as is known in the art . a transmission lever 23 is supported intermediate its ends by a flexible coupling member 26 that is connected with the vertically adjustable support member 28 . at one end , the transmission lever 23 is connected with the load receiver member 19 via coupling member 22 , and at its other end , the transmission lever carries the conventional electromagnetic load compensation coil 24 that is arranged for displacement within the annular gap contained within stationary permanent magnet means 25 . the electromagnetic load compensation system is well known in the art , as evidenced by the aforementioned u . s . pat . nos . 3 , 786 , 884 , and 4 , 489 , 800 . thus , when the transmission lever 23 is pivotally displaced about coupling member 26 upon the application of load to the weighing pan 11 , a position responsive signal ( produced , for example , by stationary photoelectric cell means ) is transmitted to the position signal generating means 50 that supplies a signal to the load compensation means 52 which supplies compensation current to compensation coil 24 via conductor 54 , thereby to maintain the transmission lever 23 and coil 24 in the initial no - load position . the amount of the compensation current supplied to the coil 24 is a function of the applied load , as indicated by the display means 56 . in accordance with the characterizing feature of the present invention , the printed circuit board 7 -- which carries electronic circuitry associated with the weighing system -- is supported in spaced relation above the housing bottom wall 27 by support members 29 arranged adjacent the edge portions of the printed circuit board . thus , first pairs of support members 29a are provided at the ends of the printed circuit board , and intermediate support members 29b are provided at opposite edges of the intermediate portions of the printed circuit board . thus , the printed circuit board -- which is formed of a suitable generally - resilient synthetic plastic material , such as a phenolic resin -- is supported solely at its edge portions relative to the bottom wall 27 . connected with the central portion of the printed circuit board by means of bolts 31 is the bottom section 5b of the load cell , which section has a u - shaped configuration as shown in fig2 . spacer sleeves or the like 33 are provided on the bolts to maintain the load cell 5 in spaced relation above the printed circuit board 7 . the permanent magnet system is , in turn , bolted to the upper ends of the bolts 31 . thus , the spacer sleeves 33 insure that the weighing cell is connected with the printed circuit board only at the precisely determined fastening locations within the central portion of the printed circuit board , whereby owing to the inherent resiliency of the printed circuit board , the load cell means 5 is resiliently supported in a protected manner relative to the bottom wall 27 of the housing 3 . there is no other connection of the weighing cell 5 with the housing 3 or base 15 . furthermore , load receiver 19 , which is guided for movement outside of the weighing cell and which carries the support arm 7 and weighing pan 11 -- is in no place connected with base 15 or housing 3 . thus , if , as a result of careless shipment , the weighing apparatus 1 is deposited roughly or dropped , the mass of the weighing cell 5 -- to which the sensitive force transmission and force guidance elements are fastened -- is resiliently cushioned in an attenuated manner upon the housing as impact takes place . according to a further advantage of the invention , the arrangement of the weighing cell on the printed circuit board simultaneously has the benefit of the effect of a mechanical low pass filter . this results in decoupling between the weighing cell and its environment , thereby reducing the effect of any possible disturbing oscillations upon the performance of the scale . if desired , the printed circuit board 7 could be supported solely by four supports 29 &# 39 ; arranged at its corners , as shown in phantom in fig3 . thus , omitting the intermediate supports 29b considerably improves the damping characteristic with respect to blows and bumps , resulting in improved protection of the mechanical components . on the other hand , with supports 29b omitted , a different sensitivity to vibrations affecting the operation of the balance will result . thus , in practice , the number and positioning of supports 29 , as well as the positioning of the connecting bolts 31 , is a compromise depending on the respective circumstances and demands on the performance of the scale . while , in accordance with the provisions of the patent statutes , the preferred form an embodiment of the invention has been illustrated and described , it will be apparent that various changes and modifications may be made in the apparatus described without deviating from the inventive concepts set forth above . | 6 |
referring to fig1 , a train track 100 , according to a first exemplary embodiment , includes two train rails 10 and a number of ties 20 . the two train rails 10 are laterally spaced apart one from the other by a distance sufficient to establish the desired gauge of the train track 100 . the ties 20 are parallel to each other and arranged between the two train rails 10 . each tie 20 is perpendicular to the two train rails 10 . referring to fig2 , the train rails 10 are approximately i - shaped in cross - section . each train rail 10 includes an upper rail head 12 , a lower rail head 14 , a web 16 connecting the upper rail head 12 to the lower rail head 16 , a first piezoelectric plate 17 , and a second piezoelectric plate 18 . the upper rail head 12 has an upper curved surface 120 to engage with the wheels of a train ( not shown ) and defines a first receiving groove 122 . the first receiving groove 122 is arranged within the upper rail head 12 and the length direction of the first receiving groove 122 coincides with the length direction of the train rail 10 . the first piezoelectric plate 17 is received in the first receiving groove 122 . the depth of the first piezoelectric plate 17 is less than half of the depth of the upper rail head 12 . the lower rail head 14 is substantially parallel to the upper rail head 12 . the lower rail head 14 defines a second receiving groove 142 . the second receiving groove 142 is arranged within the upper rail head 12 and the length direction of the second receiving groove 142 coincides with the length direction of the train rail 10 . the second piezoelectric plate 18 is received in the second receiving groove 142 . the depth of the second piezoelectric plate 18 is less than half of the depth of the lower rail head 14 . wires ( not shown ) connected to the first piezoelectric plate 17 and the second piezoelectric plate 18 extend through the train rails 10 to connect electronic devices or a storage battery on the train track 100 . each of the first piezoelectric plate 17 and the piezoelectric plate 18 is made of piezoelectric material , such as organic piezoelectric material , inorganic piezoelectric material , or compound piezoelectric material . in this embodiment , the organic piezoelectric material may be polyvinylidene fluoride . the inorganic piezoelectric material may be piezotransistor or piezoceramics . the piezotransistor includes quartz crystal , lithium gallium oxide , lithium germinate , lithium niobate and lithium tantalite . the piezoceramics includes barium titanate , barium zirconate titanate , modified barium zirconate titanate , and modified lead titanate . the compound piezoelectric material includes a polymer base , organic piezoelectric material and inorganic piezoelectric material . the organic piezoelectric material and the inorganic piezoelectric material are embedded in the polymer base . pressure on the train rails 10 from passing trains will be applied to the first piezoelectric plate 17 and the piezoelectric plate 18 . then , the two piezoelectric plates 17 and 18 transform the mechanical energy to electric energy . the two piezoelectric plates 17 and 18 will transmit the electric power to the electronic devices and / or the storage battery on the train track 100 . thus , the pressure of the trains can provide additional electric energy for charging the battery and / or powering the electronic devices on the train track 100 , achieving good energy conservation . referring to fig2 - 3 , a train rail 30 , according to a second exemplary embodiment , is shown . the differences between the train rail 30 of this embodiment and the train rail 10 of the first embodiment are : the first and second receiving grooves are omitted , and two piezoelectric plates 32 are arranged at opposite sides of the web 36 perpendicular to the upper and lower rail heads . referring to fig2 - 4 , a train rail 40 , according to a third exemplary embodiment , is shown . the differences between the train rail 40 of this embodiment and the train rail 10 of the first embodiment are : the first receiving groove is omitted , the second receiving groove 442 is exposed at the lower rail head 44 , and the second piezoelectric plate 48 is received in the second receiving groove 442 and is exposed at the lower rail head 44 . the advantages of the second and third embodiments are similar to those of the first embodiment . it is to be understood , however , that even though numerous characteristics and advantages of the present embodiments have been set fourth in the foregoing description , together with details of the structures and functions of the embodiments , the disclosure is illustrative only , and changes may be made in details , especially in matters of shape , size , and arrangement of parts within the principles of the disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed . | 7 |
referring firstly to fig1 there are shown in this figure three cables 10 , 11 and 12 which have been pulled , in a manner which is conventional and well known in the art and which is therefore not described herein , through a bundle or stringing block indicated generally by reference numeral 14 . the bundle block 14 is provided with three freely rotatable pulleys or rollers 15 , 16 and 17 . the cables 10 , 11 and 12 are received in peripheral grooves 19 , 20 and 21 , respectively , formed in the rollers 15 , 16 and 17 , respectively . the peripheral grooves 19 , 20 and 21 are lined , in conventional manner , with a relatively soft metal , e . g . aluminum , to avoid damage to the cables 10 , 11 and 12 . the roller 16 is also provided with a peripheral groove 23 for receiving a steel pulling cable ( not shown ), which is employed in conventional manner for pulling the cables 10 , 11 and 12 through the block 14 , the groove 23 being lined with a harder metal e . g . steel , to reduce wear thereon by the pulling cable . the bundle block 14 is connected by connecting pins 24 in suspension from and beneath a cable suspension bracket or yoke 25 which , in turn , is suspended from a cross - arm of a tower ( not shown ) by strings of insulators arranged in v - array , of which only the lowermost insulators 26 and 27 are , for convenience of illustration , shown in fig1 . prior to clamping or &# 34 ; clipping in &# 34 ; of the cables 10 , 11 and 12 to the suspension bracket 25 , the cables 10 , 11 and 12 are raised from their rollers 15 , 16 and 17 and temporarily supported , free of but close to the stringing block 14 , in temporary support hooks 28 , 29 and 30 . the support hook 28 is suspended from the suspension bracket 25 in order to load the latter , by the weight of the cable 10 , and thus to maintain the insulator strings in a taut condition after the cables 10 , 11 and 12 are lifted from the stringing block 14 . to maintain the stringing block 14 in balance during movement of the cables from the positions in which they are shown in fig1 to those in which they are shown in fig2 the cables 10 and 12 are preferably firstly lifted from their respective rollers 15 and 17 , while the cable 11 remains in its groove 20 which , as can be seen from fig1 is close to the centre of the stringing block 14 , in order to load the insulator strings . the cable 10 is then supported by the hook 28 from the suspension bracket 25 , after which the cable 11 is lifted from its roller 16 by the suspension hook 29 . the suspension hooks 29 and 30 are suspended by lines 31 which , in conventional manner , run over pulleys ( not shown ) supported by the tower . with the three cables supported as shown in fig2 the bundle block 14 is removed from the suspension bracket 25 by removal of the connecting pins 24 , the right - hand insulator string is uncoupled , as described in greater detail hereinafter , and the cable 12 is then raised upwardly through the right - hand insulator string , as indicated diagrammatically by arrows in fig3 . to enable this to be done , the insulator 26 is uncoupled from the adjacent insulator , indicated by reference numeral 32 in fig3 of its insulator string , and during such uncoupling the suspension bracket 25 is temporarily connected to that insulator string , at a position above the insulator 32 , by means of a temporary connecting tool 34 , of which only part of a lower portion or frame 35 is shown in broken - away condition in fig3 and which is also described in greater detail hereinafter . with the insulators 26 and 32 uncoupled to form a gap , indicated by reference numeral 33 in fig3 the cable 12 is raised , through the gap 33 , by means of the suspension hook 30 and the respective line 31 and is temporarily held above the top of the suspension bracket 25 , between the temporary connecting tool 34 and the insulator 26 , in the position illustrated in broken lines in fig3 and indicated by reference numeral 12a by the support hook 30 . the insulators 26 and 32 are then recoupled , and the temporary connecting tool 34 is released and removed from the suspension bracket 25 and the right - hand insulator string , so that the cable 12 can be moved upwards and secured , by means of a cable clamp indicated generally by reference numeral 36 , in the position in which it is shown in fig4 . the cables 10 and 11 both are likewise secured or &# 34 ; clipped in &# 34 ; to the underside of the suspension bracket 25 by respective cable clamps 37 and 38 , as shown in fig4 which shows the final &# 34 ; clipped in &# 34 ; cable bundle and associated suspension , the right - hand insulator string being indicated in fig4 by reference numeral 40 . the temporary connector tool 34 , which is the subject of copendng u . s . pat . application ser . no . 690 , 918 , filed may 28 , 1976 , by william h . chadwick jr ., and its manner of operation will now be described in greater detail with reference to fig5 to 8 . as can be seen from fig5 the temporary connecting tool 34 is of generally c - shaped configuration and comprises an upper portion or frame 42 , the lower portion or frame 35 , and means indicated generally by reference numeral 43 for interconnecting the lower end of the upper frame 42 and the upper end of the lower frame 35 and operable to effect longitudinal movement of the frames 35 and 42 relative to each other . the lower end portion of the lower frame 35 is bifurcated to enable it to straddle the suspension bracket or yoke plate 25 and is apertured to receive a flanged ball - lock pin 43 , which may be inserted through an aperture provided in the suspension bracket 25 in alignment with a socket clevis bolt 44 and with the longitudinal axis of the right - hand insulator string 40 . the bolt 44 serves to connect the lowermost insulator 26 of the insulator string 40 to the suspension bracket 25 , and the flange of the pin 43 is loosely connected to the lower frame 35 by a keeper cord or lanyard 46 . the upper end of the upper frame 42 is provided with clamping means , indicated generally by reference numeral 47 , which comprises a first semi - circular jaw 48 formed at the end of the frame and having a lateral extension 49 with a first slot 50 in its outer end , and a second semi - circular jaw 51 shaped complementally to jaw 52 , with a lateral extension 53 having a second slot 54 in one end aligned with the first slot 50 and pivotally mounted at its other end at 55 on the upper frame 42 . the clamping means 47 includes a bolt 56 pivotally mounted at 57 on the frame 42 for movement into and out of the slots 50 and 54 , with its free end threaded to receive a nut 59 for engagement with the lateral extension 53 , and a sleeve 60 having its inner end secured to the nut 59 and provided at its outer end with a radially extending handle 61 . the jaws 48 and 51 are adapted to embrace a metal cap 62 of one of the insulators in the string 40 , after which the lower frame is secured to the suspension bracket 25 by the pin 43 . as can also be seen from fig5 the lower portion of the upper frame 42 and the upper portion of the lower frame 35 are aligned with each other longitudinally of the temporary connection device 34 , and their outer ends are offset therefrom so that the centres of the jaws 48 and 51 and the securing means or pin 43 define a longitudinal axis which coincides with that of the insulator string 40 . the means 43 interconnecting the frames 35 and 42 includes four guide pins 64 which are parallel to that longitudinal axis . the lower part of the upper frame 42 defines a hollow housing 65 with an end portion 66 having suitable apertures for receiving the upper ends of the guide pins 64 which are secured thereto by pins 67 . the upper part of the lower frame 35 similarly defines a hollow housing 68 with an end portion 69 having apertures extending therethrough slidably receiving the guide pins 64 . stop rings 71 are mounted on and suitably secured to the lower ends of guide pins 64 to limit downward sliding of the lower frame 35 on the pins 64 . the interconnecting means 43 , as previously noted , also effects longitudinal movement of the frames 42 and 35 relative to each other . to this end it includes an hydraulic cylinder 72 ( fig6 ) having a connecting member 73 secured to its lower end , as by welding , which is disposed within the housing 68 and is connected thereto by a pin 74 . a piston 75 mounted in the cylinder 72 has its rod extending upwardly in the housing 65 and connected thereto by a pin 76 . the upper end of the cylinder 72 is connected in well - known manner to an hydraulic line or conduit 77 and the lower end of the cylinder similarly is connected to a line 78 . a double pilot operated check valve 79 ( fig5 ) is interposed in the lines 77 and 78 , and beyond the valve 79 those lines are connected to a four - way manual three - position detent control valve 81 which is controlled by a handle 82 . the interconnection of these hydraulic mechanisms is illustrated schematically in fig8 which also shows a conduit 83 connecting the valve 81 to a reservoir or source of fluid 84 and an inlet conduit 85 connecting the reservoir 84 to a hand pump 86 . the latter is operably by a handle 87 and is connected to the control valve 81 by an outlet conduit 88 . the hand pump 86 and reservoir 84 preferably are formed as an integral unit . the valve 79 prevents the cylinder 72 from bleeding down should there be a hydraulic failure in the pump 86 or the control valve 81 . this also makes it necessary to power the cylinder 72 down , instead of allowing it to bleed down by gravity or be forced down by an external load . such operation is important here because the insulators will not withstand very high shock or impact loads . it will be readily apparent from fig8 that the control valve 81 may be operated by its handle 82 to select the power - up or power - down modes of the cylinder 72 and its piston 75 in response to operation of the pump 86 by means of its handle 87 . as previously noted , the above - described temporary connector device is employed when it is desired to move the cable 12 upwardly through the insulator string 40 . to enable such movement of the cable 12 , the lineman will interconnect a portion of the insulator string 40 and the suspension bracket 25 , as shown in fig5 . to accomplish this , the jaws 48 and 51 are secured around the metal cap 62 of one of the insulators of the string 40 by means of the nut 59 and the bolt 56 , and the lower frame 35 then is mounted upon the suspension bracket 25 and connected by the pin 43 thereto . the frame 42 is then displaced downwardly relative to the lower frame 35 in the direction of the axis of the insulator string 40 by first adjusting the valve handle 81 to set the control valve in position for a power - up mode , and then actuating the pump handle 87 . this will force fluid into the upper portion of the cylinder 72 through the line 77 to move the piston 75 downwardly . only a relatively small degree of relative movement of the frames is required , i . e . just enough travel to relieve tension in the insulator string 40 to facilitate removal of the socket clevis bolt 44 or , as shown in fig5 an insulator connecting pin 90 between the insulators 26 and 32 . this provides clearance for movement of the cable 12 upwardly to the dotted line position illustrated at 12a in fig3 and 5 . upon completion of the movement of the conductor through the insulator string 40 , i . e . from one side of it to the other , the insulator string is reconnected by replacing the bolt 44 or pin 90 and the valve 81 is adjusted by moving its handle 82 to a power - down mode . subsequent operation of the pump handle 87 will move the frames 35 and 42 away from each other . the insulator string 40 thus will resume its support of the suspension bracket , and the temporary connector device 34 is then removed . the cable 12 then may be moved from its broken line position 12a and connected in its final position of fig4 to the suspension bracket 25 by the clamp 36 . as will be readily apparent to those skilled in the art , the present invention is not restricted to the stringing of a bundle of cables from a suspension bracket or yoke plate suspended by only two insulator strings . on the contrary , the invention may , for example , be employed with a suspension bracket suspended , for example , by two pairs of insulator strings in v - array , i . e . with two insulator strings disposed parallel to one another and spaced apart in the longitudinal direction of the cables at each side of the suspension bracket . in this case , a pair of temporary connecting tools such as the tool 35 are employed to enable the two insulator strings at one side of the suspension bracket to be uncoupled for passage of a cable upwardly therethrough . furthermore , while the above - described preferred embodiment of the invention makes use of the tool 34 to provide a temporary connection between one of the insulators of the string 40 and the suspension bracket 25 , it is alternatively possible , for example , to employ a modification of the tool 34 to provide a temporary connection between two of the insulators of the string 40 or between one of the insulators and a suitable link included in the string 40 or between the tower cross - arm and one of the insulators or the suspension bracket 25 . while the above - described suspension bracket 25 is designed to support only one cable , namely the cable 12 , on the top of the suspension bracket between the insulator strings , the invention can also be employed to pass a plurality of cables through one or more insulator strings in cases where the suspension bracket is designed to suspend more than three cables with more than one cable between the insulator strings at opposite sides of the suspension bracket . | 7 |
in the following detailed description of exemplary embodiments of the invention , reference is made to the accompanying drawings that form a part hereof , and in which is shown by way of illustration specific exemplary embodiments in which the invention may be practiced . these embodiments are described in sufficient detail to enable those skilled in the art to practice the invention . other embodiments may be utilized , and logical , mechanical , and other changes may be made without departing from the spirit or scope of the present invention . the following detailed description is , therefore , not to be taken in a limiting sense , and the scope of the present invention is defined only by the appended claims . installing a video surveillance system in a vehicle provides extensive visual input to operators with an otherwise limited view . camera views for full 360 ° planar horizon coverage can be accomplished with a limited number of fixed cameras depending on required resolution and field of view . fixed cameras are necessary in order to capture images that can be generated before a triggering event from an unknown direction and distance . in security surveillance scenarios , pre - positioned cameras can provide continuous video imagery before , during and after an event , such as opening a window or door equipped with a sensor . fig1 shows a hardware network diagram 100 of the video surveillance system for a vehicle as described for various exemplary embodiments , such as installed in a road - mobile vehicle . a video server 110 provides network control and application software operation and connects to workstations 120 task - specific operators . the server 110 and workstations 120 can be state machines , such as computers . these workstations 120 include client interface terminals for a vehicle commander station 122 , a lethal weapons operator 124 , and a non - lethal instruments operator 126 . the lethal operator 124 controls a large - caliber gun having an optical gunsight . the non - lethal operator 126 controls a variety of devices , such as a loudspeaker bullhorn , laser dazzler , etc . the server 110 and workstations 120 connect to a main communications bus 130 using transmission control protocol ( tcp ) communication for exchanging operational instructions and information , and a video bus switch 140 for providing user datagram protocol ( udp ) video streams to the terminals . the communications bus 130 also connects to a gun - mount video ( called remote weapons station or rws ) information 150 , infrared shot detection devices ( called “ overwatch ” or ow ) 160 , other non - video devices 170 and video devices 180 . fig2 shows a flow diagram 200 of information to and from the video switch 140 , which receives information from surveillance cameras 210 , video police tactical unit ( ptu ) 220 , ow video 160 and rws video 150 . a video computer 230 , whether integral to , in communication with , or isolated from the server 110 , submits instructions to the video switch 140 and receives information , and provides for operator comparison information accessible from video storage 240 to provide to operator terminals for the commander 122 , the lethal operator 124 and the non - lethal operator 126 . the visual information can be received by the computer 230 from the camera image providers 150 , 160 , 210 , 220 for selected retrieval and review , such as after a triggering event . video storage 240 can serve to separately buffer the input signals received from the cameras 210 . alternatively , each camera 210 may contain an individual buffer whose contents can be retrieved by the computer 230 via the video switch 140 . the video storage 240 can also provide archival storage for previously buffered images to be retrieved for subsequent review of events captured by one or more specific cameras 210 . additional sensors can be employed to augment situational awareness , such as acoustic - sensitive instruments . fig3 shows a software network diagram 300 for the workstations 120 connected to network architecture 310 . the vehicle commander station 122 includes a primary brain ( e . g ., computer ) 320 with software installed for commander instance 325 ( i . e ., for instantiation of the relevant software application ). the lethal operator 124 includes a primary failover brain 330 having installed software for lethal instance 335 . the non - lethal operator 126 includes a secondary failover brain 340 having installed software for non - lethal instance 345 . the commander instance 325 provides communication with the primary brain 320 running as a service on the same computer for operations such as target acquisition . sheriff represents an example of such application software for use in such terminals 120 . all communication for control of a resource passes through the primary brain 320 through the main communications bus 130 for passing signals through the network 310 . primary and secondary brains 330 , 340 are synchronized to the primary brain 320 , so that in the event of primary brain disablement from the network 310 , the sequentially subsequent processor , in this case the primary failover brain 330 , becomes the primary . upon returning online , the original primary is relegated to the last backup to become the new secondary failover brain . similarly , in the event of primary failover disablement from the network 310 , the secondary failover brain 340 becomes the primary . the primary brain 320 includes items 350 such as a target list , resource contention prioritization , and resource control protocol . the sheriff software 360 as code on the instances 325 , 335 , 345 , includes a graphical user interface ( gui ), state machine ( for determining and operating on logic states ) and a hardware layer for signal exchange . fig4 shows a gui display 400 including a window 410 for camera control on a pan - tilt unit . the window 410 displays the live video feed from a selected camera . an upper menu 420 provides enlarge (+), reduce (−), reset zoom to default , and magnification ratio ( 1 ×) of the captured image . a button 420 ( identified as “ vc ” for vehicle commander ) identifies the operator who currently controls the camera . a circle 430 ( located in the window &# 39 ; s center ) enables the operator to capture a still image of the current video frame on display . directional arrows 450 along the border of the window 410 enable the operator to reposition the camera on its platform in any one of eight directions . fig5 shows a first exemplary window 500 for the gui used in sheriff 360 . the upper menu 510 includes buttons for system , filter , a sequential toggle 520 for polar direction and range view , create record and delete record . a view window 530 includes a map ( featuring a naval reservation ) centered about the vehicle &# 39 ; s position 540 superimposed by a compass rose 550 . auxiliary adjacent thumbnail images of an exterior camera view 560 and a direction - range polar plot 570 are displayed to the left of the view window 530 . auxiliary cornmand side menu buttons 580 and bottom menu buttons 590 provide additional commands for operations . fig6 shows a second exemplary window 600 for the gui in response to the operator selecting the toggle 520 . in response , the toggle alters to video view icon on the button , now labeled 610 . the view window , now labeled 620 , displays a polar coordinate compass rose with geographical orientation and ranges ( in meters ) from the center icon 630 . the adjacent thumbnail images include the exterior camera view 560 and a map view 640 , as shown on the view window 530 . fig7 shows a third exemplary window 700 for the gui in response to the operator selecting the toggle 610 . in response , the toggle switches to map view icon on the button , now labeled 710 . an image view 720 includes an enlarged render of the camera imagery . several smaller images surround this window 720 , in this example showing the same image , but available for showing images 730 from alternate cameras from several vantages . the adjacent thumbnail images to the right of the window 720 include the exterior camera view 560 and the map view 630 . the image view 720 represents the full resolution display of any of the adjacent thumbnail images 730 . fig8 shows a fourth exemplary window 800 for the gui used in sheriff 360 similar to the first exemplary window 500 with the sequential toggle 520 returned to polar direction and range view . the view window 810 includes a map modestly zoomed out from the map window 530 and the compass rose 820 about the center corresponding to the vehicle &# 39 ; s map position 540 . a rounded cruciform icon 830 identifies a location relative to the vehicle &# 39 ; s position 540 where sensors detect occurrence of a triggering event . the icon 830 corresponds to an entity of unknown intent . alternate icons can be employed for friendly , neutral and confirmed hostile positions . the upper right window 840 displays a video feed from a record retrieved from an event - registering buffer corresponding to the video from the surveillance camera that pointed in the direction of the triggering event . ( the window 840 shows an interior laboratory image for demonstration purposes .) the upper left window 850 displays video stream from the gunsight optics , which can slew towards the event direction . if the operator selects the icon 830 , the permanently recorded images are then displayed to the operator in a video loop shown in the window 840 . this loop contains image sequences before , during , and after the event . thus , if an antagonist were to emerge from a place of hiding ( e . g ., the corner of a building ), fire a shot , and then retreat to resume hiding , the recorded image sequence shows the building enabling the operator to view the antagonist emerge from behind the building , shoot , and go back behind the building . thus , the system provides automatic recording of this sequence for the operator to view the pre - and post - event images and thereby assess the nature of the event for further attention . while on patrol , a vehicle equipped with multiple surveillance cameras 210 can scan a wide area while personnel remain within the confines of that vehicle to provide protection . this enables continuous spatial coverage for a limited temporal interval before the buffer memory recycles storage . shortly subsequent to an event registered by a sensor that triggers a response , the archival memory automatically retrieves buffer contents from a surveillance camera that points to the sensor - indicated direction of the event , while video recording continues into the buffer . the memory contains images over a first interval prior to the event , as well as over a second interval after the event , in order to more complete context to circumstances surrounding the event . the operator is alerted and may select the archived video recording from the archival memory . the operator can be alerted by a sensor , which may be installed in each camera , such as an optical flash photometer or an audio shock transducer . this selection can be made by the operator or performed automatically in response to a specified sensor stimulus . meanwhile the cameras 210 continue to record visual images at a specified frame rate . the archive thereby contains continually sequential visual records before , during and after the triggering event , which can be immediately reviewed to assess the event &# 39 ; s hazardous nature against which a response ( lethal or non - lethal , if any ) may then be decided . such operation enables visual information to be obtained more rapidly and completely with which to issue critical instructions in the field . because the workstations 120 have interoperable redundancy , the failover of any single platform does not jeopardize receipt and process of the visual information for evaluation . artisans of ordinary skill will recognize that such methods and systems are applicable for stationary buildings , in addition to road - mobile vehicles . videoslinger provides a subsystem for sheriff that streams video from various cameras around the vehicle to the operator of the sheriff video surveillance system . videoslinger enables the operator to interact with the camera systems to view targets , reposition , and zoom the cameras . the videoslinger subsystem includes the following capabilities in relation to various exemplary embodiments : ( a ) retrieve video from various cameras and display the video to the operator and store video for deferred viewing ; ( b ) snap still images of targets upon detection ; ( c ) enable the operator to select camera video streams for discretionary viewing ; ( d ) enable the operator to capture selected still images of the video streams ; ( e ) enable the operator to pan / tilt / zoom selected cameras under camera control ; ( f ) maintain reliability of direct control of the videoslinger cameras , such as by brain failover hardware features ; ( g ) manually control the cameras in a first - come , first - serve priority basis ; ( h ) automated control assumed of a specified camera to capture an image of a new target in response to a specified event , thereby suspending manual control by the operator until the system completes its required assignments ; ( i ) inhibition of manual control transfer to another operator until current operator has released control authority . in various exemplary embodiments , the operator maintains control of the cameras in the following manners : ( a ) monitor display for the camera shows directional buttons for directions n , ne , e , se , s , sw , w , nw , and displays a center capture image for manual screen capture ; ( b ) the directional display is configurable enabling the operator to select how and whether the buttons appear , such as always , never or hover ( i . e ., when the operator moves the cursor into a defined region ), ( c ) zoom in , zoom out , current zoom ratio and reset buttons are above the video feed ; ( d ) zoom ratio is displayed ( e . g ., “ 1 ×”, “ 2 ×”, etc .) at a screen position ( e . g ., upper right corner above the video feed ), with digital zoom indicated by a supplemental “ d ”, and reset returning the camera to the default ratio ; ( e ) identity of the operator in control is displayed at a screen position ( e . g ., in the upper left corner ), such as “ vc ” for vehicle commander , “ le ” for lethal operator and “ nl ” for non - lethal operator , or other designators as desired ; ( f ) directional indicators for the camera can be indicated by a compass rose and / or other mount indicators . while certain features of the embodiments of the invention have been illustrated as described herein , many modifications , substitutions , changes and equivalents will now occur to those skilled in the art . it is , therefore , to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the embodiments . | 7 |
fig1 shows an operating device 11 according to the invention , as it can be used on the anterior side in a control panel 12 of an electrical appliance , for instance an electric oven . the control panel 12 has a correspondingly formed recess 13 which , as shown in fig2 also , has a round and stepped form for flush insertion of the operating device 11 in the control panel 12 . the operating device 11 has a rotary knob 15 as a control element . the rotary knob 15 has a grip part 16 that projects beyond the control panel 12 and which is mounted on a base part 17 . the operating device 11 and / or rotary knob 15 are in the form of retractable knobs so that , as shown in fig3 and 4 , the grip part 16 can be displaced onto the base part 17 by pressing and then projects to only a very minor extent beyond the control panel 12 . the corresponding mechanism for this will be familiar to a person skilled in the art and does not need to be explained further . the rotary knob 15 is mounted or fixed in a receiving cup 19 . the receiving cup 19 has an outer jacket 20 that is advantageously cylindrical and round circumferential , as well as a corresponding inner jacket 23 . the lower part of the grip part 16 or , substantially the entire grip part 16 corresponding to fig4 , is in the space between the outer jacket 20 and inner jacket 23 . the outer jacket 20 and inner jacket 23 are connected to each other , are advantageously a single part and in particular are manufactured at the same time and / or with one another . to the front the receiving cup 19 or the outer jacket 20 has a collar - like extension 24 , which forms a circular ring . this can be seen in the top view in fig2 . the circular ring - like , collar - like extension 24 is divided into 4 fields of illumination 25 a to 25 d . this is described in more detail below . a rotary switch device 28 is secured to a posterior end 26 of the receiving cup 19 in a usual manner in accordance with the afore - mentioned ep 1 318 534 a1 . the rotary switch device 28 also has the usual form , for instance in accordance with ep 1 898 184 a1 . in particular it is a so - called grey code switch . a support 29 is disposed on the rear - facing end 26 of the receiving cup as known from the afore - mentioned ep 1 318 534 a1 . an axle stub 30 is mounted on this support 29 so that it can rotate , but is fixed in an axial direction . this axle stub 30 ensures transfer of the rotation from the grip part 16 to the rotary switch device 28 . a lighting means 32 d is arranged on the left and a lighting means 32 b is arranged on the right in the rotary switch device 28 , especially leds . reference is made to these in the aforementioned ep 1 898 184 a1 , wherein the lighting means 32 either have the same control / same plug connection as the rotary switch device 28 or a separate one . the light from the left lighting means 32 d is coupled on the left into the outer jacket 20 of the receiving cup 19 . for this it comprises light - conducting material 21 , as well as the corresponding illuminated field 25 d . the inner jacket 23 can also comprise light - conducting material , but this is of secondary importance . the largest part of the outer jacket 20 can be substantially of light - conducting material 21 . as is clearly seen in fig2 , both the outer jacket 20 and the illuminated fields 25 a to d can be subdivided into four regions or sectors . this subdivision is formed through separating strips 22 of non - light - conducting material . these separating strips 22 may be manufactured as a single piece with the rest in the region of the collar - like extension 24 , in particular through two - component injection moulding . they can extend from the collar - like extension 24 , i . e ., between the illuminated fields 25 , through the outer jacket 20 of the receiving cup 19 to the posterior end in front of the lighting means 32 . the separating strips 22 therefore bring about a division into four of the light - conducting material 21 as shown in fig2 in a direction in the drawing plane . a lighting means 32 , arranged behind each light - conducting region in accordance with section b - b , which can be seen in the sectional view in fig1 , sits approximately centrally when viewed in a circumferential direction and radiates light into one of the light guides formed so to speak as a result and which then exits frontally at the illuminated fields 25 a to 25 d . a greater or smaller number of divisions may be provided in place of the division into four shown here . a corresponding number of lighting means then has to be provided , wherein in a further development of the invention , more than one lighting means , for instance more than one led , is provided per illuminated field 25 . in the side view shown in fig3 it can be seen how two regions of the receiving cup 19 and / or its outer jacket 20 comprise light - conducting material 21 . they are , however , separated through a separating strip 22 , which also extends seamlessly through the collar - like extension 24 and therefore also separates the illuminated fields 25 from one another and prevents over - illumination . in the sectional view shown in fig4 according to section a - a in fig2 , the cut goes directly through the plane of two separating strips 22 . this is also recognisable through the different hatching in the region of the separating strips 22 and on the outer jacket 20 as well as on the collar - like extension 24 . furthermore , it can be seen that the separating strips 22 are also provided on the inner jacket 23 to bring about complete separation of adjoining circular ring segments . if the grip part 16 , however , is of non - light - transmitting material , then it does not matter if it is illuminated through the inner jacket 23 extending within it . through any desired control of the lighting means 32 , in principle also fully independently of whether the rotary knob 15 is pressed in or is in an out position , it is possible to control whether one or more of the illuminated fields 25 a to 25 d is illuminated . as already described , some of the lighting means 32 can be coloured , so that the illuminated fields 25 may be illuminated in different colours . whilst the afore - mentioned two - component injection moulding is the preferred manufacturing method for such a receiving cup 19 , of corresponding light - conducting material 21 with separating strips 22 in between , other possibilities are also conceivable . for instance , a plurality of parts of the same type can be grouped together to form a receiving cup 19 , with possible interspersion of non - light - conducting layers or parts . alternatively , for instance , laser irradiation of the receiving cup manufactured from actual light - conducting material along the separating strips could change it such that light is no longer conducted here or that sectors so to speak can no longer be overcome . the spring 34 , recognisable in the sectional views , of metal and connected to a metal button disposed on the anterior side of the grip part 16 , can be electrically contacted through an axle stub 30 that is also electrically conducting . this enables a capacitive touch switch to be created in accordance with us 2007 / 0181410 a1 . reference is also drawn to the german patent application de 102009006421 . 4 lodged at the same priority date by the same applicant . an alternative operating device 111 is shown in fig5 , in which a rotary knob 115 is again disposed in a control panel 112 or cut - out section 113 . this rotary knob 115 is also in the form of a rotary retractable knob and is only shown in a retracted state , a grip part 116 is therefore pushed onto a base part 117 . the receiving cup 119 here is without a collar - like extension as before , and instead has only its front face 137 in the cut - out section 113 . this yields , through the front face 137 , a narrow ring that encircles the grip part 116 . a collar - like extension 124 is displaced a little downwardly and serves to secure the receiving cup 119 in a stabile and non - tiltable manner to the control panel 112 . it cannot , however , be seen from the front . it can also be seen that an outer jacket 120 , that becomes the afore - mentioned collar - like extension 124 , is substantially of pipe section form and is not manufactured as a single part with an inner jacket 123 of the receiving cup 119 , but instead is disposed on top of it and is advantageously connected to it or bonded to it . here too , a rear - facing end 126 of the receiving cup 119 , in this case within the outer jacket 120 , is connected to a rotary switch device 128 . an axle stub 130 is mounted in a support 129 and in turn engages in the base part 117 of the rotary knob 115 . in addition , it should further be noted that the rotary switch device 128 is disposed on a circuit board 131 and in particular is also electrically connected . the circuit board 131 also bears lighting means 132 , advantageously in the form of leds and / or smd leds . not shown in fig5 are corresponding separating strips between the light - conducting material , which substantially forms the outer jacket 120 and the inner jacket 123 . this can , however , have a form analogous to the previous embodiments . above all , however , it is possible or envisaged with an operating device 111 according to fig5 for the outer jacket 120 and inner jacket 123 of the receiving cup 119 to be connected to one another in a non - light - conducting manner , and for this reason different lighting means 132 are provided . they can be separated by a coating or intermediate layers . so , for instance , the coupling of light into the outer jacket 120 can bring about a narrow , circular segment - like light appearance at the front faces 137 on the control panel 112 , with a division that embraces a 90 ° elbow angle similar to fig2 , or less or more . the illumination of the inner jacket 123 can be used to create an optical display through lights on the anterior side of the grip part 116 . for this the anterior side of the grip part 116 can be formed from corresponding light - transmitting material . so , for example , different functional states of the operating device 111 can also be shown on the rotary knob 115 . illumination of the knob on the one hand or the control panel on the other hand can , in line with the general concept of the invention , be achieved together or only individually . above all , different illuminations and different colours can thus be generated . furthermore , a segmentation of the inner jacket 123 and outer jacket 120 through corresponding separating strips can be different , in particular through angular displacement , relative to one another . this enables any desired illuminated representation to be achieved . | 6 |
laser beam scanning optical devices embodying the present invention will be described below . with reference to fig1 the laser beam scanning optical device comprises a light source unit 1 having a laser diode and a collimator lens incorporated therein , beam shaping slit plate 2 , cylindrical lens 3 , polygonal mirror 4 , toroidal lens 5 , spherical mirror 6 , plane mirror 7 , sos sensor 9 for detecting an image writing position , and mirror 8 for guiding a laser beam to the sensor 9 . these components are mounted on a base plate 10 and covered with an unillustrated cover . the laser diode is ( on - off ) controlled for modulation based on image data fed to an unillustrated control unit , and when it is on , a laser beam is emitted by the light source unit 1 . the laser beam is formed by the collimator lens into a bundle of convergent rays concentrating at a rearward definite position , and is thereafter changed by the cylindrical lens 3 in its spot form to a substantially linear shape the lengthwise direction of which is parallel to the main scanning direction , whereupon the beam reaches the polygonal mirror 4 . the polygonal mirror 4 is drivingly rotated in the direction of arrow a at a constant speed , whereby the laser beam is deflected at a constant angular velocity within a plane perpendicular to the axis of rotation of the mirror 4 and guided to the toroidal lens 5 . the toroidal lens 5 is provided with a surface of incidence and a surface of emergence which are concentric in scanning section , and has a definite power in a direction perpendicular to the plane of deflection . the combination of the toroidal lens 5 and the cylindrical lens 3 corrects the inclination of deflecting plane of the polygonal mirror 4 . the laser beam is further reflected at the spherical mirror 6 . the reflected beam is reflected downward at the plane mirror 7 , passes through a slit 11 provided in the bottom of the base plate 10 and forms images on an unillustrated photosensitive drum . the formation of images on the drum is accomplished by the main scanning movement of the laser beam due to the rotation of the polygonal mirror 4 in the direction of arrow a and the subscanning movement of the beam due to the rotation of the photosensitive drum . the spherical mirror 6 has an fθ function ( distortion correcting function ) for correcting the main scanning speed of the laser beam and also a function of correcting curvature of field on the photosensitive drum . the toroidal lens 5 and the spherical mirror 6 are each integrally molded of a resin material ( such as polycarbonate or acrylic resin ). the structures for mounting these components in place will be described below . with reference to fig2 the toroidal lens 5 is provided on its bottom surface with a projection 5a at the lengthwise midportion thereof and projections 5b , 5c at its opposite ends . on the other hand , the base plate 10 is formed with holes 12a , 12b , 12c for inserting the projections 5a , 5b , 5c thereinto respectively . the projections 5a , 5b , 5c and the holes 12a , 12b , 12c are provided with seats 5a &# 39 ;, 5b &# 39 ;, 5c &# 39 ;, 12a &# 39 ;, 12b &# 39 ;, 12c &# 39 ;, respectively . these seats serve to accurately position the toroidal lens 5 at a specified level when the lens 5 is mounted on the base plate 10 . the central hole 12a is an elongated hole extending in a direction parallel to the optical axis x for the inserted projection 5a to fit to the hole portion only with respect to a direction orthogonal to the optical axis x . the end holes 12b , 12c are each in the form of an elongated hole extending in a direction orthogonal to the optical axis x , so that the inserted projections 5b , 5c fit to the respective hole portions only with respect to a direction in parallel to the optical axis x . thus , when the projections 5a , 5b , 5c are forced into the respective holes 12a , 12b , 12c , the toroidal lens 5 is positioned in place with respect to the direction orthogonal to the optical axis x by the engagement of the projection 5a in the hole 12a , and is positioned in place with respect to the direction in parallel to the optical axis x by the engagement of the projections 5b , 5c in the respective holes 12b , 12c . the projection 5a is fixed in the hole 12a with an adhesive , and each end of the toroidal lens 5 is elastically held in position from above by a plate spring 13 ( see fig1 ). with the arrangement described above , the toroidal lens 5 made of resin is susceptible to deformation , especially to longitudinal expansion or shrinkage , due to variations in ambient conditions . the midportion of the toroidal lens 5 is restrained in position with respect to the direction orthogonal to the optical axis x by the engagement of the projection 5a in the hole 12a and adhesion , while at the opposite ends of the lens 5 , the protections 5b , 5c are movable relative to the holes 12b , 12c in the direction orthogonal to the optical axis x . accordingly , deformation of the toroidal lens 5 is absorbed by the projections 5b , 5c slightly moving within the holes 12b , 12c . this obviates the likelihood that the distortion of the toroidal lens 5 will impair its optical performance , incidentally , the hole 12a in the midportion is elongated in the direction parallel to the optical axis x to make the projection 5a easily insertable thereinto . fig3 shows a structure for mounting the spherical mirror 6 on the base plate 10 . the relation between projections 6a , 6b , 6c on the spherical mirror 6 and holes 14a , 14b , 14c formed in the base plate 10 is the same as the relation between the projections on the toroidal lens 5 and the corresponding holes . the spherical mirror 6 is fixedly mounted on the base plate 10 by inserting the projections 6a , 6b , 6c into the respective holes 14a , 14b , 14c , fixing the projection 6a in the hole 14a with an adhesive and causing a plate spring 15 ( see fig1 ) to press each end of the mirror 6 against the base plate 10 . the deformation of the spherical mirror 6 to be caused by variations in the ambient conditions is absorbed in the same manner as in the case of the toroidal lens 5 by the movement of the projections 6b , 6c in the respective holes 14b , 14c in a direction orthogonal to the optical axis x . seats 6a &# 39 ;, 6b &# 39 ;, 6c &# 39 ;, 14a &# 39 ;, 14b &# 39 ;, 14c &# 39 ; are provided for positioning the spherical mirror 6 at a specified level . especially with reflecting optical elements like the spherical mirror 6 , the distortion of the reflecting surface produces approximately twice as great an adverse influence as is the case with transmission optical elements like the toroidal lens 5 . accordingly , the foregoing mount structure which will not permit distortion of the optical element is effective for the spherical mirror 6 and like reflecting optical elements . moreover , the structure eliminates the likelihood that the spherical mirror 6 will rise off the base plate 10 because the deformation of the mirror 6 is absorbed at its opposite end portions and further because the mirror midportion is fixed to the plate 10 by the adhesion of the projection 6a to the hole portion 14a . if the midportion of the spherical mirror 6 rises off the base plate , the scan line on the photosensitive member will be bent , whereas the present embodiment is free of such a drawback . the second embodiment has the same construction as the embodiment of fig2 except that the midportion projection 5a on a toroidal lens 5 is fittable into a hole 12a which is circular . this embodiment is similar to the first in operation and advantage . in addition , the projection 5a is restrained in position with respect to any of directions in parallel to the optical axis x and orthogonal thereto . the midportion is therefore positionable in place more reliably . with this third embodiment , the midportion projection 5a on a toroidal lens 5 is fittingly inserted into a hole 12a which is circular , and the hole 12b for the end projection 5b to be inserted thereinto is a circular hole having a slightly larger diameter than the projection 5b . the hole 12c for receiving the other end projection 5c therein is an elongaged hole in which the projection 5c is fittable only with respect to a direction parallel to the optical axis x as in the first and second embodiments described . according to the third embodiment , the toroidal lens 5 is positioned in place on the base plate 10 by fitting the projection 5a into the hole 12a and inserting the projection 5c into the hole 12c to thereby fit the projection 5c to the hole portion 12c with respect to the direction parallel to the optical axis x . the hole 12b is given a larger diameter than the projection 5b to make the toroidal lens 5 fixedly mountable on the base plate 10 without trouble even if the position where the projection 5b or the hole 12b is formed involves a slight error . the hole 12b absorbs the deformation of the end portion of the toroidal lens 5 with respect to any direction . with this fourth embodiment , a toroidal lens 5 is formed with holes 5d , 5e , 5f like those of the first embodiment , and a base plate 10 is provided with projections 12d , 12e , 12f as positioned in corresponding relation with the respective holes 5d , 5e , 5f . seat 5d &# 39 ;, 5e &# 39 ;, 5f &# 39 ;, 12d &# 39 ;, 12e &# 39 ;, 12f &# 39 ; are provided for positioning the toroidal lens 5 at specified level . this embodiment has same construction as the first with the exception of the above feature . the laser beam scanning optical device of the present invention is not limited to the foregoing embodiments but can be modified variously within the scope of the invention . for example , the mount structure shown in fig4 and 6 are applicable not only to the toroidal lens 5 but also to the spherical mirror 6 . these mount structures and those shown in fig2 and 3 are further applicable to plane mirrors and other elongated optical elements . although the present invention has been fully described by way of examples with reference to the accompanying drawings , it is to be noted that various changes and modifications will be apparent to those skilled in the art . therefore , unless otherwise such changes and modifications depart from the scope of the present invention , they should be construed as being included therein . | 6 |
embodiments of the present invention are explained in conjunction with the drawing in detail hereinafter . an optical system and a playback signal output system of the first embodiment are shown in fig1 . the laser beam emitted from a semiconductor laser 201 is diffracted with a diffracting device 202 . the 0th light of the laser beam from a diffracting device 202 is converted into a parallel light beam with a collimating lens 203 and focused on an information recording layer of an optical disk 205 with an objective lens 204 . the light reflected by the information recording layer progresses in a reverse direction with respect to an outward path and converted into a parallel light beam with the objective lens 204 . the parallel light beam is converted into a convergence light beam with the collimating lens 203 and incident on the diffracting device 202 . the diffracting device 202 is divided into three division regions 202 a to 202 c . the region 202 a and the regions 202 b and 202 c are divided by a division line in a disk radial direction indicating a radial direction of the optical disk . the regions 202 b and 202 c are divided by a division line in a disk tangential direction indicating a tangential direction of the optical disk 205 . a photodetector 106 having light receiving regions 106 a to 106 f is disposed in association with the diffracting device 202 so that the light diffracted by the region 202 a of the diffracting device 202 is led to the light receiving regions 106 a and 106 b of the photodetector 106 and the light diffracted with the regions 202 b and 202 c are led to the light receiving regions 106 f and 106 e of the photodetector 106 , between which an array of the regions 106 a to 106 d are arranged . the signals output from the light receiving regions 106 a and 106 b by the light beam diffracted by the region 202 a are used for obtaining a focusing error signal by a single knife edge method . based on this focusing error signal , an objective lens actuator ( not shown ) positions the objective lens 204 in an optical axis direction . the signals output from the light receiving regions 106 e and 106 f by the light beams diffracted with the regions 202 b and 202 c are used for obtaining a tracking signal by a push - pull method or a dpd ( differential phase detection ) method . based on this ( tracking error signal , a tracking device ( not shown ) positions the objective lens 204 in the disk radial direction . the light receiving regions 106 a to 106 f of the photodetector 106 shown in fig1 generate output signals sa , sb , sc , sd , se and sf corresponding to incident light beams , respectively . the signals sa , sb , se and sf are supplied to a noninverting input terminal of an operational amplifier 11 serving as a signal processor , and the signals sc and sd are input to an inverting input terminal thereof . as a result , a playback signal ( hfs ) is played back according to the following equation ( 1 ): this playback signal is a signal indicating information recorded on the optical disk 205 . the auxiliary light receiving regions 106 c and 106 d are provided for reducing dc offset of the focusing error signal occurring due to interlayer crosstalk . the playback signal is generated by subtracting a sum signal of signals sc and sd from these auxiliary light receiving regions 106 c and 106 d from a sum signal from the other light receiving regions 106 a , 106 b , 106 e and 106 f with the operational amplifier ( signal processor ) 11 . the method of generating a focusing error signal by a single knife edge method and the method of generating a tracking error signal by a push - pull method or dpd method are executed by the block circuit of fig4 according to the following equations ( 2 ), ( 3 ) and ( 4 ). fes ( single knife edge method )= sb + g 1 * sc −( sa + g 2 − sd ) ( 2 ) in fig4 , an amplifier 13 corresponds to g1 of the equation ( 2 ) and amplifies the signal sc with an amplification factor g1 . an amplifier 14 corresponds to g2 of the equation ( 2 ) and amplifies the signal sc with an amplification factor g2 . the method of generating a tracking error signal uses a push - pull method if the optical disk is dvd - ram , for example , and a dpd method if it is dvd - rom . the light receiving regions 106 a to 106 f are light receiving regions necessary for generating the focusing error signal and tracking error signal . a light receiving region for reducing dc offset occurring on the playback signal needs not to be provided newly , so that the configuration is extremely simplified . effect of the above calculation method will be explained . fig2 a shows a beam profile of the light reflected by the playback layer and landing on a photodetector surface , and a beam profile of undesired light reflected by the 1st information recording layer ( non - playback layer ) and landing on the photodetector surface , when the light beam is focused on the 0 - th information recording layer ( playback layer ). fig2 b shows a beam profile when the light beam is focused on the 1st information recording layer . in either case , it is found that an undesired light from the non - playback layer extends over the main light receiving region 106 a and 106 b and the auxiliary light receiving region 106 c and 106 d . if the playback signal is generated by calculating a difference between the sum of the signals of the main light receiving regions 106 a and 106 b and the sum of the signals of the auxiliary light receiving regions 106 c and 106 d according to the equation ( 1 ), it is found that influence of undesired leakage light can be reduced . when a monolayer disk is played back , light does not leak to the auxiliary light receiving regions 106 c and 106 d . therefore , the output signals from the auxiliary light receiving regions 106 c and 106 d are zero . in this case , the playback signal may be generated by the equation ( 1 ). as described above , according to the method of the present invention , dc offset occurring on the focusing error signal and playback signal in the double - layer disk can be reduced effectively . as a playback signal output unit shown in fig3 , it is preferable that an amplifier 12 is provided after the photodetector 106 to improve an effect of reducing the interlayer crosstalk by adjusting a level of the signal . the method of calculating a playback signal ( hfs ) in this case is executed according to the following equation ( 5 ): where g represents a given gain of the amplifier 12 . the first embodiment uses a single knife edge method as a method of detecting a focusing error . however , the present invention is not limited to this method . fig5 shows an optical system according to the second embodiment , which uses a double knife edge method as the method of detecting a focusing error . the second embodiment differs from the first embodiment in a division configuration of a diffracting device and a light receiving surface configuration of a photodetector . as shown in fig5 , a diffracting device 1401 is divided into six division regions , and the light receiving surface of the photodetector 1402 is divided into twelve division regions . the diffracting device 1401 and photodetector 1402 are shown in fig6 in detail . the diffracting device 1401 is divided into six regions 1401 a to 1401 f by a dividing line 1501 in a disk radial direction and division curves 1502 and 1503 reflecting ± 1st light diffracted from a land / groove disk as shown in fig6 . the photodetector 1402 has main light receiving regions 1402 a to 1402 d for focusing error detection , auxiliary light receiving regions 1402 e to 1402 h , and light receiving regions 1402 i to 14021 for tracking error detection . two light beams diffracted by the regions 1401 a and 1401 b of the diffracting device are led to the light receiving regions 1402 a to 1402 h , and used for generating a focusing error signal by a double knife edge method . four light beams diffracted by the regions 1401 c to 1401 f of the diffracting device are led to the light receiving regions 1402 i to 14021 , and used for generating a focusing error signal by a push - pull method or a dpd method . the output signals from all light receiving regions are used for producing a playback signal . fig7 a , 7b and 7 c show patterns of light beams ( signal light beams ) from the playback layer in defocusing . fig7 a , 7b and 7 c show beam profiles on the photodetector when the disk is far from a focusing position , at the focusing position , and near than the focusing position . assuming that the output signals from the light receiving regions 1402 a to 14021 are sa to sl respectively , the focusing error signal ( fes ) is generated by a block circuit shown in fig8 , for example , according to the following equation ( 6 ): where g1 represents a given gain of the amplifier 15 . the tracking error signal ( tes ) based on the push - pull method or dpd method is generated according to the following equations ( 7 ) and ( 8 ), respectively . the method of playing back the playback signal ( hfs ) is executed according to the following equation ( 9 ). where g2 represents a given gain of the amplifier 16 . like the first embodiment , a playback signal generating method of the present invention directed to reduction of interlayer crosstalk uses only light receiving regions for generating the focusing error signal and tracking error signal and needs not to provide newly a light receiving surface to make it possible to be executed in simple configuration . the beam patterns of undesired leakage light incident on the photodetector from a non - playback layer are shown in fig9 a and 9b to explain effect of the playback signal generating method . fig9 a shows a beam profile of light reflected by the playback layer and landing on the photodetector surface , and a beam profile of the undesired light reflected by the first information recording layer ( the non - playback layer ) and landing on the photodetector surface , when the light beam focuses on the information recording layer ( the playback layer ). fig9 b shows a beam profile on the photodetector surface when the light beam is focused on the first information recording layer . in either case , it is found that undesired light reflected by the non - playback layer expands over the main light receiving regions 1402 a to 1402 d and auxiliary light receiving regions 1402 e and 1402 h . accordingly , if the playback signal is generated by calculating differences between the signals of the main light receiving regions 1402 a to 1402 d and the signals of the auxiliary light receiving regions 1402 e and 1402 h as indicated by the equation ( 9 ), it is found that influence of undesired leakage light can be reduced . when a monolayer disk is played back , light is leaked to the auxiliary light receiving regions 1402 e to 1402 h to output no signal therefrom . therefore , there is no problem at all in playing back the monolayer disk . an optical system of the third embodiment of the present invention is shown in fig1 . this embodiment differs from the first and second embodiments with respect to a configuration that a diffracting device 1805 for generating a servo signal / playback signal and a quarter - wavelength plate 1806 are driven integrally with an objective lens 1807 . the linearly polarized laser beam emitted from the semiconductor laser 1801 is converted into a parallel light beam with a collimator lens 1802 , transmitted through a polarization beam splitter 1803 , and reflected by an up - rise mirror 1804 . subsequently , the laser beam is incident on the diffracting device 1806 and the quarterwave plate 1805 driving integrally with the objective lens 1807 . the laser beam is converted from a linearly polarized light beam to a circularly - polarized light beam with the quarterwave plate 1805 and focused on the information recording layer of the optical disk 1808 with the objective lens 1807 . the laser beam reflected by the information recording layer follows a path opposite to the outward path and is converted into a parallel light beam with the objective lens 1807 . the parallel light beam is diffracted by the division type diffracting device 1806 . the diffracted light beam is converted from the circularly - polarized light beam into the linearly - polarized light beam perpendicular to that in the outward path with the quarterwave plate 1805 , and reflected by the polarization beam splitter 1803 . the reflected light beam is conversed with the condenser lens 1810 and incident on the photodetector 1811 for generating a servo signal / playback signal . the division shape of the division type diffracting device may be similar to that of the first and second embodiments . in the third embodiment , a five - division type diffracting device shown in fig1 is used . the light beam diffracted by a diffracting device region 1806 a is led to light receiving regions 1811 a to 1811 d to be used for producing a focusing error signal by a single knife edge method . the light beams diffracted with the diffracting device region 1806 b to 1806 e are led to light receiving regions 1811 e to 1811 h respectively , to be used for generating a tracking error signal by a compensation push - pull method or a dpd method . assuming that output signals from the light receiving regions 1811 a to 1811 h are sa , sb , sc , sd , se , sf , sg , sh respectively , a focusing error signal based on the single knife edge method ( fes ), a tracking error signal based on the compensation push - pull method or dpd method ( tes ), and a playback signal ( hfs ) are produced according to the following equations ( 10 ), ( 11 ) and ( 12 ) by a block circuit shown in fig1 . the compensation push - pull method is a method for reducing offset of the tracking error signal caused by radial shifting of the objective lens . the detail principle of this method is described by toshiba review vol . 57 no . 7 p 32 - p 34 ( 2002 ), the entire contents of which are incorporated herein by reference . fes ( a knife edge method )= sb + g 1 * sc −( sa + g 2 * sd ) ( 10 ) fig1 a shows a beam profile of light reflected by the playback layer and landing on the photodetector surface and a beam profile of the undesired light reflected by the first information recording layer ( the non - playback layer ) and landing on the photodetector surface , when the light beam focuses on the information recording layer ( the playback layer ). fig1 b shows a beam profile on the photodetector surface when the light beam is focused on the first information recording layer . since the undesired light from the non - playback layer expands over the main light receiving regions 1811 a to 1811 b and auxiliary light receiving regions 1811 e , 1811 h , the dc offset due to interlayer crosstalk can be reduced by generating a playback signal according to the equation ( 13 ), similarly to the first and second embodiments . as a result , when playing back a double - layer disk , an optical disk apparatus having good playback signal quality can be realized . according to the present invention , an optical disk apparatus of high reliability reducing dc offset occurring on a playback signal due to interlayer crosstalk , and having good playback signal quality can be realized . additional advantages and modifications will readily occur to those skilled in the art . therefore , the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein . accordingly , various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents . | 6 |
referring to fig1 the installation illustrated therein comprises a tank 1 containing a liquid cooling medium which may be water and which is circulated by pumps ( not shown ) through heat exchangers ( not shown ) to remove the decay heat of the radioactive material . five pipe circuits 2 ( of which only one is shown ) are immersed side - by - side in the cooling medium in the tank 1 . each pipe circuit 2 is manufactured from seamless stainless steel tube and is provided with a side arm 3 which has a pulsing chamber 4 . the liquid in the pulsing chamber is caused to oscillate by air - flow controllers 5 , 6 which alternatively introduce air into the pulsing chamber 4 and withdraw it . the oscillating motion of the liquid in the pulsing chamber is converted by a fluidic pump 7 into a circulatory motion around the pipe circuit 2 in the direction of the arrows . the fluidic pump 7 operates on the pulsed fluid diode principle and has no moving parts within the tank 1 . a further side arm 8 extends from the pipe circuit to a point above the liquid level in the tank and this further side arm is used for filling and emptying the pipe circuit 2 , for removing samples of the liquid for analysis and for providing access for instruments to be lowered into the liquid , for example to measure the temperature of the liquid . conveniently the pipe circuit 2 shown in the figure may be manufactured from 10 &# 34 ; diameter seamless stainless steel tube and may contain 450 feet of such tube . a pipe circuit so formed would have a capacity of 7 cubic meters . the pipe circuits 2 are placed in the tank 1 in close packed array to maximise the number of pipe circuits in the tank . pipe circuits of different shapes , sizes and pipe diameters may be utilised within a tank to maximise the utilisation of the space within the tank . in use the fluidic pump 7 circulates the liquid radioactive material round the pipe circuit 2 . this circulation minimises the possibility of sediment depositing on the walls of the coil which reduces the heat transfer properties of the walls . if water is used as the cooling medium in the tank , it is chemically treated to ensure minimum corrosion of the pipe circuits and tank . the cooling liquid is preferably monitored to detect any increase in radioactivity level which would indicate that a pipe circuit was leaking . in the event that one pipe circuit in a tank leaks only the radioactive material in that circuit has to be transferred to alternative storage facilities . thus the amount of spare storage capacity which has to be provided is less than is required for storage in tanks . if one pipe circuit leaks the remaining pipe circuits can remain in the tank and the faulty circuit can be isolated or replaced . thus the failure of one pipe circuit does not necessitate abandoning the tank and its associated shielding whereas a failure in the tank used for tank storage of radioactive liquids may mean that the tank and the shielding surrounding it become heavily contaminated and cannot be re - used . an alternative embodiment may be manufactured from tubing having two co - axial tubes . the liquid radioactive material is stored in the inner tube and the cooling medium is circulated through the annular gap between the tubes . the pipe circuit formed from co - axial tubes may be placed in a tank , for example as shown in fig1 and may be further cooled by the circulation of a liquid medium such as water in the tank . referring now to fig2 a tank 1 and a pipe circuit 2 are shown . the pipe circuit is similar to that shown in fig1 and the same reference numerals are used to identify the parts thereof . in normal use the cooling medium is withdrawn from the tank 1 through a pipe 10 and passed through a heat exchanger 11 by a pump 12 and returned to the base of the tank 1 . the heat exchanger is cooled by water which is circulated by a pump 13 and which is passed down a cooling tower 14 . the tank 1 is fitted with an air - cooled condenser 15 to condense any vapour evaporating from the cooling medium and return it to the tank . in the event of a malfunction of any of the components of the cooling system which prevent or reduce the circulation of the cooling medium the decay heat emitted by the liquid radioactive material in the pipe circuit 2 will raise the temperature of the liquid material in the pipe circuit and of the cooling medium in the tank . if the rise in temperature proceeds for a sufficient length of time the temperature of the cooling medium will rise to its boiling point . the cooling medium then boils and the vapour condenses in the condenser 15 and is returned to the tank 1 . as the liquid medium boils , its latent heat of evaporation is extracted from the pipe circuits and the temperature in the pipe circuits will be maintained at a value similar to the boiling point of the medium . the use of a cooling medium having a boiling point in the range 60 °- 80 ° c . ensures that the temperature within the pipe circuits does not rise to the boiling point of the liquid radioactive material or to a point where the corrosion rate of the pipe circuits by the liquid radioactive material becomes excessive . in normal use the circulating cooling medium ensures that the temperature of the liquid radioactive material is kept as low as possible and it is only in the situation where the normal circulatory cooling is not operative that the secondary cooling system utilising the condenser 15 is operative . the cooling medium surrounding the pipe circuits in the present invention acts as an additional barrier facilitating the containment of any leakage which may occur from the pipe circuits . storage in the pipe circuits rather than in tanks facilitates criticality control of liquids containing plutonium as the pipe circuits can be designed to be safe by geometry . the construction of storage installations according to the present invention is facilitated as the pipe circuits can be tested before being installed . the circulation of the liquid radioactive material and of the cooling medium and the large surface area of the pipe circuits facilitates heat transfer from the liquid radioactive material to the cooling medium . | 8 |
fig1 depicts a typical cellular network 51 in which the instant invention may be employed . included within the typical cellular network 51 are cells 53 , 56 , and 59 in which are located cell sites 63 , 66 , and 69 . radio antennas 73 , 76 , and 79 are electrically coupled to the cell sites 63 , 66 , and 69 . the cell sites 63 , 66 , and 69 are also electrically coupled to a mobile switch 83 , which in turn is coupled to a public switched telephone network ( pstn ) 86 . a telephone call initiated through the cellular network 51 will eventually reach a call destination device 89 via the public switched telephone network 86 . the call destination device 89 may be any telephonic interface or other media linked to the public switched telephone network 86 , such as a telephone , facsimile , computer or other device as known to those skilled in the art . traveling from cell to cell in the network 51 is a mobile unit 91 . in the exemplary case of fig1 the mobile unit 91 is located within an automobile , but may also comprise a hand held unit or other mobile cellular unit as is well known in the industry . essentially , the cellular network 51 of fig1 operates as follows . a telephone call is initiated and established between the mobile unit 91 and the call destination device 89 . from the mobile unit 91 , signals are transmitted through the air to the closest radio antenna 73 , 76 , or 79 . the signals are then routed from the cell site 63 , 66 , or 69 connected to the respective radio antenna 73 , 76 , or 79 which receives the signals from the mobile unit 91 . from the respective cell site 63 , 66 , or 69 , the signals are routed to the mobile switch 83 , and then through the pstn 86 to the ultimate call destination device 89 . as the mobile unit 91 travels from cell to cell , the particular radio antenna 73 , 76 , or 79 and accompanying cell site 63 , 66 , or 69 through which the signals are routed will be switched to the radio antenna and cell site of the cell 53 , 56 , or 59 into which the mobile unit 91 travels . thus , several radio antennas 73 , 76 , and / or 79 may be employed in the course of a single cellular telephone call , depending upon how many different cells 53 , 56 , and / or 59 into which the mobile unit 91 travels . the switching of a telephone call from one cell to the next adjacent cell is customarily referred to in the art as a “ handoff ”. turning to fig2 shown is the cellular network of fig1 including cells 53 and 56 , with cell sites 63 and 66 which are coupled to radio antennas 73 and 76 , respectively . the cell sites 63 and 66 are coupled to the mobile switch 83 . within each cell site 63 and 66 are several channels 93 through which a cellular call can be linked . in some cellular network configurations , a voice echo canceler ( vec ) 96 may be provided for each channel 93 to cancel echoes on the particular telephone call initiated , as is known in the art . it is assumed herein that the cellular network 51 is digital with the ability to handle analog cellular as well . each channel 93 is ultimately linked to a radio antenna 73 or 76 which establishes radio transmission to the mobile unit 91 , as known in the art . a channel 93 working in conjunction with the radio transmission antenna 73 or 76 together are generally termed a “ radio ” in the cellular field . thus , there are several radios within each cell site 63 and 66 . each channel 93 , or radio , facilitates analog cellular communication on a different frequency as known in the industry . at times , a cellular telephone call may experience interference due to physical obstruction or other phenomena while the mobile unit 91 is within a particular cell 53 or 56 . in such a case , the call may be switched to a new channel 93 within the particular cell 53 or 56 that does not experience significant interference . switching channels 93 within a particular cell 53 or 56 as such is also customarily referred to as a “ handoff ” in the cellular industry . it is important to note that the radio transmission from the mobile unit 91 to a cell site 53 or 56 may be either analog or digital . analog cellular transmission uses frequency modulation techniques which do not add appreciable delay to the overall signal . the actual frequencies used may vary and may also depend upon the call capacity of a particular cellular network . an example of analog transmission is that which transmits according to the advanced mobile phone service ( amps ). due to the fact that oftentimes the delay is not significant , echo cancelers 96 normally are not brought on - line with analog communication , unless the call is over a long distance . on the other hand , digital cellular transmission involves the process of digitizing and compressing the voice signal by the mobile unit 91 before transmission to a cell site 53 or 56 and vice versa . these digitizing and compression processes generally add significant delay to the transmission of the signal , resulting in a significant echo signal . consequently , voice echo cancelers 96 are usually brought on - line to cancel echo signals created by this significant delay . such digital cellular networks generally provide for analog cellular communication as well . the echo cancelers 96 that are brought on - line for digital cellular communication may also be employed in analog cellular communication as well . turning to fig3 shown are the components that make up a mobile unit 91 according to the preferred embodiment of the present invention . the cellular telephone 99 is coupled to modem 100 . the modem 100 will communicate a digital data signal to the cellular telephone 99 which , in turn , will transmit the digital data as a voice signal to be received by the cellular antennas 73 , 76 , and 79 ( fig1 ). within the modem 100 are a digital signal processor 103 and memory 106 . the digital signal processor 103 performs the various operations according to the instant invention based on the echo canceler disabling system 109 located in the memory 106 . note that the digital signal processor 103 and the memory 106 may be incorporated into a single integrated circuit as is known in the art . in order to communicate with a second modem at the call destination device 89 , for example , the modem 100 will synchronize its digital data transmission with the transmission of the second modem . according to the echo canceler disabling system 109 , if at any time synchronization with the second modem is lost , the modem 100 will execute a retrain sequence in which the modem 100 reestablishes synchronization with the second modem . a “ loss of synchronization ” is defined herein as either a total loss of synchronization between the modems or a degradation of modem performance . the loss of synchronization may be caused , for example , by the introduction of an echo canceler on - line which will generally result in a complete disruption of digital data communication . other transmission problems may also cause the disruption of digital data transmission resulting in the loss of synchronization . when initiating a telephone call via modem 100 , the cellular telephone 99 and the cell site 56 ( fig2 ) will perform predetermined handshaking routines in which the specific channel 93 ( fig2 ) to be used for communication is established . once the call is established , the modem 99 will undergo a handshaking routine with the modem contacted at the call destination device 89 ( fig1 ) in which a 2100 hz . tone is with phase reversals transmitted , disabling any echo cancelers that come on - line . this is done to prevent a voice echo canceler 96 from disrupting the digital data transmission . once digital data transmission from modem 100 to a second modem at the call destination device 89 is established , it is possible that the digital data transmission will be disrupted if a handoff occurs . in this regard , handoffs cause a new channel 93 to be established . when the new channel 93 is established , a new echo canceler 96 may be brought on - line which causes a loss of synchronization resulting in the complete disruption of digital data communication . according to the preferred embodiment , when modem 100 loses signal synchronization , the digital signal processor 103 operating according to the echo canceler disabling system 109 reestablishes synchronization and digital data communication with the second modem by transmitting a retrain sequence . the retrain sequence includes an echo canceler disabling signal which will disable any echo cancelers which have been brought on - line after the handoff . turning to fig4 a diagram of the flow of logic executed by the modem 100 ( fig3 ) is shown . in particular , the steps shown are preferably performed by the programmed digital signal processor 103 in the modem 100 . beginning with step 113 , the modem 100 will constantly monitor for proper signal synchronization . in step 116 , if the synchronization is not lost , the modem 100 will revert back to step 113 . according to the present invention , if synchronization is lost , as would be the case with a handoff , the logic will proceed to step 118 where an echo canceler disabling tone is transmitted . in the case of the preferred embodiment , the echo canceler disabling signal is a 2100 hz . tone which is transmitted for 1000 milliseconds with 180 degree phase reversals every 450 milliseconds . note that this tone will disable the echo cancelers that are brought on - line due to the occurrence of a handoff as previously discussed . after the 2100 hz . tone is transmitted , in step 119 , a retrain sequence is sent to reestablish synchronization and digital data transmission . the logical flow will then revert back to step 113 where the loop is repeated . the 2100 hz . tone with phase reversals every 450 milliseconds is the standardized signal that is employed to disable any echo canceler worldwide . turning now to fig5 a , shown is a retrain sequence of a call modem 125 and an answer modem 127 for a standard v0 . 34 modem according to the prior art . in fig5 a , the call modem 125 initiates the retrain sequence with a pause of silence 129 , followed by a “ b ” tone . the answer modem 127 responds with a pause 129 and then an “ a ” tone followed by a phase reversal of the a tone denoted “ a ′”. the call modem 125 responds with a phase reversal of the b tone denoted b ′. subsequent communication establishes the digital data link between the call modem 125 and the answer modem 127 by establishing timing and other parameters as known in the art . it should be noted that the sequence used in fig5 a for v0 . 34 modems is simply used as an example and is not a restriction of the preferred embodiment . this example is further illustrated in the international telecommunications union ( itu ) draft recommendation v0 . 34 dated oct . 16 , 1997 , the entire text of which is incorporated herein by reference . however , the principles discussed herein apply to any modem type . referring now to fig5 b , shown is a retrain sequence according to the preferred embodiment of the present invention . the sequence for the call modem 125 further includes the ans tone 133 which is the 2100 hz . tone that disables voice echo cancelers . according to the preferred embodiment of the present invention , the echo canceler disabling signal is transmitted with the retrain signal that is sent to reestablish modem communication after synchronization is lost . in addition to synchronization loss due to handoffs , it is possible that synchronization may be lost due to other transmission difficulty , in which case an echo canceler disabling signal would be sent even though no echo canceler is brought on - line . although transmitting the signal with every retrain may not be necessary , the instant invention will in effect address virtually all of the unique problems presented with digital data communication using the cellular networks . alternatively , circuitry may be employed whereby the echo canceling tone is only sent during retrains resulting from loss of synchronization due to a handoff . referring back to fig3 it is important to note that the instant invention may be employed on an integrated cellular modem which combines the functions of the cellular telephone 99 and the modem 100 . in such a case the operation of the integrated cellular modem would be substantially the same as that presented by the combination shown in fig3 . the primary difference would be that circuitry may be employed whereby the cellular components of an integrated cellular modem which communicate with a cell site in establishing a new channel would inform the modem circuitry of the impending occurrence of a handoff . in such cases , the modem would send an echo canceler disabling tone and a retrain immediately after the handoff before synchronization is lost , thereby ensuring rapid recovery of digital data transmission from a handoff . also , it would be possible that independent cellular telephones 99 and modems 100 could communicate with each other in similar fashion . such permutations of the instant invention are intended to be included herein . it would be apparent to those skilled in the art that variations and modifications may be made to the embodiments of the invention discussed above which are within the spirit and principles of the invention . all such variations and modifications are intended to be included herein within the scope of the present invention , as defined by the following claims . | 7 |
for the purposes of promoting and understanding the principles disclosed herein , reference is now made to the preferred embodiments illustrated in the drawings , and specific language is used to describe the same . it is nevertheless understood that no limitation of the scope of the invention is hereby intended . such alterations and further modifications in the illustrated devices and such further applications of the principles disclosed and illustrated herein are contemplated as would normally occur to one skilled in the art to which this disclosure relates . the following specification includes by reference all figures , disclosure , claims , headers , titles , of international applications nos . pct / us08 / 75374 , filed sep . 5 , 2008 , and entitled “ dynamic mixing of fluids ”, pct / us08 / 075366 , also filed on sep . 5 , 2008 , and entitled “ method of dynamic mixing of fluids ”, and pct / us2009 / 043547 , filed on may 12 , 2009 , and entitled “ system and apparatus for condensation of liquid from gas and method of collection of liquid ” along with u . s . nationalized and original filings u . s . application ser . no . 12 / 529 , 625 , filed sep . 2 , 2009 , and entitled “ dynamic mixing of fluids ”, ser . no . 12 / 529 , 617 , filed sep . 2 , 2009 , and entitled “ method of dynamic mixing of fluids ,”, ser . no . 12 / 990 , 942 , filed on nov . 3 , 2010 , and entitled “ system and apparatus for condensation of liquid from gas and method of collection of liquid ”, ser . no . 12 / 886 , 318 , filed on sep . 20 , 2010 , and entitled “ fluid mixer with internal vortex ”, ser . no . 12 / 859 , 121 , filed on aug . 18 , 2010 , and entitled “ fluid , composite , device for producing thereof and system of use ”, and ser . no . 12 / 947 , 991 , filed on nov . 17 , 2010 , and entitled “ device for producing a gaseous fuel composite and system of production thereof .” the parent application shows as what was previously fig1 a to 15d . fig1 a shows the volumetric structure after the first stage of activation , when the volume made of foam bubbles have not started to be transformed in space of the fuel pipeline and are as though pressed to each other . fig1 b shows the structure when the bubbles are being transformed in the fuel mix and separate from each other . fig1 c and 13d show the internal processes in the activated volume of a fuel mix as it moves in the fuel pipeline . this process shows how volumetrically , small spheres are formed and how as the pressure of the gas inside of the sphere changes , the thickness of the fuel shell thins . this process as illustrated is found at zones 906 to 909 as shown at fig9 , greater detail is provided below . in general , as shown at fig2 a - d , micro - bubbles of fluid are formed and include a core of compressed gas 201 surrounded by a shell of liquid such as fluid or fuel 202 or a shell made of fuel mixed with another liquid such as water . a new foam - like composite called herein the fluid composite 1 is formed including a very large number of very small cells 200 each with a very large number of very small compressed gas cores 201 . the cells are small and numerous and are formed as part of the fluid composite 1 in a very high energy state with dynamic and kinetic energy . the whitish foam of micro - bubbles 200 also called the fluid composite 1 , the fluid and the gas are energized and dynamic . while this disclosure is directed to the creation of any fluid composite 1 made of imbedded pressurized compressed gas 201 core over a shell 202 , having different dynamic components , in one embodiment , the composite is a fuel composite 1 where the liquid is fuel and the gas is air needed to burn the fuel . within this disclosure , while the term fluid composite 1 is used , one of ordinary skill in the art will understand that the composite 1 can be made of any liquid or liquids mixed in with gas for any commercial application . as a way of a non limiting example , water for irrigation and plant nourishment can require aeration to help with seeping and plant absorption . the water may also require mixing with a fraction portion of fertilizer . in a fluid composite 1 example , the creation and the merger of a fixed fraction of gas into the liquid is based on a stoichiometric ratio of air to fuel exists where burning is optimal . for some applications , a fraction of this air may be imbedded into the fluid composite 1 to enhance the properties of the fuel . in one example , 10 %, 20 %, or even 30 % of stoichiometric air in weight can be merged into the fuel as part of the fluid composite 1 . the density of air at ground level is approximately ρ air = 0 . 0012 kg / l while the density of gasoline is approximately ρ gz = 0 . 703 kg / l and diesel ρ dz = 0 . 85 kg / l . with a stoichiometric ratio for diesel fuel to air of 14 . 6 to 1 and for gasoline of 14 . 7 to 1 , the ratios at the above suggested gas to liquid ratio will vary from about 1 . 47 to 1 ( e . g . 10 % or 14 . 7 to 1 ) to 4 . 38 to 1 ( e . g . 30 % of 14 . 7 to 1 ). for the ratio to be 10 %, a quantity of 0 . 085 kg / l must be inserted , or approximately 70 . 3 liters of air per liter of fuel . at a level of 20 % in weight of air , 140 . 6 liters of air must be mixed in the fuel , and at 30 % a quantity of 210 . 9 liters of air must be inserted into 1 liter of fuel . these values are only illustrative of possible ratios and other ratios are contemplated within the acceptable parameters of the fluid composite 1 . at these volumetric ratios , for every 1 liter of fuel , 70 . 3 to 210 . 9 liters of air are mixed in the fluid composite 1 . since the fluid composite 1 is a pressurized medium , and that only the gas portion of the fuel cells 200 is compressible ( at pressures below 1000 bars ), a fluid composite at 17 bars of pressure and a ratio of a 10 % mix will correspond to a volume of gas of 4 . 14 liters of pressurized gas cells 201 inside of a volume of 1 liter of fuel ( i . e . 70 . 3 liters / 17 bars ). while some ratios are given , what is contemplated is the merger of any ratio of air into the fluid composite either at initial stages of formation or at a second stage after the first fluid composite has been prepared . the size of the micro - bubbles can also vary based on a plurality of characteristics and components of the apparatus for the creation of the fluid composite 1 as shown at fig1 . fluid viscosity , surface tension , the temperature , the speed , the pressure , to kinetic energy , are only a small fraction of the different parameters that play a role into the determination and control of a created by a device with small channels 115 where gas flows of a thickness of 5 to 50 μm . small bubbles of a diameter of 5 to 50 μm are created as shown on fig1 and 2d . once again , the size of these channels 115 is only illustrative of one contemplated embodiment , for one type of fluid to create one type of fluid composite 1 with unique properties . these sizes of bubbles 201 correspond for example to an internal radius ( r g ) of small spheres of 2 . 5 microns 25 microns . the absolute volume of gas ( v g ) is given by v g = p *( 4 / 3 ) πr g 3 where p is the pressure inside the sphere . v g can be calculated to be in a range for channels 115 of 5 to 50 μm from v g = 65 . 5 * p to 65 , 500 * p μm 3 . in a network structure where cells are arranged as shown in the configuration of fig2 b , the volume of fuel ( v f ) in the shell surrounding a single bubble is v f =( 4 / 3 ) πr f 3 − v g / p where r f is the radius of the sphere of liquid and v g is the volume of a sphere of gas . as shown on fig2 b , in one embodiment , the shell of the bubbles have a thickness in proportion with the thickness of gas inside the bubble ( i . e . where r f ˜ 2r g ). in such a sample case , v f = 1151 to 524 , 000 μm 3 . while one ratio of thickness of the fuel 202 over the size of the gas 201 is shown and used to help described the fluid composite 1 , one of ordinary skill in the art will understand that fluid composites 1 can be produced having a very wide range of geometries based on the evolution , calibration , of different properties , such as the ratio of the flow rate of incoming gas to the flow rate of incoming liquid , the ratio of volume at the different phases alongside the device shown at fig1 , etc . returning to the above example , in order to obtain stoichiometric gas to liquid ratio of 10 %, i . e . a fluid composite having a volume of gas of 4 . 14 liters the volume of liquid over the volume of fuel is taken to be v g / v f = 4 . 14 where for example a 5 μm gas bubble is used , a pressure of 17 bars = vf * 4 . 14 / vg so a ratio of 1151 * 4 . 14 / 65 . 5 = 4 . 10 is calculated . with a fixed internal bubble of 5 μm , with a reverse calculation we can determine volume of fluid of 268 . 5 μm 3 and thus determine a radius for the external shell of fuel of 9 . 75 μm . within the confines of testing , in one embodiment , at a stoichiometric air to fuel ratio of 10 %, the pressure of the fluid composite is 17 bars for an air entry of 45 bars , for a ratio of 20 %, the pressure rises to 35 bars , and for a ratio of 30 % the pressure becomes 50 bars for the same air entry pressure . this calculation is a sample calculation and one of ordinary skill in the art will recognize that the thickness of the outer shell of liquid may vary based on a plurality of static and dynamic conditions created within the device as shown at fig1 . a volume of 1 liter of fluid represents a volume 1 × 10 15 μm3 which can contain up to 1 . 8 × 10 9 cells of a volume of 5 . 24 × 10 5 cubic micrometers . the inventor has calculated that in one embodiment , the fluid composite had a density of approximately 2 . 7 × 10 7 cells / l . while fig2 b teaches a fluid composite where each cell 200 touches the adjacent cell , the fluid composite 1 remains a fluid composite even if the density of cells within the composite drops . for example , the inventor has determined that at density concentrations of 1 . 5 % of the maximum cell density , the fluid composite 1 remains a fluid composite and the associated properties . further , in order for the micro - bubble to remain stable for a length of time prior to entry of the micro - bubble into a combustion chamber , the shell of the liquid surrounding the compressed gas is thick enough to prevent the micro - bubble from bursting . in a dynamic mixture , the energy stored within the composite fluid in the form of brownian movement must first be reduced greatly before the bubbles can collapse . in a regular flow , the fluid molecules in the static walls around pockets of gas thins down as the fluid migrates down under the force of gravity . the walls thin up to a value equivalent to the surface tension forces within the liquid . in a stable flow made of micro - bubbles , an equilibrium must be such that surface tension forces of the liquid shell of a bubble is sufficient to prevent a bubble to collapse with an adjacent bubble having similar properties . small liquid droplets such as the micro - bubbles are describes and defined by the young - laplace equation : where γ is the surface tension of the external liquid shell of a bubble , r x and r y are curvature radius in x and y axis respectively , and δp is the pressure difference in bars between the internal and the external of the bubble . for the interface water / air at room temperature , γ is approximately 73 mn / m . for an interface between most fuel / air the surface tension is in the range of γ = 20 to 40 nm / m . for the micro - bubbles to maintain coherent in a network of cells as shown on fig1 a to 13d , the pressure variation between the inside portion of the bubble and the outside must be coherent . for droplets of water at standard room temperature and pressure , internal pressure of the bubble cannot rise above 0 . 0014 bar for a bubble of 1 mm in radius , 0 . 0144 bar for a bubble of 100 μm , 1 . 43 bar for a bubble of 1 μm in radius , and 143 bar for a bubble of 10 ηm in radius . in the above example where the surface tension fuel / air is approximately half of the surface tension as the water / air figure , these values are taken to be half of the listed values . these values do not take into effect that the bubbles operate in a fixed volume of incompressible liquid . in a fixed volume area such as the area within a pipe , the effect of small bubble walls collapsing into a single larger bubble , thus breaking the fluid composite would result in a reduction of the surface between the liquid and the gas , an increase in the compactness of the liquid , and thus a diminution of the internal pressure of the gas . at equilibrium , the fluid composite is in a state where surface tension is such that the pressure difference between the inside of the bubbles when compared to the pressure inside the incompressible fluid acting on the outside of the bubbles is inferior to the young - laplace value . at these values , the collapse of a bubble no longer results in a negative value of the gibbs free energy per unit area . fig2 a shows a gaseous compressed kernel or cell 200 of a fluid composite 1 as shown on fig2 b . each cell 200 as shown includes a compressed gas center 201 surrounded by a shell of incompressible liquid 202 . shells are held in shape under the external pressure of the fluid composite 1 and in situations where the pressure is uniform in the fluid composite , the structure of the cell 200 is spherical . d 2 illustrates both the external diameter of the liquid cell 200 and the distance between centers of adjacent fuel cells 200 . fig2 c illustrates a situation where pressure in the fluid composite 1 is not uniform . the illustration is of a slice in thickness of oval shape cells 200 where the distance in one direction remains d 2 , but is compressed in the other direction to ½ of d 2 . in this context , the distance between centers of two adjacent cells is only ¾ of d 2 . pressure as shown on fig2 c is greater in the horizontal axis by a factor of 2 . in one contemplated embodiment , the pressure is caused by external sources such as the pressure of the fluid entering the fluid composite device as shown on fig1 and the like . the fluid composite 1 as shown , unlike the liquid , is compressible in part . the partly compressible nature the fluid composite allows for the composite to evolve past structures of variable geometries and expand / contact locally in yet another advantageous property of the fluid composite 1 . fig2 d shows a portion of the device for the production of the fluid composite 1 as shown at fig1 where the gaseous fuel cells 201 are dynamically being created . fig1 shows an illustration to help understand the interface where the gas cells 201 connect with the activated liquid or gasified liquid portion . returning to fig2 d , air is accelerated and split into small linear channels 115 . the gas as shown is pushed at a speed where it becomes fully turbulent . in addition to molecular movement and linear average displacement of the gas molecules , small vortices structures are created in the flow creating small circulating structure within the gas at the area of release as shown . these vortices have the pressure of the gas within the channel 115 and store dynamic and kinetic energy in surplus of linear kinetic energy . the molecules of gas arrange in what is described as a dynamic evolution . in one embodiment , the dynamic evolution is a series of vortices where the gas is arranged in structures with rotational energy . other structures and movements of the gas is contemplated as part of the dynamic evolution . once gas as part of these structures leave the channels 115 , they have strong dynamic and turbulent activity . their coherent structure has a average diameter of d 1 shown to be the diameter of the channel 115 corrected by the depression ratio created within a ring channel 113 . the illustration shows in a simplified fashion how the vortices align along the wall and move up in the ring channel 113 but this alignment is shown for illustration purposes only , the cells 201 already with turbulent movement move in this area in a turbulent fashion under a high rate of speed that is equal to the flow of speed of the fluid composite 1 in the device . the distance between the two coaxial reflectors between the hydraulic and the pneumatic sections 110 is shown with a thickness of h creating a turbulent fluid flow of thickness h . in one embodiment , the thickness h is in the range of 5 to 100 microns , in another embodiment , h is in the range of 10 to 50 microns but thicker ranges such as 100 to 500 microns or even greater are also contemplated . the liquid accelerated and having highly turbulent and dynamic velocity is then projected into the ring channel 113 area where it expands in the increased volume . fig1 shows how the fluid 1208 may expand to encompass the entire area 1209 considered to be a local ring zone between a hydro - dynamical area and the aerodynamic area where both streams 110 , 115 travel . the pressure varies within the area 1209 and as a consequence , vortex bubbles are created at 1206 and travel upwards to a zone of settled low pressure and high linear speed 1207 before entering a zone 1212 of low pressure and linear movement where the streams merge to form the fluid composite 1 and settles into a channel 123 . the fluid when released at 1208 , is turbulent and dynamic . at 1210 , an elastic resistance wave is shown where compressed cells 1212 connect with the fluid 110 to create a network of fast moving cells as part of the fluid composite 1 as shown with greater detail at fig2 a - c . one of ordinary skill in the art will understand that while a regular array of cells is shown , each with a gas center 201 surrounded by a shell of incompressible liquid 202 , the energy poured into the creation of the fluid composite 1 is greater and much of the energy remains stored as dynamic elements within the fluid composite 1 . for example , the different cells 1211 shown on fig1 have relative movement and translate , move and shake as would molecules based on a brownian movement . the gas within the gas center 201 also retains kinetic and dynamic energy , and the fluid also moves turbulently between the pockets of compressed gas . in an embodiment , the energy is sufficient to help dilute a large fraction of gas molecules , such as gas of nitrogen from the air into the fluid . in another embodiment , the energy is sufficient to break chemical bonds in water and in air and create chemical radicals that can reattach in a plurality of useful ways . for example , if the fluid and the gas are at different temperatures , the resulting mixture may be at the average temperature of the input fluids but a higher energy fluid can be used to help promote nitrogen dilution , chemical reactions , or even cracking of the water for hydrogen ion production . what is shown and described is a pressurized fluid composite 1 within a vessel such as an external case 106 shown in one embodiment as a portion of a cylindrical pipe . in one embodiment , the external case 106 is a pipe of uniform diameter . fluid as shown on fig1 enters at 101 and the fluid composite 1 exits at 126 as the stabilized fluid composite 1 on the right of the device . the fluid composite 1 is made of a network of fuel cells 200 in dynamic contact with each other as shown at fig2 b or even fig1 . the structure includes a plurality of fuel spheres or fuel cells 200 each multilevel fuel sphere including a core of compressed gas 201 in dynamic evolution , and a shell 202 surrounding the core of compressed gas 201 made of a liquid in dynamic movement . the dynamic contact of fuel cells shown as a neatly packed array of cells 200 is a turbulent displacement of adjacent and connecting cells 200 in a three dimensional environment moving in relation to each other . the dynamic movement of the liquid of the shell 202 of each cell 200 is a turbulent movement of liquid molecules within the thickness of the shell 202 , and the dynamic evolution of the compressed gas 201 is a turbulent movement with vortices . within the scope of this disclosure , the term dynamic as part of the expression dynamic contact , dynamic movement , dynamic evolution , or any other expression is to be read and understood as an open handed word to include in addition to any ordinary meaning the fact the different molecules , particles , and constituents of a fluid or gas have a higher level of energy and that as a consequence the molecular agitation , either in term of the linear velocity , angular velocity , spin , brownian movement , or even temperature are greater than a non dynamic state in contrast to a static state that is non dynamic . the term dynamic include kinetic energy , positive enthalpy changes , positive entropy changes , etc . in another embodiment , the turbulent displacement is a brownian movement , a movement that seemingly appears random but is a continuous - time stochastic process . in another embodiment , the fluid composite 1 is made of an incompressible liquid such as a hydrocarbon based fuel and the gas is compressed air . a ratio of the volume of the core of compressed gas over the volume of the fuel cells is 10 % to 30 % of the stoichiometric air , or a ratio of 1 . 47 to 4 . 38 to 1 where stoichiometric ratio is 14 . 7 of air over fuel and 10 % is 1 . 47 time the volume of air to fuel . fig1 shows a device 100 for the production of a fluid composite 1 . this device is explained partly in united states under application ser . no . 12 / 529 , 625 , filed sep . 2 , 2009 , and entitled “ dynamic mixing of fluids ”, and ser . no . 12 / 529 , 617 , filed sep . 2 , 2009 , and entitled “ method of dynamic mixing of fluids ” both applications are incorporated by reference in their entirety . this device 100 is shown with a plurality of different embodiments at fig3 to 7 , and is shown as part of a system for the production of a fluid composite at fig8 to 11 . this device 1 is used to conduct the dynamic mixing and the production of a fluid composite 1 for a plurality of uses including but not limited to the injection of aerated and compressed fuel into an injection chamber of a combustion cycle . the gas serving as the oxide must be brought in immediate contact with the fuel for optimum combustion of the fuel . when compressed gas 201 as shown on fig2 is released into a non - compressed area , such as a combustion chamber or any other opened area , the gas will immediately expand to reach atmospheric pressure by increasing in size in proportion with its pressure . the external shell 202 under the expansion force , will rip apart the fuel and create a very uniform mist of fuel where combustion is enhanced . high efficiency in fuel burning corresponds to high efficiency in burning of thermal equipment . in a diesel type fuel , greater burning and cleaner burning rates can result from using the composite fuel 1 . a larger quantity of compressed air , up to 20 times more can be used as carburant of the diesel fuel . the volume of the fluid composite 1 can be increased several times fold , for example the volume of gas reaches for diesel up to 20 times the volume of fuel . pressure can also be increased during the process of aeration or formation of the fluid composite 1 by adding pressurized gas to an already pressurized inlet of liquid . in one embodiment , the linear speed of the composite fuel 126 over the arrival fuel 101 as shown on fig1 can be up to 20 to 1 or a proportion of the aeration ratio . pressure can be increased up to five times , the output flame created by the release of the composite fuel 1 in an open area can be increased multiple times because of the added pressure and internal expansion . in one embodiment , an increase in length of a torch in a flame in a burner of 3 × is measured . the volume of flame of the fuel is also increased with the same proportion . as a result of greater and cleaner combustion using the fluid composite 1 over ordinary fuel and the lesser the release of waste such as no x , co , co 2 , and soot particles . the fluid composite 1 is a fuel with new properties . adding gas does more than create a dual state mixture . the fluid composite 1 has a new physical structure , a new dynamic state that is compressible , can be expanded , may be further merged with other sources of gas or liquids , and results in a fuel with different performance and properties . the fluid composite 1 has increased thermal efficiency , increased burning capacity , reduction of the specific charge of the fuel . further , as part of the process of creation of the fluid composite 1 , gas is added and the volume and resulting speed of the fluid composite 1 is increased . the fluid composite 1 is a three - dimensional mixture made of a mixture of components in dynamic movement . the nature of the fluid composite 1 allows for an easier flow thought variable geometry designs cause by the compressible / expansive nature of the composite 1 . in another embodiment , water is added to the fluid composite to enhance hydrocarbon burning as known in the art . further , the compressed gas will serve to propel the fluid composite 1 out of the nozzle head . once the fluid composite 1 is formed , the mass ratio of gas over liquid is fixed and does not change until the fluid composite 1 is finally expanded at a point of combustion , if it is expanded into an open volume with gas or liquid present ; for example in a burning chamber of a burner or the piston of a diesel engine . since the gas is compressible and the liquid is generally not compressible , as the pressure varies , the volumetric ratio unlike the mass ratio changes . as for any composite 1 , such as diesel fluid composite , or any other composite , a compressibility limit exists . in an ordinary liquid , when a pressure change enters the medium , the liquid does not significantly change in volume . in an ordinary gas the medium is compressible and as the pressure changes in proportion with the pressure change ( e . g . pv = nrt ). for example , an increase by 100 % of the pressure results in a decrease of half of the volume of the gas . in the fluid composite , as the pressure changes , the liquid remains incompressible but the small spheres of gas 201 are compressible and will change in volume based on the evolution of volume of a sphere . for the above increase of the pressure by 100 %, the volume of gas of a sphere v g =( 4 / 3 ) πr g 3 must be halved so the pressure inside of a small gas bubble doubles . a sphere of gas 201 of diameter 50 μm and a radius of r g = 25 μm ( v g = 65 , 500 μm 3 ) will increase in pressure twofold once the volume is halved ( here to 32 , 750 μm 3 ). the new radius of the gas sphere 201 associated with this volume is r g =˜ 20 μm . as the gas spheres grow smaller , understandably their capacity to shrink under pressure will reduce . the fluid composite 1 evolves when a large fraction of gas is present in the composite 1 from a gas like composite and morphs into and acts more like an incompressible liquid once the volumetric fraction of gas decreases . in the above example , if the composite is viewed in two dimensional , the gas proportion will evolve from an initial gas surface of s 1 = 1964 μm 2 = πr 1 2 to a final gas surface of s 2 = 1256 μm 2 = πr 1 2 . so the change in surface of the volume is s 2 / s 1 = 1256 / 1964 = 0 . 64 or 64 % for a decrease of the volume of the spheres of 50 %. as the fluid composite 1 has a ratio of gas to liquid that closure to a liquid , this proportion changes accordingly . the fluid composite 1 has evolving unique properties based on partially and evolving compressible nature . other properties such as latent heat , thermal capacity , specific heat , also evolve as a fluid composite 1 and not as two individual mixed elements . what is described and understood as the composite is a material , that includes a very large quantity of small volumes having different characteristics that result in creating an overall material called the composite 1 with characteristics and properties that different from a sum of its constituents . fig1 and associated fig3 illustrate an incoming stream 101 of incompressible liquid made in one embodiment of hydro - carbons or a fuel . a hydraulic section of the device 102 is connected to an inlet such as a fuel pipeline or any other connector . as the stream 101 travels up the device illustrated here from left to right , it passes an entrance 103 and is split outwardly over a conical reflector 104 . at the base of the conical reflector 104 , the fuel reaches the opening channels 107 in the shape of a ring after traveling in the fixed external diameter cavity 106 where the fluid is accelerated . the stream 101 is split and enters the channels 107 and then reaches ring channel 109 to create a homogenous turbulent stream after a second step acceleration . element 108 is an alignment element to help assemble and align the hydraulic and pneumatic parts . the gas from an external source enters at channels 122 and travels up 121 until it expands at 120 around a conical shaped section . another inner cone 119 serves as a guide element to direct the gas past the zone 117 and because of a reduction in section around the code to accelerate the gas into another ringed area with channels 116 . after the gas is flipped at the tip of the channels 116 , it then moves down opened channels 115 to meet the turbulent fluid . the fluid and the gas pass on opposite sides of the double coaxial reflector 111 before entering and mixing into the ring channel 112 and ultimately the ring 113 where merger and formation of the fluid composite 1 occurs . line 114 illustrates the border at which the fluid composite 1 is formed and ultimately travels down the channels 123 for the accumulation of the fluid composite down in the apertures 124 into a single stream at the axial aperture 125 . a casing 127 is used for example as a heat sink or is used to help with post processing and alteration of a characteristic of the fluid composite 1 after it is formed . greater details are given of this device and apparatus in the parent application hereby fully incorporated by reference . fig3 describes shows as 3 a and 3 b two sections , the first where a gas enters the device 100 and where the fluid composite 1 where the fluid composite 1 evolves . at fig3 a air or compressed gas enters at 301 at apertures for fastening pipelines where air arrives from a compressor . the gas evolves up channels 122 and reach the center 121 where the air then proceeds upwards to the area for the production of the fluid composite 1 . fig3 a further illustrates four channels 123 where the fluid composite 1 travels back to the area illustrated by fig3 b . in fig3 b the fluid composite 1 after traveling down from the main portion of the device past the area shown at 3 a merges back via channels 124 to the axial aperture 125 . both fig3 a and 3b show a x shape system with four apertures or four channels for the transfer of the gas and the fluid composite 1 respectively , but one of ordinary skill in the art will recognize that while one possible configuration is shown , any geometry , number of apertures , or number of channels is contemplated . fig4 is a cross - section of the device for producing a fluid composite of fig3 including a post production chamber is used to further alter the fluid composite according to another embodiment of the present disclosure . at the back end ( right side on the figure ), an area is reserved 401 for post processing of the fluid composite 1 before it is released . for example , the device can include a coil or a cooling element to alter the temperature of the fluid composite 1 . fig5 is a cross - section of the device for producing a fluid composite of fig1 including an acceleration nozzle 501 for entry of a secondary fluid such as air or water to be merged with the fluid composite 1 at 503 after it is released via the channel 502 . the passageway 503 can be a flat vortex creator with inclined passageway or be on a conical shape section 703 as shown at fig7 . fig6 is a cross - section of the device shown at fig5 further including a secondary fluid inlet according to an embodiment of the present disclosure . fluid pressurized or not is added such as additional combustion air to help push or accelerate the fluid composite 1 or simply to further increase the quantity of air in the mixture . the spiral 701 with tangential channels 704 is shown and is designed to create a vortex movement in the fluid composite 1 before it enters the outlet . fig7 further includes an additional fluid inlet 705 for the entry of a fluid but this time directly in the area of the device 100 where the fluid composite 1 is created . fig6 shows how a fluid inlet 602 includes an opening 603 for the passage of liquid into the area of interest 604 . in the illustrated embodiment , a groove 601 can be made to help guide the incoming liquid to the area of interest 604 . what is described is a fluid activation device 100 to generate a aerated fluid composite 1 with a hydrodynamic portion in contact with the fuel 101 for activating at least a fuel by subsequently pressurizing the fuel 101 over for example a cone 104 and depressurizing the fuel 101 into a low pressure zone 113 for mixing of the liquid such as the fuel with a compressed gas entered via 122 to form a fluid composite 1 a shown on fig2 . the device 100 further includes an aerodynamic portion shown as elements 118 , 119 , and 127 overlapping with the hydrodynamic portion at an interface region with conical shaped reflectors 111 for mixing a compressed gas from an external source 122 such as a compressor into the at least an input compressed fuel 101 at the low pressure zone of mixing 113 by subsequently pressurizing the gas , and changing a flow direction of the gas into the fluid composite 1 . further , the device 100 includes a secondary gas inlet 501 as shown at fig5 to introduce gas or a different fluid into the fluid composite 1 to form an aerated fluid composite shown by the arrow on the right side of the device 100 . in one embodiment , the hydrodynamic portion includes a housing 105 with a cavity having a center cone 104 for pressuring the liquid 101 and directing the liquid 101 to a plurality of channels 107 and ultimately to capillary ring channel 110 between two conical shaped surfaces 111 for depressurization into the low pressure zone 113 . in yet another embodiment , the secondary gas inlet 122 or as shown by a cross 301 on fig3 a is in a housing 127 of the aerodynamic portion 118 , 119 , and 127 . in another embodiment , the aerated fluid composite 540 as shown on fig5 is a fluid composite 1 with more than a stoichiometric volume of gas in weight or a regulated stoichiometric volume for further compression of the fluid composite 1 . in fig3 a , the gas inlet 310 is radial to the housing , in another embodiment the housing further includes an external device for altering a characteristic of the aerated fluid composite 401 as shown on fig1 . in addition to providing information about the fluid composite 1 , and a device 100 for the production of the fluid composite 1 , what is also contemplated is a system 1000 where the device 100 for producing the fluid composite 1 is connected functionally . fig8 to 11 illustrate respectively each of the devices shown at fig1 , and 6 respectively as part of an integrated functional system 1000 with a device 100 where the fluid composite is used . the system 1000 as shown includes the device 100 for the production of a fluid composite 1 . the system includes a compressor 806 with a pump and a nanometer 807 for the calibration and control of the flow of gas from the compressor 806 to the entry port 122 of the device 100 . the second input is a fluid pumped up from a tank 801 having a gauge or a level 802 and is pumped via the pump 803 through a meter 804 or filters / gauge 805 . in one embodiment , the tank 801 is filled with hydrocarbons or fuel . as drawn on fig8 , an additional tank 811 is used to collect surpluses of fluid composite that is settled down in an depressurized state through a gauge or safety valve 810 and is recycled into the tank 801 . finally , the fluid composite 1 produced by the device 100 is sent to a use , such as in one example an atomizer 8 for a combustion chamber 809 . while one use and one configuration of the system 1000 is shown , what is contemplated is the use of the device 100 as part of any system , with any technology , that requires the fluid composite 1 . fig9 shows the same structure as in fig8 with the added description of the different zones for the creation of the fluid composite 1 . these zones are described as zones 901 to 909 . as described above , gas enters from the compressor 806 from one end while fluid enters from the tank 801 from the opposite end of the device 100 . the steps 901 to 909 are listed in this succession as the fluid passes from 901 to 905 , merges with the gas coming from the compressor 806 in zone 906 and finally moves out as shown in zones 907 to 909 . zone 901 is a state the fluid passes from a continuous cylindrical flow to a ring shaped flow . based on the angle of the different cones in this region and the associated effective surfaces open to the flow of fluid , the speed of the fluid is increased , slowed , or unchanged . in the configuration as shown , the speed of the fluid is accelerated in zone 901 and enters zone 902 the ring shape is formed so it aligns with the channels in zone 903 . small streams of uniform cross section , such as cylindrical diameters of 5 to 50 micrometers are made . these channels have a fixed length so as to create a pressure drop in the fluid . at zone 904 , a buffer zone allows for the collection of a small quantity of fluid before it may continue down to zone 905 and is dispersed . zone 905 is a conic ring dispenser where the distance can be up to 200 micrometers but in one embodiment , the distance is 5 to 50 microns . as the streams move in this zone , the streams split in zone 903 take on a unique dynamic and kinetic configuration . expansion based on the bernoulli principle further increases the dynamic configuration of the stream of liquid . at zone 906 , the volume of the ring is such that pressure drops below a certain pressure so conditions of expansion and partial vaporization occurs . as observed , the flow downstream from zone 906 is of such a size as to allow for the ring at zone 906 to be in depression ( i . e . where the flow is unclogged ). at this border shown by 114 the fluid mixes in with the gas and the fluid composite 1 is formed in a partially compressible medium . zone 907 is a zone of intensive formation of cells of the fluid composite and a zone of high energy before the stream can stabilize in zone 908 as an accumulation of cells with a fixed pressure . finally , at zone 909 , this area includes in one embodiment a vortex creator capable of creating a spiral movement within the fluid composite 1 by using some internally stored energy in the composite 1 . fig1 shows the configuration of fig8 where the system further includes a second source of compressed air connected to the compressor 806 via a nanometer 1001 and a gauge for the determination and calibration of the flow and charge of compressed air for calibration . the system further includes as shown a second gauge 1003 for the primary flow of air . finally , fig1 includes other elements of one possible embodiment of the system 1000 such as a connector 1104 for entering a second source of fluid at zone 905 using a reservoir 1101 , a gage 1102 , and a load charge gauge 1103 . other elements such as control elements 1005 and 1006 can be added to the use element 808 to better utilize the fluid composite 1 as a compressed media . what is further described is a system 1000 for producing an aerated fluid composite with a source of fuel from the tank 801 connected to a hydrodynamic portion for activating at least a fuel in at least one of zones 901 by subsequently pressurizing the fuel 902 and depressurizing the fuel 903 into a low pressure zone for mixing 906 of the liquid with a compressed gas from the compressor 806 to form a fluid composite 1 . the source of compressed gas 806 is then connected to an aerodynamic portion as shown on fig9 overlapping with the hydrodynamic portion at an interface region shown at 905 for mixing a compressed gas into the at least an input compressed fuel at the low pressure zone 906 of mixing by subsequently pressurizing the gas , and changing a flow direction of the gas at zone 905 into the fluid composite 1 created at 907 . the system 1000 also includes a secondary gas inlet 501 to introduce gas also from a compressor 806 or any other source into the fluid composite 1 and connected to the source of compressed gas to form an aerated fluid composite . in another embodiment , an aerated fluid composite outlet 766 is connected to an element 808 for use of the aerated fluid composite . the aerodynamic portion and the secondary gas inlet may also be connected to two different sources of compressed gas ( not shown ). while in at least some examples described above , the fuel activation device is described generally as mixing fuel and water , the fuel activation device can mix various types of liquid components . for example , the fuel activation device can mix two dissimilar liquid components such as fuel and water . in some additional examples , the fuel activation device can mix two homogeneous components , such as gasoline and ethanol . in yet additional examples , the fuel activation device can mix at least three diverse components , such as gasoline , ethanol and water . in such embodiments , two of the components are provided to one of the liquid inputs to the hydrodynamic portion of the fuel activation device . as shown in fig1 d , as the fuel - air mix stabilizes , the bubbles of fuel align to form a foam . while one regular quadratic cell configuration is shown , any configuration of optimized contact area based on the geometry of the cell is contemplated . in the stabilized fuel air mix , the average diameter of the fuel spheres ( e . g ., the diameter of the compressed gas core if present and the shell of fuel ) becomes similar since the boundary conditions are the same across the entire fluid composite . while the average diameter of the fuel spheres is constant , the diameter of the kernel of compressed gas can vary between fuel spheres based on the local pressure of the fluid . for example , some fuel spheres , have a core of a small or minimal diameter while others have a kernel that is so large that the coating on the fuel sphere has an insufficient thickness to provide stability due to forces of superficial tension . smaller pressure allows for the gas kernel to expand creating a bubble with a smaller shell . over time , fuel spheres are likely to burst . in some thermodynamic arrangements , in order to reduce the number of fuel spheres that burst prior to combustion , the time between formation of the foamed fuel and combustion of the fuel can be short . in general , it can be desirable to form micro - bubbles having a ratio of the radius of the kernel of compressed to the thickness of the shell of liquid of between about 0 . 8 and 2 . 5 ( e . g ., between about 1 and about 2 , between about 1 . 5 and about 2 , about 2 ). such a ratio again based on boundary conditions can provide a stable micro - bubble that is less likely to burst while still providing an increased surface area of the fuel . the foamed fuel ( e . g ., such as the fuel shown in fig1 d ) is inserted into a combustion chamber . when injected into the combustion chamber during a running cycle , the kinetic parameters of the activated volume of the fuel mix , in combination with the large active surface area of an activated unit dose of fuel , makes the burning process highly efficient . different flows of liquid diesel fuel were entered into the device as shown on fig1 at 101 . a rate of 7 . 5 gallons / hour , 4 . 5 gallons / hour and a rate of 2 gallons / hour , with an added weight ratio of 10 % of the needed stoichiometric air used for burning to form composite fuel . the combustion performance was increased in the range of 25 to 45 % in equal condition without the added air in the form of fuel . a reduction in toxic exhaust gasses has been observed . one parameter was adjusted , such as the pressure of the compressed air to regulate the nature and composition of the fuel composite 1 . upon expansion of the composite fuel , this mixture remain a composite . instead of 7 . 5 gallons of fuel producing 100 mj of energy in one hour , the fuel composite made of 5 . 25 gallons of fuel and 89 . 25 gallons of air at a pressure of 17 bars will produce the same energy output , thus saving 2 . 25 gallons of fuel well within the range of 25 to 45 %. testing conditions were within 23 % of calculated values and corresponds in a commercial boiler to an increase of fuel performance from a value of 75 % to approximately 87 %. one term that may be used to described the liquid fluid composite 1 is an emulsion or micro - emulsion of liquid where the mixture inside the different droplets is of a geometry based on the different size of the structure of the device for the production of the emulsion . for example , the different channel are of a diameter to produce the emulsion or the fuel composite of determined size without the need of surfactants or other chemicals made to change the property of the fuel . in one embodiment , the flow rate of the different liquids / gas entering the device are varied to alter the pressure , geometry , and different dynamic proportions of the emulsion . the term fluid composite 1 as part of this disclosure must be construed to be , for example a highly structure mixture , with either microscopic structured mix or macroscopic structured mix as described and shown . emulsions or what is generally described as highly structured mixtures or more generally composites can be used in many different fields of technology including for combustion chambers , in the food industry , in the pharmaceutical industry , or for general mixing of fluids , liquids , liquids and gas , or fuel and gas . returning to fig1 , and the structures shown at fig1 a to 13d , as described above , instead of using a liquid as the first stream 110 and a gas as the second stream 115 , what is contemplated as disclosed in the incorporated references is the use of two liquids to form what can be described as an emulsion , a nanoemulsion , or a microemulsion based on the size of the device used . for example a mixture of water and water , or fuel and water or any other two fluid can be used . as shown at fig1 , a first fluid 1208 is drawn into the device rapidly and with great energy and broken into narrow streams 110 sliding past two conical walls 102 , 111 . the fluid 1208 then enters a circular ring area 1209 when it is free to expand to encompass the entire area 1209 considered to be a local ring zone between a hydro - dynamical area and what was called above as the aerodynamic area , now the second hydro - dynamic area . the pressure varies within the area 1209 and as a consequence there is an expansion of the first and second fluids as long as the ring area 1209 is of sufficient size to at least process the volumetric flows of the two streams combined . fluid from the second stream 115 when it arrives at point 1206 has a level of dynamic energy including vortices created from the shearing forces on the conical reflector . the fluids when released at 1208 and 1206 are turbulent and dynamic . at 1210 , an elastic resistance wave is shown where compressed cells 1212 connect with the fluid 110 to create a network of fast moving cells as part of an emulsion also described and shown as a fluid composite 1 as shown with greater detail at fig2 a - c . one of ordinary skill in the art will understand that while a regular array of cells is shown , each with a liquid center 201 surrounded by a shell of incompressible liquid 202 , the energy poured into the creation of the fluid composite 1 is greater and much of the energy remains stored as dynamic elements within the fluid composite 1 . for example , the different cells 1211 shown on fig1 have relative movement and translate , move and shake as would molecules based on a brownian movement . the liquid within the liquid center 201 also retains kinetic and dynamic energy , and the fluid also moves turbulently between small pockets of internal fluid . in an embodiment shown at fig1 to 20 , the dynamic mixing energy is sufficient to help dilute a large fraction of the secondary liquid into the fluid and / or to create smaller structures within the primary liquid . in another embodiment , the energy is sufficient to break chemical bonds in either of the fluids to create chemical radicals that can reattach in a plurality of useful ways or to create small shells having a stable surface caused by excluded volume repulsion , electrostatic interaction , van der waals forces , entropic forces , or even steric forces . for example , if the fluids are at different temperatures , pressures , or flow speeds , the resulting mixture may be at the average temperature of the input fluids or can result in the creation of different microscopic structures within the mixture . gases in comparison to most liquids are highly compressible , and when located as described above in the inner portion of a fuel composite cell once released into an open cavity at a lower pressure , the gas will expand in a much greater proportion than the liquid and in turn any wall of the cell formed with a liquid with be expanded outwardly and stretched to increase the gas to liquid contact surface and thus the burn ratio . pressurized fluids all have different bulk modulus and while generally considered non compressible in relation with gases , the liquids are in fact compressible to some limited ratio . when two liquids form an emulsion , and the emulsion is pressurized or changes in pressure over time , the volumetric ratio of both phases will change as the pressure varies and so with any structural composition . the pressurization of an emulsion made of cells with an internal volume of a first fluid and an external wall made of a second liquid is easier and does not require the compression and management of an important decrease of the volume of the fluid . as the pressure increases in an emulsion , there can be important changes in certain of the characteristics of the fluids . for example , the heat storage capacity , or the evaporation temperature . highly pressurized fluids also have different viscosities , and shear modulus than their unpressured counterparts . organic and inorganic compounds such as oil can break down at very high pressure rates as the shear forces increase . in the case of emulsions , the dynamic effect that keep the cell structure apart can radically change when pressure is varied . fig1 shows on the right a clear fuel that is not an emulsion , and on the left an opaque emulsion formed of little droplets of one liquid into the structure of the other liquid as shown at fig1 with greater detail . the white haze of the emulsion is a stable structure described hereafter . in the example given and shown at fig1 , a mixture of 15 % of water to 85 % of fuel shows droplets of approximately 1 to 2 micrometers of a pressurized emulsion at 3 bars of pressure . once pressure is lowered , the structure can evolve into what is shown at fig1 . in fig1 , the larger cell clearly shows white spots concentric to the center . the other smaller cells also have white structures within the larger cell . fig1 , and 18 show a close up view of the nebulous feature of each cell along with the regular shape outer cell wall . the larger droplet , can also as some level of mixing include a different type of mixed structure within the larger cell . what is shown as a white hue is a complex nano - structure within a larger micro - structure stable based on different properties to form the unique emulsion described herein . pressure variations , as part of the dynamic system to create these emulsions is important . when pressure on the overall emulsion is changed , the pressure on each complex nano - structures also changes . for example , the white hue at fig1 may be caused by light scattering on pressure variations in the structure , or a partly evaporated water vapor pressurized within smaller cells . what is observed is the unique properties of the emulsion , how it reacts when pressure , temperature , and other external conditions change . what is also observed is how the structure also changes with the different proportions of the mixture , the speed and pressure of entry into the mix . what is shown and described is a pressurized emulsion 1 within a vessel such as an external case 106 shown in one embodiment as a portion of a cylindrical pipe . in one embodiment , the external case 106 is a pipe of uniform diameter . fluid as shown on fig1 enters at 101 and the emulsion 1 exits at 126 as the stabilized emulsion 1 on the right of the device . the emulsion 1 is made of a network of fuel cells 200 in dynamic contact with each other as shown at fig2 b or even fig1 . the structure includes a plurality of fuel spheres or fuel cells 200 each multilevel fuel sphere including a core of a different liquid 201 in dynamic evolution as shown at fig1 , and a shell 202 surrounding the core of liquid such as water 201 made of a liquid in dynamic movement . the dynamic contact of fuel cells shown as a neatly packed array of cells 200 is a turbulent displacement of adjacent and connecting cells 200 in a three dimensional environment moving in relation to each other . the dynamic movement of the liquid of the shell 202 of each cell 200 is a turbulent movement of liquid molecules within the thickness of the shell 202 , and the dynamic evolution of the liquid 201 is a turbulent movement with vortices . in another embodiment , the turbulent displacement is a brownian movement , a movement that seemingly appears random but is a continuous - time stochastic process . in another embodiment , the fluid composite 1 is made of an incompressible liquid such as a hydrocarbon based fuel and water without or without small solid particles such as soot into the water . fig1 shows a device 100 for the production of both a fluid composite 1 made of two gases ( gas composite ), two liquids ( emulsion dynamic composite ), a liquid and a gas ( gaseous composite ). this device 100 is shown with a plurality of different embodiments at fig3 to 7 , and is shown as part of a system for the production of a dynamic emulsion composite at fig8 to 11 . this device 1 is used to conduct the dynamic mixing and the production of an emulsion 1 for a plurality of uses including but not limited to the emulsion injection of compressed fuel into an injection chamber of a combustion cycle . in a combustion system , such as an engine piston , if a dynamic emulsion composite is used with both a fuel and a fraction of water and without air , the composite will rely on external oxidation gas inserted into the chamber . the unique properties of the emulsion with a fraction of a second fluid such as water serves to alter the combustion properties , for example by cooling the reaction or serving as vehicle for the recycling of unburnt hydrocarbons in the form of soot . as a result of greater and cleaner combustion using the emulsion 1 over ordinary fuel and the lesser the release of waste such as no x , co , co 2 , and soot particles . the emulsion 1 is a composite with new properties . mixing liquids does more than create a dual state mixture . the emulsion 1 has a new physical structure , a new dynamic state that is partly compressible , can be partly expanded , may be further merged with other sources of gas or liquids , and results in a fuel with different performance and properties . the emulsion 1 has increased thermal efficiency , results in increased burning capacity , reduction of the specific charge of the fuel . the emulsion 1 is a three - dimensional mixture made of a mixture of components in dynamic movement . one of ordinary skill in the art of mixing will understand that at a total level of mixing , molecules of two liquid phases , while capable of holding as a liquid , will be mixed and surrounded with molecules of the other liquid in a total dissolution . non total mixing will result in partial mixing where pockets of one type of molecules are surrounded by pockets of other molecules . what is described herein is an emulsion that is a non total mixing , but that is of a greater mix than any known emulsion . fig1 shows a regular bent of the surface of a cell at the interface between the two liquids . the bend is caused by the surface tension between both liquids / phases of the emulsion , and where the shape of the minimal surface of contact is inherent to the mixing level because the pressure difference across the fluid interface is proportional to the mean curvature as seen in a young - laplace equation . fig2 shows at a different level of resolution the surface of a shell within the structure . when two fluids are mixed , the thickness of the channels shown as h on both side of the surface at fig2 d may be calibrated to different thicknesses , for example 50 microns and 25 microns so different pressures of both fluids will result in one fluid being laminar and one fluid being turbulent thus creating a misbalance in the flow rates . for example , a laminar flow at 50 % of the surface of a turbulent flow may result in a total flow of 60 % in the mixture . as a consequence , the different size of the water droplets and the distribution of the water in the fuel will not be proportional to the surface of the streams but will be function of the state of the flow in the layer of thickness h . it is understood that the preceding is merely a detailed description of some examples and embodiments of the present invention and that numerous changes to the disclosed embodiments can be made in accordance with the disclosure made herein without departing from the spirit or scope of the invention . the preceding description , therefore , is not meant to limit the scope of the invention but to provide sufficient disclosure to one of ordinary skill in the art to practice the invention without undue burden . | 1 |
reference will now be made in detail to exemplary embodiments of the present invention , examples of which are illustrated in the accompanying drawings , wherein like reference numerals refer to the like elements throughout . exemplary embodiments are described below to explain the present invention by referring to the figures . fig1 is a diagram illustrating a configuration of a simulation - based interface testing automation system for robot software components according to an embodiment of the present invention . the system of fig1 includes a testing automation server 200 , a plurality of test build agents 300 , and a robot hardware simulator 400 . the testing automation server 200 may be implemented as a web - based automatic testing engine server ( web - based testing automation engine server ) that is accessible by a user through a web service . the testing automation server 200 may generate a test case for an interface test of robot software components . additionally , the testing automation server 200 may generate a test driver component , a test stub component , and a simulation control component that are required for testing , and may connect the generated components to each other . the testing automation server 200 may include a test case generator 210 , a test application generator 220 , an automatic build manager 230 , and a database 240 that will be further described with reference to fig2 below . the test case generator 210 may be used as an interface test case generator , and may receive interface representation information ( for example , an interface definition language ( idl ) or an extensible markup language ( xml )) and test specification information of a test target component that are input by a user 100 , and may automatically generate a plurality of test cases . here , the test cases may be stored as files in xml format in the database 240 . additionally , the user 100 may modify the test cases in the database 240 and input expected result values for each test case , through a web interface . the test case generator 210 may include an interface parser 211 , a test case candidate generator 212 , and a test case combination generator 213 , as shown in fig2 . the interface parser 211 may parse and analyze the interface representation information ( for example , the idl or the xml ) of the test target component , and may extract type information regarding input and output parameters of the test target component . the test case candidate generator 212 may generate candidate values of the test cases based on the test specification information input by the user 100 . here , the test case candidate generator 212 may generate candidates of a type of a test case for input parameter ( hereinafter , referred to as “ tcip ”), and a type of a test case for simulation control ( hereinafter , referred to as “ tcsc ”). when the test specification information for each parameter indicates values in a range , not a specific value , the test case candidate generator 212 may automatically generate test case candidates using an equivalence partitioning scheme or a boundary value analysis scheme . the equivalence partitioning scheme may be performed to partition an input domain into equivalence classes , based on range input conditions , restrictions to a specific value , conditions regarding whether the classes belong to a collection , and logic conditions . the equivalence partitioning scheme may enable a selection of a representative test case candidate for each class , assuming that when an error occurs in data in a class , the same error may occur in another data in the class . the boundary value analysis scheme is a modification of the equivalence partitioning scheme , and may be used to increase an error detectability based on a fact that errors frequently occur in boundary values of each range when input and output domains are partitioned into equivalence classes . in other words , when selecting a test case in each of the equivalence classes , data on an edge of each class may be used instead of optional data . the test case combination generator 213 may combine the test case candidates generated by the test case candidate generator 212 using a pair - wise scheme , to reduce a number of test cases . here , the pair - wise scheme is an effective test case generation technique that is based on the observation that most faults are caused by interactions of parameters . the pair - wise scheme may be implemented so that a minimum number of pairs of parameters may be formed in all test cases . the test case combination generator 213 may enable a 2 - way combination ( namely , pair - wise ), a 3 - way combination ( namely , tri - wise ), and all available combinations of parameters , so that the user 100 may remove overlapping test cases among combination pairs of parameters . as a result , a last test case combined by the test case combination generator 213 may be stored in the database 240 . the test application generator 220 may generate a test driver component used for testing for each test case based on information on the test cases and test target component , and a test stub component for a required interface of the test target component . the test application generator 220 may include a test driver component generator 221 , a test stub component generator 222 , and a simulation control component generator 223 , to respectively generate a test driver component , a test stub component , and a simulation control component . the test application generator 220 may generate a simulation control component used for a connection to a robot hardware simulator that enables a simulation instead of robot hardware , and may connect the generated components to each other so that a test may be automatically executed . the automatic build manager 230 may be used as an automatic test build manager , may be connected to the plurality of test build agents 300 that are installed in a test target environment , and may request a test build . additionally , the automatic build manager 230 may download a test case and a test application source code in the test target environment , and may store a result of compiling the source code , or performing a test . the automatic build manager 230 may include a test build scheduler 231 , and a test build agent connector 232 , as shown in fig2 . when requesting a test build , the automatic build manager 230 may perform an instant build , a reserved build , and a periodical build , through the test build scheduler 231 . the test build agent connector 232 may be connected to the plurality of test build agents 300 , may transfer a test build request to the plurality of test build agents 300 , and may receive a test result from a test build agent that performs a test among the plurality of test build agents 300 . the plurality of test build agents 300 may individually exist in various test target environments , for example , a windows ® environment and a linux environment , and may communicate with the automatic build manager 230 in the testing automation server 200 . additionally , the test build agents 300 may compile a test application source code received from the automatic build manager 230 , and may automatically perform a test . fig3 further illustrates an agent 1 300 - 1 among the test build agents 300 . referring to fig3 , the agent 1 300 - 1 may include a build agent manager 310 , a test application compiler 320 , a test application 330 , and an automatic test executor 340 . the build agent manager 310 may be a module for managing automatic test build agents , and may receive a test build request from the automatic build manager 230 of the testing automation server 200 , and may initiate a test build . the test application compiler 320 may automatically compile components required for testing , and may upload , to the database 240 of the testing automation server 200 , a compile log , an execution file , or a dynamic library file that are generated by the compiling . the test application 330 may be connected to a robot hardware simulator , and may test a test target component . specifically , the test application 330 may include required components , test cases , and test result files , and may be automatically executed by the test build agents (* the agent 1 installed in the test target environment . additionally , the test application 330 may control a test simulation environment , an object in the environment , and an operation of a target robot using the required components and the robot hardware simulator based on the test cases . the automatic test executor 340 may execute the test application 330 , and may upload a log and a test result to the testing automation server 200 . here , the log and the test result may be output during testing . the robot hardware simulator 400 may simulate a movement instead of having actual robot hardware perform movement , and may provide a virtual test environment . in particular , the robot hardware simulator 400 may be manually implemented so that the virtual test environment may be matched to characteristics of the test target component . accordingly , the robot hardware simulator 400 may be connected to the test build agents 300 , and may perform a simulation of virtual robot hardware and a robot test environment based on operations of the test build agents 300 . the robot hardware simulator 400 may be connected to the test application 330 of the agent 300 - 1 , may control the virtual robot hardware , and may dynamically change a test environment for each test case , and may perform a test . fig4 through 6 are flowcharts illustrating a simulation - based interface testing automation method for robot software components according to an embodiment of the present invention . fig4 illustrates operation 510 of generating test cases and operation 520 of generating a test application source code , and fig5 illustrates operation 520 in further detail . fig6 illustrates a scheme of automatically performing a test by operations 611 through 628 . referring to fig4 , in operation 511 , the user 100 may request the test case generator 210 of the testing automation server 200 to generate test cases , through a web interface . in operation 512 , in response to a request for generation of test cases , the test case generator 210 may analyze a type of a test target interface , and may receive test specification information input by the user 100 . additionally , in operation 512 , the test case generator 210 may generate test cases based on a result of the analyzing of the test target interface and the test specification information , and may store the generated test cases in the database 240 . hereinafter , operation 512 will be further described with reference to fig5 . referring to fig5 , the test case generator 210 may automatically generate test cases to perform interface testing of an actual robot software component . according to an embodiment of the present invention , an interface of the robot software component may be implemented as a getdistancevalue interface of a robot infrared ( ir ) sensor component based on an open platform for robotics service ( opros ) component structure . a black box test scheme may be adopted for a robot software component without any source code . however , the present invention is not limited thereto . here , the getdistancevalue interface may be used to measure a physical distance between an ir sensor and an obstacle , and to return the measured distance . the getdistancevalue interface may include a single output parameter , namely ‘ double ’, and two input parameters , namely ‘ int / indexofsensor ’, and ‘ int / numofsensor ’, as shown in table 1 below . in operation 512 a , an interface type of a test target component may be analyzed , and information on an input parameter of the test target component may be extracted . specifically , in operation 512 a , the interface parser 211 may parse and analyze interface representation information ( for example , an idl or an xml ) of the test target component , and may extract the input parameter and type information regarding the input parameter . in operation 512 b , test specification information regarding each input parameter and robot hardware - related parameters of the interface may be generated . specifically , the test specification information generated in operation 512 b may be associated with the input parameter extracted in operation 512 a , and a simulation control parameter . in particular , the user 100 may input a range value of the input parameter of the interface , or a specific candidate value . when the test target component is connected to robot hardware , the user 100 may further input simulation control - related parameter information . here , the user 100 may input values from 0 to 10 for the “ indexofsensor ” parameter of the getdistancevalue interface , and may input values from 1 to 5 for the “ numofsensor ” parameter of the getdistancevalue interface . additionally , since the getdistancevalue interface may be used to measure a distance between an ir sensor ( not shown ) and an obstacle 20 , and to return the measured distance , the user 100 may add a “# distance ” parameter , and may input the values from 0 to 10 . here , the “# distance ” parameter may be used to control a location of the obstacle 20 that is a virtual obstacle existing in a test simulation environment . in operation 512 c , test case candidate values may be generated for each parameter satisfying a test specification . specifically , the test specification information generated in operation 512 b may be used to generate the test case candidate values . in operation 512 c , when the test specification information indicates values in a range , not a specific value , test case candidates may be automatically generated using the equivalence partitioning scheme or the boundary value analysis scheme . in operation 512 c , candidate values for each parameter for testing the getdistancevalue interface may be generated , as shown in table 2 below . in table 2 , the “ indexofsensor ” and “ numofsensor ” parameters of the getdistancevalue interface may be of the type of tcip , and the “# distance ” parameter may be of the type of tcsc . in operation 512 d , the test case candidate values for each parameter may be combined . specifically , in operation 512 d , the pair - wise scheme may be used to combine the test case candidate values generated in operation 512 c , thereby reducing the number of test cases . referring to table 2 , the “ indexofsensor ”, “ numofsensor ”, and “# distance ” parameters may respectively include four candidate values . as a result , a number of all available combinations may be 64 , as shown in table 3 below . however , when faults are caused by interactions of two parameters in the same manner as the getdistancevalue interface , the pair - wise scheme may be applied so that overlapping test cases may be removed among combination pairs of two parameters , such as i * n , d * i , and n * d . specifically , referring to table 3 , ( i * n ) 1 ={− 1 ,− 1 }, ( d * i ) 1 ={− 1 . 0 ,− 1 }, and ( n * d ) 1 ={− 1 ,− 1 . 0 } may be generated as combination pairs of parameters in a first test case . a value of ( i * n ) 1 may overlap with a value of ( i * n ) 2 of a 2 nd test case , and a value of ( d * i ) 1 may overlap with a value of ( d * i ) 13 of a 13 th test case . additionally , a value of ( n * d ) 1 may overlap with a value of ( n * d ) 17 of a 17 th test case . in other words , the pairs of each two of the parameters in the first test case overlap with other pairs in another test case and accordingly , overlapping test cases may be removed . when overlapping test cases are removed in the same manner as described above , a number of test cases may be reduced to 17 , thereby obtaining a minimum number of combination pairs of two parameters . the user 100 may remove overlapping test cases for a combination pair of two parameters , or a combination pair of three parameters . in operation 512 d , the parameters may be combined in a 2 - way combination ( namely , pair - wise ), a 3 - way combination ( namely , tri - wise ), and all available combinations . in operation 513 , the test case generator 210 may transmit the generated test cases to the user 100 . in operation 514 , expected result values for each test case that are input by the user 100 may be transmitted to the test case generator 210 . in operation 515 , the expected result values may be set for each test case , and may be stored in the database 240 . to generate a test application source code , in operation 521 , the user 100 may transmit a request for generation of a test application source code to the test application generator 220 of the testing automation server 200 . in operation 522 , the test application generator 220 may transfer a test case information request to the test case generator 210 . in operation 523 , the test case generator 210 may transmit the test cases that are generated in advance to the test application generator 220 . in operation 524 , the test application generator 220 may generate source codes of a test driver component and a simulation control component , based on the received test cases . in operation 524 , when a test target component includes a required interface , the test application generator 220 may generate a test stub component including a provided interface with the same type as that of the test target component . in operation 525 , the test application generator 220 may generate connection information in the xml format , and may store the generated connection information in a file . here , the connection information may be used to connect the test target component to each of the generated components . additionally , codes stored in the file may be used as source codes of the test application . in operation 526 , the test application generator 220 may transmit the file to the user 100 , so that the user 100 may check or modify the generated source code of the test application , using a web user interface ( ui ). fig6 further illustrates operation 512 of automatically performing a test , and operation 512 of fig6 may be initiated by generating the test application and the source code of the test application through the operations described with reference to fig4 and 5 . in operation 611 , the user 100 may transfer a test application build request to the automatic build manager 230 of the testing automation server 200 . here , information of the test application build request may include identification information to identify the test build agents 300 , for example an internet protocol ( ip ) address . in operation 612 , the automatic build manager 230 may determine whether the agent 1 300 - 1 associated with the information of the test application build request among the plurality of test build agents 300 is connected . when the agent 1 300 - 1 is determined to be connected , the automatic build manager 230 may send a request for a test application build to the build agent manager 310 . when the test application build is requested by the automatic build manager 230 , the build agent manager 310 may download , from the testing automation server 200 , the test case and the test application source code , and may transfer the downloaded test case and test application source code to the test application compiler 320 in operation 613 . additionally , in operation 613 , the build agent manager 310 may send a compile request to the test application compiler 320 . in operation 614 , the test application compiler 320 may compile the received test case and test application source code , and may generate a log file . in operation 615 , a compile result and the log file obtained in operation 614 may be transferred to the build agent manager 310 . in operation 616 , the build agent manager 310 may determine whether an error occurs during the compiling in operation 614 . when the error is determined to occur in operation 616 , the compile result and the load file may be uploaded to the testing automation server 200 in operation 617 , because the test application is not able to be executed due to the error . and in operation 618 , a compile result and the log file obtained in operation 617 may be transferred to the user 100 . conversely , when determining that there is no error in operation 616 , the build agent manager 310 may request the automatic test executor 340 to execute the test application in operation 619 . in operation 620 , the automatic test executor 340 may generate a new test application process , and may execute a new test application . in operation 621 , the test case may be loaded from the executed test application 330 . in operation 622 , the simulation control may be performed by a connection to the robot hardware simulator 400 . in operation 623 , robot hardware simulation information generated based on a control result may be transferred to the test application 330 . in operation 624 , the test application 330 may determine continuation or termination based on whether the robot hardware simulation information for the test is completely transferred and acquired . operations 622 and 623 may be repeated based on a result of the determining in operation 624 . when the termination is determined in operation 624 , the test application 330 may transfer a termination message to the automatic test executor 340 in operation 625 , and the automatic test executor 340 may transfer the termination message to the build agent manager 310 in operation 626 . in operation 627 , the build agent manager 310 may upload , to the testing automation server 200 , the compile result and a test execution result of the test application . in operation 628 , the automatic build manager 230 may analyze the uploaded compile result and test execution result to obtain a test build result , so that the test build result may be transferred to the user 100 . the user 100 may determine , based on the received test build result , whether an error occurs in an interface targeted for testing . fig7 is a diagram illustrating configurations and operations of the test application 330 and the robot hardware simulator 400 . referring to fig7 , the test application 330 may include a test driver component 331 , a simulation control component 332 , and a test target component 333 . the test driver component 331 may be used to control an overall test operation , and may function to read a test case file and to test a test target interface . the test driver component 331 may divide a test case inputted during a test into a tcsc and a tcip , and may set a test simulation environment through an interface of a simulation control component using the tcsc . additionally , the test driver component 331 may call the test target interface using the tcip , may perform the test , and may store a test result in a file . the simulation control component 332 may be used to set a test simulation environment based on the tcsc , and may control an object in the test simulation environment using a simulation control application programming interface ( api ) 410 provided by the robot hardware simulator 400 . additionally , the simulation control component 332 may distinguish a test driver from a simulation control part during the test , may control the robot hardware simulator 400 variously based on input parameters of the same interface , and may perform the test so that a reusability of a test case may be increased . the test target component 333 may function to receive robot hardware information from the robot hardware simulator 400 using a robot hardware api for simulation 420 that includes an identical interface to that of an actual robot hardware api , during the test . here , when the test target component 333 includes a required interface , and when there is no component including a provided interface with the same type as the required interface , any function may be performed . since this situation may occur in development of component - based software , the test application 330 may further include a test stub component 334 including a virtual interface having the same type as the required interface . the test stub component 334 may be used instead of an actual robot software component , to support the test target component 333 so that the test target component 333 may perform its function . the robot hardware simulator 400 may include the simulation control api 410 , and the robot hardware api for simulation 420 , as shown in fig7 . the simulation control api 410 may be used to control a virtual test environment . the simulation control component 332 of the test application 330 may dynamically change a test environment for each test case using the simulation control api 410 , to perform a test . the robot hardware api for simulation 420 may be used to control virtual robot hardware or to receive data . the test target component 333 of the test application 330 may control the virtual robot hardware or receive data , using the robot hardware api for simulation 420 . the test application 330 and the robot hardware simulator 400 may be connected to each other , and may perform the following operations to test a target interface . the test driver component 331 may load a test case file , and may transmit the tcsc through a simulation control interface of the simulation control component 332 , to set a virtual test environment . the simulation control component 332 may change a location of an object existing in the virtual test environment based on the tcsc , using the simulation control api 410 provided by the robot hardware simulator 400 . when the virtual test environment is completely set , the test driver component 331 may call a test target interface using the tcip as an input parameter . the test target component 333 may call an interface of the test stub component 334 , and may process or receive data using the robot hardware api for simulation 420 . when the operation is completed , a result value of the operation may be returned to the test driver component 331 . the test driver component 331 may compare the returned result value with the expected result values , and may store information indicating whether the test succeeds in a test result file , to complete the test . fig8 is a diagram illustrating an example of the test application 330 and the robot hardware simulator 400 of fig7 . referring to fig8 , to describe an availability and effects of the example and embodiments of the present invention , a test application 330 - 1 may be implemented to perform a test for the getdistancevalue interface of the robot ir sensor component based on the opros component structure , and may analyze a result of the test . for example , when a location of an obstacle 20 is changed , the test application 330 may test whether the getdistancevalue interface of a robot 10 equipped with an ir sensor is able to receive a distance between the ir sensor and the obstacle 20 of which the location is changed . accordingly , the robot hardware simulator 400 may be installed with an opros simulator . since the required interface does not exist in an opros ir sensor component , the test application 330 - 1 may not generate the test stub component 334 . the testing automation server 200 may generate test cases for the getdistancevalue interface . the generated test cases may be shown in table 3 and fig9 . the user 100 may manually insert expected result values for each test case , and the test application generator 220 of the testing automation server 200 may generate a source code of a test application . fig1 illustrates an example of the source code of the test application generated by the test application generator 220 . the test for the getdistancevalue interface may be performed by the test application 330 - 1 and the robot hardware simulator 400 . specifically , the test driver component 331 - 1 may load the test case file , and may input a “# distance value ” to the simulation control component 332 - 1 , to set a test environment . the simulation control component 332 may transfer the input “# distance value ” to an obstacle distance control api 410 - 1 , namely , the simulation control api 410 of the robot hardware simulator 400 . the test driver component 331 - 1 for the getdistancevalue interface may load a test case file in the xml format , and may classify the loaded test case file into a type of tcsc , namely # distance , and a type of tcip , namely indexofsensor , and numofsensor . accordingly , the simulation control component 332 - 1 may move the obstacle 20 from the ir sensor by a test case value of “# distance ”, using the obstacle distance control api 410 - 1 provided by the robot hardware simulator 400 . when the obstacle 20 is completely moved , the test driver component 331 - 1 may call the getdistancevalue interface of the test target component 333 - 1 using test case values of “ indexofsensor ”, and “ numofsensor ” as input parameters . the test target component 333 - 1 may be used as an opros ir sensor component , to calculate a distance value representing a distance between the obstacle 20 and the robot 10 with the ir sensor ( not shown ) and to return the distance value to the test driver component 331 - 1 , using an ir sensor simulation api 420 - 1 provided by the robot hardware simulator 400 . the test driver component 331 - 1 may compare the distance value returned by the test target component 333 - 1 with the expected result values input by the user 100 , and may store information indicating whether the test succeeds in a test result file , to complete the test . fig1 illustrates a result of the test for the getdistancevalue interface performed by the test application 330 - 1 and the robot hardware simulator 400 of fig8 . referring to fig1 , first through third columns , namely “ indexofsensor ,” “ numofsensor ,” and “# distance ,” may indicate test cases . additionally , a fourth column , namely “ return ,” may indicate an actual result value that is returned , and a fifth column , namely “ result ,” may indicate whether the test result is “ pass ” or “ fail ”. specifically , # distance may denote a distance between the ir sensor and the obstacle 20 , and a value of “− 1 ” may be outside of a range . for example , in a first test case of fig1 , values of “ 5 ”, “ 1 ”, and “− 1 ” may be respectively input as values of the test cases , namely indexofsensor , numofsensor , and # distance . in this example , a value of “ 1 ” may be output as an actual result value , and a test result may be determined as “ pass ” since the test is successfully completed . as another example , in a sixth test case of fig1 , values of “ indexofsensor ”, “ numofsensor ”, and “# distance ” may be respectively represented as “ 5 ”, “ 4 ”, and “ 0 . 5 ”. in other words , the value of “# distance ”, namely the distance between the ir sensor and the obstacle 20 , is expected as “ 0 . 5 ”, and a value of “ 0 . 5 ” may also be output as an actual result value . in this example , a test result may be determined as “ pass ” based on the fifth column . referring to the fifth column of fig1 , tests for all test cases may be determined to be successfully completed . thus , it is possible to test whether opros ir sensor components are functioning normally . the methods according to the embodiments of the present invention may be recorded in non - transitory computer - readable media including program instructions to implement various operations embodied by a computer . the media may also include , alone or in combination with the program instructions , data files , data structures , and the like . the program instructions recorded on the media may be those specially designed and constructed for the purposes of the embodiments , or they may be of the kind well - known and available to those having skill in the computer software arts . although a few exemplary embodiments of the present invention have been shown and described , the present invention is not limited to the described exemplary embodiments . instead , it would be appreciated by those skilled in the art that changes may be made to these exemplary embodiments without departing from the principles and spirit of the invention , the scope of which is defined by the claims and their equivalents . | 6 |
the present invention has utility as a mixture promoting plant growth through multiple modes , and specifically includes the simultaneous application of multiple fertilizer granules substantially independent of an active agent in concert with the delivery of multiple active agent granules mixed therewith where the active agent granules are substantially independent of fertilizer . the combination of fertilizer granules and active agent ( s ) granules in a single mixed composition allows for a single broadcast application to deliver fertilizer and one or more active agent ( s ) inhibitive of an organism interfering with plant growth , or causing growth regulation , or the like thereby saving on labor of application . additionally , as the granules are substantially devoid of dust cross contamination allowing them to operate without interference from the to the intermixed granule . in contrast to the prior art where fertilizer and pesticide have been formulated as a single unified particle , the combination of the present invention promotes ease of manufacture in allowing bulk production of fertilizer granules separate from active agent granules and the separate storage of each with custom blending of the two types of granules in response to custom needs associated with regulatory usage of particular active agents , a deleterious organism outbreak , seasonal conditions , soil nutrient depletion , or any combination thereof . additionally , with the reduced processing associated with modifying a fertilizer granule to include a pesticide and instead only mixing two types of fully formulated granules together , an inventive mixture shows less granule dusting and fragmentation associated with handling . as a result , the usage of inert adhesion and dusting agents conventional to the art to promote particle integrity is eliminated or at least greatly diminished , thereby affording ease of manufacture and higher efficacy through avoidance of unintended chemical or physical interactions between inert ingredients , various plant nutrients , active agent ( s ) and granule mixtures under application conditions . it is appreciated that the tolerance of a specific composition of fertilizer or active agent granule to cross contamination is readily determined through routine experimentation and the nature of the mode of action . for instance , pest attractant containing active agent granules are diminished by adherence of a quantity of fertilizer making the active agent granules less active to pests . through control of the specific identity of the fertilizer in the fertilizer granule and the quantity of fertilizer adherent tot the active agent granules through routine experimentation , a pest attractant in an active agent granule remains attractive to pests thereby bringing the pest into contact with the toxic agent and in so doing reduces the overall quantity of toxin needed in the active agent . a fertilizer granule operative in the present invention need only be well sized for broadcast distribution and inert towards active agent granules mixed therewith for broadcast distribution . a typical fertilizer granule has a size of from 500 to 3 , 000 microns . the fertilizer granule includes a quantity of a bioavailable source of nitrogen , phosphorus , potassium , or a combination thereof . the bioavailable n — p — k ingredients are present in the fertilizer granule in an amount ranging from 5 to 99 weight percent of the total dry weight of the fertilizer granules . more preferably , the n — p — k components are present in amounts ranging from 30 to 99 percent by weight of the dry weight of fertilizer granules . still more preferably , the n — p — k components are present in amounts ranging from 50 to 99 percent by weight of the total dry weight of the fertilizer granules . exemplary fertilizer n — p — k contributing constituents contain one of the plant nutrients nitrogen , phosphate or potassium and illustratively include urea , sulfur - coated urea , isobutylidene diurea , ammonium nitrate , ammonium phosphates varying degrees of ammonation , ammonium polyphosphates , triple super phosphate , phosphoric acid , potassium sulphate , potassium nitrate , potassium metaphosphate , potassium chloride , dipotassium carbonate , potassium oxide , phosphate rock , nitrophosphate , and a combination of these . it is also appreciated that a fertilizer granule readily incorporates other substances stimulative of target plant growth and illustratively include soil conditioners , trace elements , plant hormones active in the target plant , and dust control , flowability and / or storability additives . additionally , the fertilizer granule optionally includes conventional fillers , binders , and additives as exemplified in u . s . pat . no . 6 , 884 , 756 . preferably , the fertilizer granule includes at least 20 units of n — p — k nutrients , where a “ unit ” is used herein to define an increment of 1 % of a guaranteed plant nutrient as defined by the american association of plant food control officials ( aapfco ), which is the uniform standards - setting association of state fertilizer control officials in the united states . a binder component is present in a carrier particle an amount ranging from 0 . 1 % to 75 % by weight of the total dry weight of the carrier particle . in a further embodiment , the binder component is present in an amount ranging from 1 % to 25 % by weight of the total dry weight of the particle . a binder component is included in a particle as necessary to produce or promote cohesion in forming a particle capable of retaining a specified form during transport and / or distribution . a binder component may be bentonite clay , carbohydrate , protein , lipid , synthetic polymer , glycolipid , glycoprotein , lipoprotein , lignin , a lignin derivative , a carbohydrate - based composition , and a combination thereof . in a preferred embodiment the binder component is a lignin derivative and is optionally calcium lignosulfonate . alternatively , the binder component is selected from the group consisting of : a monosaccharide , a disaccharide , an oligosaccharide , a polysaccharide and combinations thereof . specific carbohydrate binders illustratively include glucose , mannose , fructose , galactose , sucrose , lactose , maltose , xylose , arabinose , trehalose and mixtures thereof such as corn syrup ; celluloses such as carboxymethylcellulose , ethylcellulose , hydroxyethylcellulose , hydroxy - methylethylcellulose , hydroxyethylpropylcellulose , methylhydroxyethyl - cellulose , methylcellulose ; starches such as amylose , seagel , starch acetates , starch hydroxyethyl ethers , ionic starches , long - chain alkyl starches , dextrins , amine starches , phosphates starches , and dialdehyde starches ; plant starches such as corn starch and potato starch ; other carbohydrates such as pectin , amylopectin , xylan , glycogen , agar , alginic acid , phycocolloids , chitin , gum arabic , guar gum , gum karaya , gum tragacanth and locust bean gum ; vegetable oils such as corn , soybean , peanut , canola , olive and cotton seed ; complex organic substances such as lignin and nitrolignin ; derivatives of lignin such as lignosulfonate salts illustratively including calcium lignosulfonate and sodium lignosulfonate and complex carbohydrate - based compositions containing organic and inorganic ingredients such as molasses . suitable protein binders illustratively include soy extract , zein , protamine , collagen , and casein . binders operative herein also include synthetic organic polymers capable of promoting or producing cohesion of particle components and such binders illustratively include ethylene oxide polymers , polyacrylamides , polyacrylates , polyvinyl pyrrolidone , polyethylene glycol , polyvinyl alcohol , polyvinylmethyl ether , polyvinyl acrylates , polylactic acid , and latex . in a preferred embodiment , the binder is calcium lignosulfonate , molasses , a liquid corn starch , a liquid corn syrup or a combination thereof . an inventive fertilizer granule is produced by a number of processes . in the preferred process , the granule components are wet - granulated through a process of steps , including mixing of various dry components , wet - massing the dry powder mixture with liquid surfactants , binders or the like , alone or with the addition of a solvent to arrive at a suitable consistency for granulating . of the binders detailed herein , methyleneurea is particularly preferred . in order to preclude undesirable inventive mixture interactions , a fertilizer granule is substantially devoid of an active agent . prior art interactions associated with single particles containing both fertilizer and the pesticide have included chemical foliage burning when such single particles are applied under high humidity , high temperature conditions . as used herein “ substantially devoid ” is defined to mean that the interior of a granule is formulated free from a given substance and that surface adhesion of dust associated with the given substance amounts to less than 20 % of the total dry weight of the granule , preferably less than 10 % of the total dry weight , more preferably less than 5 % of the total dry weight and most preferably , less than 1 % of the total dry weight . for example , a fertilizer granule if formulated devoid of active agent and most preferably less than 1 % of the active agent present as active agent granules intermixed with the fertilizer granules becomes adhered to fertilizer granules . an active agent granule carrier particle operative in the present invention need only be well sized for broadcast distribution and be inert towards the active agent coating . typically , a base carrier particle has a size from 500 to 3000 microns . suitable carrier particles include fragmented materials such as rock dust , clay , corncob , cereal or grain hulls , peanut hulls , plant pulp , other plant - based cellulosic materials , clays , and granular baits . the carrier component is specifically excluded from the definition of a fertilizer as used herein with respect to the present invention . specific examples of base carrier particles include : limestone particulate having a mean particle size of 1000 microns ; processed snack food ; and defatted , extruded corn granules having a mean particle size of 1500 microns . alternatively , a carrier particle is formed through the combination of a binder component with fine grain particle as detailed above and has 90 % of the particles having a diameter less than 150 microns . particulate is typically present from 0 . 1 to 99 . 9 total weight percent and preferably from 5 to 98 total weight percent . an exemplary composite carrier particle is disclosed in u . s . pat . no . 6 , 884 , 756 . a binder component is present in an active agent carrier particle in an amount ranging from 0 . 1 percent to 75 percent by weight of the total dry weight of the active agent granule . in a further embodiment , the binder component is present in an amount ranging from 1 percent to 25 percent by weight of the total dry weight of the active agent granule . an active agent binder component is included in an active agent granule as necessary to produce or promote cohesion in forming the granule capable of retaining a specified form during transportation and / or distribution . the identity of a binder component is the same as the binder components detailed with respect to a fertilizer granule where these binders are specifically excluded from the definition of a fertilizer as used herein with respect to the present invention . optionally , the active agent granule incorporates a pest attractant . in an active agent granule incorporating a pest attractant , the pest attractant is present in an amount ranging from 0 . 05 % to 50 % by weight of the total dry weight of the carrier particle . in a more preferred embodiment , the pest attractant active ingredient is present in an amount ranging from 0 . 1 % to 30 % by weight of the total dry weight of the particle . pest attractants are foodstuffs , scents , or pheromones attractive to a target pest . it is appreciated that when a pest attractant is a scent or pheromone the amounts needed are quite small and typically range from 0 . 0001 to 0 . 05 total weight percent of an inventive granule . the nature of the pest attractant foodstuff , scent , or pheromone is readily selected by reviewing the existing literature as to pest diet , and sexual hormones . representative of the literature is “ destructive turfgrass insects : biology , diagnosis , and control ” by d . a . porter ( 1995 ). an active agent in solid or liquid form is present in or on an active agent granule . the active agent is added virtually without limit and includes any active agent solid or liquid active to inhibit an organism deleterious to the target plant and includes herbicide , insecticide , fungicide , growth regulator , nematicide , or other biologically active agent or pesticide . representative herbicide active agents illustratively include dinitroanilines such as benefin , trifluralin , pendimethalin , and prodiamine ; oxadiazoles such as oxadiazon ; triazines such as atrazine and simazine ; triazolinones such as carfentrazone and sulfentrazone ; aryloxyphenoxy propionates ; arylaminopropionic acid ; cineole ( such as cinmethylin ); cyclohexanediones ; sulfonylureas such as trifloxysulfuron and metsulfuron - methyl ; imidazolinones ; pyrimidinylthio - benzoate ; triazolopyrimidine ; pyridazine ; phenoxys ( or phenoxies ); benzoic acids ; carboxylic acids ( such as dcpa , clopyralid , trichloroacetic acid , and fluoroxypyr ); quinoline carboxylic acid ; semicarbazone ; triazinones ; uracils ; pyridazinone ; phenyl - carbamates ; nitriles ; benzothiadiazoles ; organoarsenicals ; phenyl - pyridazine ; triketones such as mesotrione ; ureas and substituted ureas ( such as diuron , linuron , siduron , tebuthiuron , dymron etc . ); amide ( such as propanil and bromobutide ); thiocarbamates ; pyrazolium ( such as difenzoquat ); phosphoric acid compounds ( such as glufosinate - ammonium and glyphosate ); triazole ; pyridazinone ; nicotinanilide ; pyridinone ( such as fluridone ); isoxazolidinone ; diphenylethers ; n - phenylphthalimides ; oxadiazole ; triazolinone ; chloroacetamides ; oxyacetamides ; phthalamate ; phthalamate semicarbazone ; nitrile ; n - phenylphthalimides ; oxadiazole ; triazolinone ; acetamides ; benzoylisoxazole ; isoxazole ; pyrazole ; pyrazolium ; triketone ; and benzofuran ; various als inhibitors ; and plant extract herbicides such as the allelopathic exudates of various plants . representative microbiocidal and fungicidal active agents illustratively include plant and general disease control agents including fungicides , fungistats , antibiotics and bacteriocides of the following chemical families and functional groupings ; various acetamides , sterol inhibitors or demethylase inhibitors , dicarboximides ( such as iprodione ), phthalides , phthalmic acids , triadiazoles , isophthalates , triazines , triconazoles , strobilurins , benzimidazoles , benzithiazoles , dithiocarbamates , carboxamides , carboxides or anilides , chlorphenyls , indolecarboxylic acids , isoxazoles , imidazoles , oxazolinediones , guanidines , diguanidines , piperidines , pyridines , sulfenamides , sulfonamides , quinolines , cyanoimidazoles , pyrazoles , pyrrolecarbonitriles , spiroketalamines , thiazoles , various chemical families of oomycete ( pythium ) fungicides , nitriles , chlorinated hydrocarbons , phenylpyrroles , polyoxins , pyridazinones , mycotoxins ( e . g . penicillin ) or other antibiotics ( e . g . streptomycin , kasugamycin , blasticidin , polyoxins , validamycin , mildiomycin , and oxytetracyline ), morpholines , other organic compounds such as piperalin , piperazine derivatives and tolylfluanid , bronopol , organic compound mixtures ( e . g . bacticin and harpin protein ), organic acids such as cinnamic acid and its derivatives , bacteria such as agrobacterium radiobacter , bacillus subtilus , erwinia carotovora , pseudomonas flourescens and p . chlorophis , and any varieties or strains thereof , fungi such as candida oleophila , fusarium , tricoderma , gliocladium , streptomyces , and ampelomyces and any species , varieties or strains thereof , and viruses such as tomovax . for purposes of this invention , plant growth regulators are ingredients such as trinexepac - ethyl , gibberellic acid , gibberellins , cytokinins , benzyladenine , glycines , quinolenes , phosphoric acid compounds , organic carbamates , quaternary ammonium compounds , acetamides , ethychlozate , azoles , paclobutrazol , anilides , pyradazidine , pyrimidines , napthaleneacetamide , phthalmides , phenoxies , pyrimidines , hybridizing agent , biostimulants , seaweed extracts and herbicides ( typically at low use rates ), phthalmides , phenoxies , organic or carboxylic acids ( e . g . gamma amino butyric acid and l - glutamic acid , naphthalene acetic acid , clofencoet , sintofen , nicotinic acids ), and herbicides ( typically at low use rates ). for purposes of this invention , other pesticides include animal and bird repellants , bitter flavors , irritants , and malodorous ingredients , molluscicides ( e . g ., slugs and snails ), nematicides , rodenticides , defoliants , chemosterilants , plant defense boosters ( harpin protein and chitosan ) desiccants ( may also be used as a harvest aid ), and other beneficial or detrimental agents applied to plant or other surfaces . pesticides suitable to form a liquid coating on an active agent carrier particle include pyrethroids such as bifenthrin , permethrin , deltamethrin , lambda cyhalothrin , cyfluthrin , or betacyfluthrin ; organophosphates such as chlorpyrifos and trichlorfon ; limonoids such as azadirachtin or meliartenin ; phenyl pyrazoles or oxadiazines such as indoxacarb ; phthallic acid diamides such as flubendiamide and anthranilic diamides ; neonicitinoids such as imidacloprid and clothianidin , and diacylhadrazines such as halofenozide ; and carbamates such as carbaryl and indoxacarb . additionally , it is appreciated that a number of conventional adjuvant systems used to solubilize a pesticide for application as a coating onto an active agent carrier particle are rendered more effective by the present invention . by way of example , pyrethroids degrade to yield organic acids that in proximity to certain pesticide powders such as carbamates function to extend the carbamate activity half - life . for purposes of this invention , other protectants and beneficial ingredients include attractants , baits , herbicide safeners , antidessicants , antitranspirants , frost prevention aids , inoculants , dyes , brighteners , markers , synergists , pigments , uv protectants , antioxidants , leaf polish , pigmentation stimulants and inhibitors , surfactants , moisture retention aids , molluscicides ( e . g ., slugs and snails ), nematicides , rodenticides , defoliants , desiccants , sticky traps , and ipm lures . it is appreciated that multiple active agents are readily formulated within an active agent granule . preferably , synergistic combinations of active agents such as two pesticides that have complementary modes of action such that the total amount of the multiple active agents needed to provide a given level of organism inhibition interfering with plant growth is reduced relative to the active agent administered separately . active agent granules are optionally compounded with inner fillers , dust control and flow aids , solvents , surfactants , and / or other adjuvants , alone or in combination with up to several other active agents . a collection of fertilizer granules and active agent granules are preferred each formulated such the density difference between fertilizer granules and active agent granules is less than 1000 %. more preferably , the density difference between fertilizer granules and active agent granules is lass than 500 %. it is appreciated that by controlling the density difference , the propensity of the mixture to segregate during transit is reduced . settling is also disfavor in a mixture of fertilizer granules and active agent granules that vary in average diameter by less than 30 diameter % and preferably , less than 10 diameter %. the mixture that is made up of fertilizer granules varies between 10 and 99 number % of the granules present . active agent granules vary between 0 . 0005 and 90 number percent with the inclusion of an inert carrier particle akin to an active agent granule less the active agent is also considered to be part of the present invention . inert granules making up from 0 to 30 number percent of the particles present . the inventive mixture affords a formulator the ability to maintain separate stocks of fertilizer and or active agent granules and blend fertilizer granules and active agent granules in response to customer orders , or field conditions . as a result an inventive mixture is broadcast onto soil surrounding a target plant with specificity as to factors such as soil chemistry , interfering organism outbreaks , rainfall , drought , or the like . a fertilizer granule is readily formed by conventional techniques or purchased commercially , e . g ., andersons golf products turf fertilizer 18 - 6 - 15 ( the andersons , maumee , ohio ). techniques commonly used to form a fertilizer granule containing fertilizer and any other optional adjuvants illustratively includes drum or pan agglomeration , pastille formation , molten droplet spray , crystallization , extrusion , and compaction . techniques for the formation of a fertilizer pellet are provided in granulated fertilizers , robert a . hendrie , noyes data corporation , park ridge , n . j ., 1976 . other techniques include those disclosed in example a of u . s . pat . no . 6 , 884 , 756 . an active agent granule is readily formed by conventional techniques or purchased commercially ( the andersons , maumee , ohio ). such techniques are detailed in u . s . pat . no . 6 , 231 , 660 . the mixing of fertilizer granules and active agent granules occurs through conventional techniques with preference to mixing technologies that provide minimized granule fracture and dusting . mixing techniques operative herein illustratively include mechanical , air , spraying , and tumbling . it is appreciated that fertilizer granule stock and active agent granule stock are readily stored separately and blended in response to a particular order . alternatively preselected mixtures of fertilizer granules and active agent granules are bagged and stored . patent documents and publications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains . these documents and publications are incorporated herein by reference to the same extent as if each individual document or publication was specifically and individually incorporated herein by reference . the foregoing description is illustrative of particular embodiments of the invention , but is not meant to be a limitation upon the practice thereof . the following claims , including all equivalents thereof , are intended to define the scope of the invention . | 0 |
this invention is directed to a method of selectively separating olefinic hydrocarbons from paraffinic hydrocarbons using a membrane containing certain polyimide polymers , copolymers and blends thereof . the polymers which form these polyimides have repeating units as shown in the following formula ( i ): in which r 2 is a moiety of composition selected from the group of consisting of formula ( a ), formula ( b ), formula ( c ) and a mixture thereof , z is a moiety of composition selected from the group consisting of formula ( l ), formula ( m ), formula ( n ) and a mixture thereof ; and r 1 is a moiety of composition selected from the group consisting of formula ( q ), formula ( t ), formula ( s ), and a mixture thereof , in a preferred embodiment the polyimide that forms the selective layer of the membrane has repeating units as shown in the following formula ( ii ): in this embodiment , moiety r 1 is of formula ( q ) in 0 - 100 % of the repeating units , of formula ( t ) in 0 - 100 % of the repeating units , and of formula ( s ) in a complementary amount totaling 100 % of the repeating units . a polymer of this structure is available from hp polymer gmbh under the tradename p84 and is much preferred for use in the present invention . p84 is believed to have repeating units according to formula ( ii ) in which r 1 is formula ( q ) in about 16 % of the repeating units , formula ( t ) in about 64 % of the repeating units and formula ( s ) in about 20 % of the repeating units . p84 is believed to be derived from the condensation reaction of benzophenone tetracarboxylic dianhydride ( btda , 100 mole %) with a mixture of 2 , 4 - toluene diisocyanate ( 2 , 4 - tdi , 64 mole %), 2 , 6 - toluene diisocyanate ( 2 , 6 - tdi , 16 mole %) and 4 , 4 ′- methylene - bis ( phenylisocyanate ) ( mdi , 20 mole %). in another preferred embodiment , the polyimide that forms the selective layer has repeating units of compositions selected from among those shown in the following formulas ( iiia and iiib ): the repeating units can be exclusively of formula ( iiia ) or formula ( iiib ). preferably , the repeating units are a mixture of formulas ( iiia ) and ( iiib ). in these embodiments , moiety r 1 is a composition of formula ( q ) in about 1 - 99 % of the repeating units , and of formula ( t ) in a complementary amount totaling 100 % of the repeating units , and a is in the range of about 1 - 99 % of the total of a and b . a preferred polymer of this structure is available from hp polymer gmbh under the tradename p84 - ht325 . p84 - ht325 is believed to have repeating units according to formulas ( iiia and iiib ) in which the moiety r 1 is a composition of formula ( q ) in about 20 % of the repeating units and of formula ( t ) in about 80 % of the repeating units , and in which a is about 40 % of the total of a and b . p84 - ht325 is believed to be derived from the condensation reaction of benzophenone tetracarboxylic dianhydride ( btda , 60 mole %) and pyromellitic dianhydride ( pmda , 40 mole %) with 2 , 4 - toluene diisocyanate ( 2 , 4 - tdi , 80 mole %) and 2 , 6 - toluene diisocyanate ( 2 , 6 - tdi , 20 mole %). in yet another preferred embodiment , the selectively permeable portion of the membrane can be formed of a material comprising a blend of the above mentioned polymers . for example , it is contemplated that a membrane can be formed from a blend comprising a first polymer having repeating units of formula ( iiia ), formula ( iiib ) as defined above , or a mixture of formulas ( iiia ) and ( iiib ) and a second polymer having repeating units of formula ( ii ) as defined above . greater preference is given to a membrane of a blend consisting essentially of the first and second polymers . in such preferred composition , the second polymer should constitute about 10 - 90 wt . % of the total of the first polymer and the second polymer . the polyimides should be of suitable molecular weight to be film forming and pliable so as to be capable of being formed into continuous films or membranes . the polyimides of this invention preferably have a weight average molecular weight within the range of about 20 , 000 to about 400 , 000 and more preferably about 50 , 000 to about 300 , 000 . the polymer can be formed into films or membranes by any of the diverse techniques known in the art . the polymers are usually glassy and rigid , and therefore , may be used to form a single - layer membrane of an unsupported film or fiber of the polymer . such single - layer films are normally too thick to yield commercially acceptable transmembrane flux of the preferentially permeable component of the feed mixture . to be more economically practical , the separation membrane can comprise a very thin selective layer that forms part of a thicker structure . this structure may be , for example , an asymmetric membrane , which comprises a thin , dense skin of selectively permeable polymer and a thicker micro - porous support layer which is adjacent to and integrated with the skin . such membranes are described , for example , in u . s . pat . no . 5 , 015 , 270 to ekiner . in a preferred embodiment , the membrane can be a composite membrane , that is , a membrane having multiple layers of typically different compositions . modern composite membranes typically comprise a porous and non - selective support layer . it primarily provides mechanical strength to the composite . a selective layer of another material that is selectively permeable , is placed coextensively on the support layer . the selective layer is primarily responsible for the separation properties . typically , the support layer of such a composite membrane is made by solution - casting a film or spinning a hollow fiber . then the selective layer is usually solution coated on the support in a separate step . alternatively , hollow - fiber composite membranes can be made by co - extrusion of both the support material and the separating layer simultaneously as described in u . s . pat . no . 5 , 085 , 676 to ekiner . the membranes of the invention may be housed in any convenient type of separation unit . for example , flat - sheet membranes can be stacked in plate - and - frame modules or wound in spiral - wound modules . hollow - fiber membranes are typically potted with a thermoset resin in cylindrical housings . the final membrane separation unit can comprise one or more membrane modules . these can be housed individually in pressure vessels or multiple modules can be mounted together in a common housing of appropriate diameter and length . in operation , a mixture of one or more olefin compounds and one or more paraffin compounds is contacted with one side of the membrane . under a suitable driving force for permeation , such as imposing a pressure difference between the feed and permeate sides of the membrane , the olefin compounds pass to the permeate side at higher rate than the paraffin compounds of the same number of carbon atoms . that is , a three carbon olefin permeates faster than a three carbon paraffin . this produces an olefin - enriched stream which is withdrawn from the permeate side of the membrane . the olefin - depleted residue , occasionally referred to as the “ retentate ”, is withdrawn from the feed side . the novel process can operate under a wide range of conditions and is thus adapted to accept a feed stream supplied from diverse sources . if the feed stream is a gas that exists already at a sufficiently high , above - atmospheric pressure and a pressure gradient is maintained across the membrane , the driving force for separation can be adequate without raising feed stream pressure farther . otherwise , the feed stream can be compressed to a higher pressure and / or a vacuum can be drawn on the permeate side of the membrane to provide adequate driving force . preferably the driving force for separation should be a pressure gradient across the membrane of about 0 . 7 to about 11 . 2 mpa ( 100 - 1600 psi ). the novel process can accept a feed stream in either the gaseous state or the liquid state . the state of matter will depend on the composition and on the pressure and temperature of the olefin / paraffin feed stream . when the feed stream is in the liquid state , the separation can be carried out by the pervaporation mechanism . basically , in pervaporation , components of the liquid feed mixture in contact with the membrane permeate and evaporate through the membrane , thereby separating the component in the vapor phase . this invention is particularly useful for separating propylene from propylene / propane mixtures . such mixtures are produced as effluent streams of olefin manufacturing operations , and in various process streams of petrochemical plants , for example . thus in a preferred embodiment , the process involves passing a stream comprising propylene and propane in contact with the feed side of a membrane that is selectively permeable with respect to propylene and propane . the propylene is concentrated in the permeate stream and the retentate stream is thus correspondingly depleted of propylene . the membranes of this invention exhibit unexpectedly high propylene / propane selectivity which distinguishes them from prior art membranes . furthermore , the membranes of this invention exhibit stable performance over long periods of time under conditions where membranes of the prior art degrade significantly in performance . contacting one side of the membrane with a feed mixture comprising an olefin compound and a paraffin compound having a number of carbon atoms at least as great as the olefin compound , causing the feed mixture to selectively permeate through the membrane , thereby forming on the second side of the membrane an olefin - enriched permeate composition which has a concentration of the olefin compound greater than that of the feed mixture , removing from the second side of the membrane the olefin - enriched permeate composition , and withdrawing from the one side of the membrane an olefin - depleted composition which has a concentration of the olefin compound less than that of the feed mixture . this invention is now illustrated by examples of certain representative embodiments thereof , wherein all parts , proportions and percentages are by weight unless otherwise indicated . all units of weight and measure not originally obtained in st units have been converted to si units . the entire disclosures of u . s . patents named in the following examples are hereby incorporated by reference herein . asymmetric hollow - fiber membrane of p84 was spun from a solution of 32 % p84 , 9 . 6 % tetramethylenesulfone and 1 . 6 % acetic anhydride in n - methylpyrrolidinone ( nmp ) with methods and equipment as described in u . s . pat . nos . 5 , 034 , 024 and 5 , 015 , 270 . the nascent filament was extruded at a rate of 180 cm 3 / hr through a spinneret with fiber channel dimensions of outer diameter 559 μm and inner diameter equal to 254 μm at 75 ° c . a fluid containing 85 % nmp in water was injected into the bore of the fiber at a rate of 33 cm 3 / hr . the nascent fiber traveled through an air gap of 5 cm at room temperature into a water coagulant bath at 24 ° c . and the fiber was wound up at a rate of 52 m / min . the water - wet fiber was washed with running water at 50 ° c . to remove residual solvent for about 12 hours and then sequentially exchanged with methanol and hexane as taught in u . s . pat . nos . 4 , 080 , 744 and 4 , 120 , 098 , followed by vacuum drying at room temperature for 30 minutes . after that the fibers were dried at 100 ° c . for one hour . samples of fiber were formed into four test membrane modules of 52 fibers each . the fiber in the modules was treated to seal defects in the separating layer with a method similar to the method described in u . s pat . no . 4 , 230 , 463 . the fiber was thus contacted with a solution of 2 % wt . 1 - 2577 low - voc conformal coating ( dow corning corporation ) in 2 , 2 , 4 - trimethylpentane for 30 minutes and then dried . the modules were measured in permeation of a feed of mixed propylene / propane ( 50 : 50 mole %). the feed mixture was provided in the vapor state by controlling the feed pressure at 2 . 8 mpa ( 400 psig ) and the feed temperature at 90 ° c . the feed mixture was supplied to contact the outside of the fibers and the permeate stream was collected at atmospheric pressure . the permeate flowrate was measured by volumetric displacement with bubble flowmeters . the feed flowrate was maintained at greater than twenty times the permeate flowrate . this rate was high enough that the composition on the feed side remained roughly constant while the feed mixture permeated the membrane . this was done to simplify calculation of the membrane permeation performance . the composition of the permeate stream was measured by gas chromatography with a flame ionization detector . the average permeate composition was 92 . 2 % propylene and 7 . 8 % propane . the performance of the membrane was expressed in terms of propylene permeance and propylene / propane selectivity . the permeance is the flowrate of propylene across the membrane normalized by the membrane surface area and the propylene partial pressure difference across the membrane . it is reported in gas permeation units (“ gpu ”). one gpu equals 10 − 6 cm 3 ( at standard temperature and pressure “ stp ”)/( sec · cm 2 · cmhg ). the propylene / propane selectivity is the ratio of the permeance of propylene divided by the permeance of propane . the performance of the four modules is shown in table 1 . a sample of the fiber from example 1 was processed and formed into a test module as in example 1 except that the fiber was not treated to seal defects in the separating layer . the propylene permeance was 1 . 7 gpu and the propylene / propane selectivity was 7 . 5 . although the selectivity was lower than the selectivity of the treated fiber of example 1 , it was high enough to suggest that the p84 fiber with acceptable performance characteristics can be produced as an asymmetric membrane without the sealing posttreatment . asymmetric hollow - fiber membrane of p84 was prepared as in example 1 with the following two changes : ( a ) the water - bath temperature was lowered to 8 ° c . and ( b ) the spinneret temperature was increased to 87 ° c . the fiber was washed , dried and built into test modules and tested in permeation of a 50 : 50 mole % mixed propylene / propane feed mixture as in example 1 . the propylene permeance was 0 . 61 gpu and the propylene / propane selectivity was 15 . asymmetric hollow - fiber membrane of p84 similar to the fiber of example 3 was tested for duration of 4 days at 90 ° c . with a 50 : 50 mole % feed mixture of propylene / propane at 2 . 8 mpa ( 400 psig ). the test was designed to simulate commercial operating conditions . results are shown in table ii . no decline in selectivity was observed . a slight decline was observed in propylene permeance , which stabilized after the second day . one of the modules of example 1 was tested using a 50 : 50 mole % feed mixture of propylene / propane . feed pressure and temperature were controlled at 2 . 8 mpa ( 400 psig ) and 50 ° c ., respectively , to place the feed mixture in the liquid state . the permeate was withdrawn at atmospheric pressure , therefore the permeate was in the vapor phase . for this type of separation the concentration difference across the membrane is usually considered to be the driving force for separation instead of the partial pressure difference as used in gas or vapor permeation . for comparison of the results of this example with permeation under vapor state feed conditions , the simplifying mathematical treatment described in j . g . wijmans and r . w . baker , a simple predictive treatment of the permeation process in pervaporation , j . membrane science 79 ( 1993 ) 101 - 113 ) was applied . such analysis assumes that the liquid feed evaporates to produce a saturated vapor phase on the feed side of the membrane and then permeates through the membrane driven by a partial pressure gradient . this analysis provides a mathematical model that includes terms for feed - side and permeate - side vapor pressures and permeance and selectivity comparable to those used in the separation of gaseous state feed mixtures . the model also contains a term related to the liquid - vapor equilibrium . with the feed mixture of 50 : 50 mole % propylene / propane in the liquid state , the membrane produced a permeate stream of 93 % propylene . by application of the model , it was determined that the propylene permeance was 0 . 46 gpu and the propylene / propane selectivity was 16 . in separate testing with feed mixture of the same composition in the vapor state at 2 . 8 mpa ( 400 psig ) and 90 ° c ., the propylene permeance was 0 . 95 gpu and the propylene / propane selectivity was 13 . this shows that the membrane of p84 can be useful for separation service for liquid propylene / propane . asymmetric hollow - fiber membrane of a 1 : 1 blend of p84 and p84 - ht325 was spun from a solution of 16 % p84 , 16 % p84 - ht325 , 9 . 6 % tetramethylene sulfone and 1 . 6 % acetic anhydride in nmp by the process described in example 1 . the spinning conditions and equipment were similar except that the spinneret temperature was 85 ° c ., the bath temperature was 8 ° c . and the air gap was 10 cm . the fiber was formed into a module which was tested for permeation of a propylene / propane ( 50 : 50 mole %) feed mixture as in example 1 . the permeation performance was 1 . 9 gpu propylene permeance and 11 . 9 propylene / propane selectivity . propylene / propane liquid feed separation with a membrane of p84 blended with p84 - ht325 the module of 1 : 1 blend of p84 and p84 - ht325 of example 6 was tested with 50 : 50 mole % feed mixture of propylene / propane . the feed mixture was maintained in the liquid state by applying the conditions described in example 5 , i . e ., the feed pressure was 2 . 8 mpa ( 400 psig ) and the temperature was 50 ° c . the permeate was withdrawn as a vapor at atmospheric pressure . the membrane produced a permeate with 93 . 6 % propylene ; the propylene permeance was 0 . 6 gpu and the propylene / propane selectivity was 15 . 5 . this shows that the membrane of 1 : 1 blend of p84 and p84 - ht325 can provide useful separation with liquid propylene / propane feed . propylene / propane liquid feed separation with a membrane of p84 blended with p84 - ht325 the test in example 7 ( i . e ., with membrane of 1 : 1 blend of p84 and p84 - ht325 ) was continued for a duration of 100 hours , to assess membrane performance stability under simulated commercial conditions . results are shown in table iii . no significant decline was observed . a thin dense film of p84 polymer was cast from a solution comprising 20 % p84 in nmp . the film was dried at 200 ° c . in a vacuum oven for four days . a sample of the polymer film was tested in a modified 47 - mm ultrafiltration style permeation cell ( millipore ), using a feed mixture of 50 : 50 mole % propylene / propane at 2 . 8 mpa ( 400 psig ) pressure and 90 ° c . temperature . the permeate pressure was 2 - 5 mm hg . the feed flowrate was high enough to ensure low conversion of the feed into permeate so that the composition on the feed side was constant . the compositions of the feed and permeate streams were measured by gas chromatography with a flame ionization detector . the permeate flowrate was determined from the increase in pressure over time in the fixed - volume permeate chamber of the permeation cell . the permeation performance of the polymer is characterized by the two parameters : propylene permeability and propylene / propane permselectivity . the permeability is the flowrate of propylene across the film normalized by the film surface area and film thickness and by the propylene partial pressure difference across the film . units of permeability are barrers . one barrer equals 10 − 10 cm 3 ( stp )· cm /( sec · cm 2 · cm hg ). the propylene / propane permselectivity is the ratio of the propylene and propane permeabilities . the propylene permeability of the p84 film at 90 ° c . and 2 . 8 mpa ( 400 psig ) was 0 . 24 barrers ; and the propylene / propane permselectivity was 15 . 5 . the permselectivity was in good agreement with the selectivity measured with hollow - fiber membranes of p84 polymer . a dense film of a copolymer of toluenediisocyanate ( tdi , a mixture of 20 % 2 , 6 - toluenediisocyanate and 80 % 2 , 4 - toluenediisocyanate ) and a 1 : 1 mixture of benzophenone - 3 , 3 ′, 4 , 4 ′- tetracarboxylic acid dianhydride ( btda ) with 3 , 3 ′, 4 , 4 ′- biphenyl tetracarboxylic dianhydride ( bpda ) was tested in permeation with 50 : 50 mole % mixed propylene / propane feed at 2 . 8 mpa ( 400 psig ) and 90 ° c . as in example 9 . the propylene permeability of the film was 0 . 48 barrers and the propylene / propane permselectivity was over 16 . samples of composite hollow - fiber membrane of matrimid ® 5218 a copolymer of 5 , x - amino -( 4 - aminophenyl )- 1 , 1 , 3 trimethyl indane and 3 , 3 ′, 4 , 4 ′- benzophenone tetracarboxylicdianhydride ( vantico , inc .) were tested in permeation over a 72 - hour period with a feed mixture of 50 : 50 mole % propylene / propane at 1 . 7 mpa ( 250 psig ) and 90 ° c . as in example 1 . the purpose of the test was to determine the membrane performance stability under simulated commercial conditions . this membrane , described in u . s . pat . no . 5 , 468 , 430 is a commercial gas - separation membrane produced by medal , lp . results of the test are shown in table iv . as apparent from these results , the membrane exhibited low selectivity and lost greater than 50 % of its initial permeance during the test , unlike the membranes of this invention . samples of asymmetric hollow - fiber membrane made from a blend of two aromatic polyamides were tested in permeation of a feed mixture of 50 : 50 mole % propylene / propane at 2 . 8 mpa ( 400 psig ) and 90 ° c . as in example 1 . this membrane is described in u . s . pat . no . 5 , 085 , 774 ( example 15 ). the fiber was spun at a draw ratio of 7 . 3 . it is an established gas - separation membrane applied in the separation of hydrogen from mixtures with hydrocarbons or carbon monoxide . it exhibited a propylene permeance of 0 . 23 gpu and a propylene / propane selectivity of 9 . 5 . this performance was less than that of the novel membranes having composition of formula ( i ). this result was unexpected because the membrane of aromatic polyamide has very high selectivity in separations of other mixtures , for example a selectivity of higher than 200 for h 2 / ch 4 at 90 ° c . although specific forms of the invention have been selected for illustration in the preceding description which is drawn in specific terms for the purpose of describing these forms of the invention fully and amply for one of average skill in the pertinent art , it should be understood that various substitutions and modifications which bring about substantially equivalent or superior results and / or performance are deemed to be within the scope and spirit of the following claims . | 2 |
hereinafter , the present invention is described in more detail with reference to reference examples , examples and pharmacological test examples . an acetone solution ( 60 ml ) of 3 - amino - 2 - naphthol ( 5 . 0 g , 31 . 4 mmol ) was added to an aqueous solution ( 20 ml ) of sodium carbonate ( 4 . 77 g , 34 . 5 mmol ). the mixture was cooled in an ice - water bath , and then acetyl chloride ( 2 . 27 ml , 32 . 0 mmol ) was added to the mixture dropwise over 5 minutes . the resulting mixture was stirred at 0 ° c . for 4 hours and then allowed to stand at room temperature overnight . 2n hydrochloric acid was added to the reaction mixture to adjust its ph to 3 . the generated insoluble matter was separated , washed with water , and then dried , giving a white powder of n -( 3 - hydroxynaphthalen - 2 - yl ) acetamide ( 4 . 9 g , yield : 78 %). n -( 3 - hydroxynaphthalen - 2 - yl ) acetamide ( 4 . 87 g , 24 . 2 mmol ) was suspended in acetonitrile ( 50 ml ). a 1 - iodopropane ( 4 . 52 g , 26 . 6 mmol ) acetonitrile solution ( 40 ml ) and potassium carbonate ( 4 . 35 g , 31 . 5 mmol ) were added thereto , and the resulting mixture was stirred for 3 hours while heating under reflux . the mixture was then cooled to room temperature and concentrated to dryness under reduced pressure . water was added to the residue , followed by extraction using dichloromethane . the thus - obtained organic layer was concentrated to dryness under reduced pressure , and the residue was then purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 20 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a white powder of n -( 3 - propoxynaphthalen - 2 - yl ) acetamide ( 5 . 64 g , yield : 96 %). n -( 3 - propoxynaphthalen - 2 - yl ) acetamide ( 2 . 5 g , 10 . 2 mmol ) was dissolved in ethanol ( 10 ml ). concentrated hydrochloric acid ( 5 . 2 ml ) was added thereto , and the resulting mixture was stirred for 4 hours while heating under reflux . the reaction mixture was cooled to room temperature , and a 5n aqueous sodium hydroxide solution ( 12 . 5 ml ) was added thereto to adjust its ph to 11 , followed by extraction using dichloromethane . the thus - obtained organic layer was concentrated to dryness under reduced pressure , and the residue was then purified using silica gel column chromatography ( dichloromethane ). the purified product was concentrated to dryness under reduced pressure , giving a white powder of 3 - propoxynaphthalen - 2 - ylamine ( 2 . 05 g , yield : 100 %). meldrum &# 39 ; s acid ( 2 . 59 g , 17 . 9 mmol ) was added to methyl orthoformate ( 16 ml ), and the mixture was stirred for 2 hours while heating under reflux . 3 - propoxynaphthalen - 2 - ylamine ( 2 . 5 g , 12 . 4 mmol ) was added thereto , and the resulting mixture was stirred for 4 hours while heating under reflux . the reaction mixture was cooled to room temperature and then concentrated to dryness under reduced pressure to recrystallize the residue from methanol , giving a pale brown powder of 2 , 2 - dimethyl - 5 -[( 3 - propoxynaphthalen - 2 - ylamino ) methylene ][ 1 , 3 ] dioxane - 4 , 6 - dione ( 4 . 19 g , yield : 95 %). 2 , 2 - dimethyl - 5 -[( 3 - propoxynaphthalen - 2 - ylamino ) methylene ][ 1 , 3 ] dioxane - 4 , 6 - dione ( 4 . 19 g , 11 . 7 mmol ) was added to diphenyl ether ( 15 ml ), and the mixture was heated with a mantle heater and then maintained under reflux for 2 hours . the mixture was cooled to room temperature and purified using silica gel column chromatography ( dichloromethane : methanol = 70 : 1 → 9 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a dark brown powder of 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 3 . 15 g , yield : 61 %). 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 2 . 66 g , 10 . 5 mmol ) was suspended in dmf ( 20 ml ). potassium carbonate ( 1 . 63 g , 11 . 8 mmol ) and iodine ( 2 . 95 g , 11 . 6 mmol ) were added to the suspension , followed by stirring at room temperature for 3 hours . the reaction mixture was poured into an aqueous sodium thiosulfate solution ( 9 . 14 g , 100 ml ), followed by stirring for 5 minutes . ethyl acetate was added to the reaction mixture and stirred . subsequently , insoluble matter was collected by filtration , and the filtrate was then separated . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution , and then concentrated to dryness under reduced pressure . the residue was added to the collected insoluble matter , followed by purification using silica gel column chromatography ( dichloromethane : methanol = 50 : 1 → 20 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a pale brown powder of 2 - iodo - 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 3 . 48 g , yield : 87 %). 1 -( 3 - propoxy - 5 , 6 , 7 , 8 - tetrahydronaphthalen - 2 - yl ) ethanone ( 8 . 88 g , 38 . 2 mmol ) was dissolved in a mixed solvent of chloroform ( 20 ml ) and methanol ( 80 ml ). hydroxylamine hydrochloride ( 4 . 05 g , 58 . 2 mmol ) and pyridine ( 9 . 46 ml , 117 mmol ) were added to the solution and stirred for 16 hours while heating under reflux . the reaction mixture was cooled to room temperature , and then concentrated to dryness under reduced pressure . 2n hydrochloric acid ( 30 ml ) and water were added to the residue , followed by extraction using dichloromethane . the thus - obtained organic layer was concentrated to dryness under reduced pressure , and the residue was then purified using silica gel column chromatography ( n - hexane : ethyl acetate = 5 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a pale yellow powder of 1 -( 3 - propoxy - 5 , 6 , 7 , 8 - tetrahydronaphthalen - 2 - yl ) ethanone oxime ( 8 . 87 g , yield : 94 %). indium chloride ( 1 . 19 g , 5 . 39 mmol ) was added to an acetonitrile solution ( 150 ml ) of 1 -( 3 - propoxy - 5 , 6 , 7 , 8 - tetrahydronaphthalen - 2 - yl ) ethanone oxime ( 8 . 87 g , 35 . 8 mmol ) and the mixture was stirred for 3 hours while heating under reflux . the reaction mixture was cooled to room temperature , and then concentrated to dryness under reduced pressure . water was added to the residue , followed by extraction using dichloromethane . the thus - obtained organic layer was concentrated to dryness under reduced pressure , and the residue was then purified using silica gel column chromatography ( n - hexane : ethyl acetate = 3 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a white powder of n -( 3 - propoxy - 5 , 6 , 7 , 8 - tetrahydronaphthalen - 2 - yl ) acetamide ( 8 . 65 g , yield : 98 %). 3 - propoxy - 5 , 6 , 7 , 8 - tetrahydronaphthalen - 2 - ylamine was produced in the same manner as in reference example 3 . 5 - bromo - 6 - propoxyindan was produced in the same manner as in reference example 2 . to a 5 - bromo - 6 - propoxyindan ( 8 . 24 g , 32 . 2 mmol ) toluene solution ( 80 ml ) were added a benzophenone imine ( 6 . 40 g , 35 . 3 mmol ) toluene solution ( 40 ml ), tris ( dibenzylideneacetone ) dipalladium ( 742 mg , 0 . 8 mmol ), 9 , 9 - dimethyl - 4 , 5 - bis ( diphenylphosphino ) xanthene ( xantphos , 936 mg , 1 . 6 mmol ), and cesium carbonate ( 15 . 72 g , 48 . 3 mmol ). the resulting mixture was stirred at 100 ° c . under a nitrogen atmosphere for 47 hours , and then cooled to room temperature . water and saturated ammonium chloride solution were added to the reaction mixture , followed by extraction using ethyl acetate . the organic layer was dried over anhydrous magnesium sulfate , and then concentrated to dryness under reduced pressure . the generated residue was dissolved in diethyl ether ( 130 ml ). concentrated hydrochloric acid ( 25 ml ) was added to the solution , followed by stirring for 2 hours . a 5n aqueous sodium hydroxide solution ( 72 ml ) was added to the reaction mixture to adjust its ph to 11 , followed by concentration under reduced pressure . the residue was dissolved in dichloromethane and washed with an aqueous saturated sodium chloride solution . the thus - obtained organic layer was concentrated to dryness under reduced pressure , and the generated residue was then purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 90 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a pale brown oily substance of 6 - propoxy - indan - 5 - ylamine ( 1 . 02 g , yield : 17 %). 1 -( 7 - hydroxychroman - 6 - yl ) ethanone ( 3 . 0 g , 15 . 6 mmol ) was dissolved in dmf ( 20 ml ). sodium hydride ( 60 % oil base , 686 mg , 1 . 1 equivalent weight ) was added thereto while ice cooling , and then stirred for 10 minutes . 1 - iodopropane ( 2 . 92 g , 1 . 1 equivalent weight ) was added to the mixture and then stirred at room temperature for 3 hours . water was added to the reaction mixture , followed by extraction using ethyl acetate . the thus - obtained organic layer was concentrated to dryness under reduced pressure , and the residue was then purified using silica gel column chromatography ( n - hexane : ethyl acetate = 1 : 0 → 0 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a white powder of 1 -( 7 - propoxychroman - 6 - yl ) ethanone ( 4 . 2 g , yield : quantitative ). 1 -( 7 - propoxychroman - 6 - yl ) ethanone oxime was produced in the same manner as in reference example 7 . n -( 7 - propoxychroman - 6 - yl ) acetamide was produced in the same manner as in reference example 8 . 7 - propoxychroman - 6 - ylamine was produced in the same manner as in reference example 3 . 1 -( 6 - propoxychroman - 7 - yl ) ethanone oxime was produced in the same manner as in reference example 7 . n -( 6 - propoxychroman - 7 - yl ) acetamide was produced in the same manner as in reference example 8 . 6 - propoxychroman - 7 - ylamine was produced in the same manner as in reference example 3 . 1 -( 5 - propoxy - 2 , 3 - dihydrobenzofuran - 6 - yl ) ethanone was produced in the same manner as in reference example 12 . 1 -( 5 - propoxy - 2 , 3 - dihydrobenzofuran - 6 - yl ) ethanone oxime was produced in the same manner as in reference example 7 . n -( 5 - propoxy - 2 , 3 - dihydrobenzofuran - 6 - yl ) acetamide was produced in the same manner as in reference example 8 . 5 - propoxy - 2 , 3 - dihydrobenzofuran - 6 - ylamine was produced in the same manner as in reference example 3 . to a 7 - bromo - 5 - methylbenzofuran ( 9 . 71 g , 46 mmol ) toluene solution ( 100 ml ) were added a benzophenone imine ( 10 . 25 g , 56 mmol ) toluene solution ( 55 ml ), tris ( dibenzylideneacetone ) dipalladium ( 1 . 1 g , 1 mmol ), 2 , 2 ′- bis ( diphenylphosphino )- 1 , 1 ′- binaphthyl ( binap , 2 . 1 g , 3 . 45 mmol ), and sodium t - butoxide ( 3 . 1 g , 31 mmol ). the resulting mixture was then stirred for 4 hours while heating under reflux in a nitrogen atmosphere . the reaction mixture was cooled to room temperature , and water and saturated ammonium chloride solution were added thereto , followed by extraction using ethyl acetate . the organic layer was dried over anhydrous magnesium sulfate and then concentrated to dryness under reduced pressure . the residue was purified using silica gel column chromatography ( n - hexane : ethyl acetate = 10 : 1 ). the solvent was removed under a reduced pressure , giving a yellow oily substance of benzhydrylidene ( 5 - methylbenzofuran - 7 - yl ) amine ( 17 . 9 g , yield : 81 %). benzhydrylidene ( 5 - methylbenzofuran - 7 - yl ) amine ( 17 . 9 g , 0 . 57 mmol ) was dissolved in thf ( 150 ml ). 5n hydrochloric acid ( 50 ml ) was added thereto , followed by stirring at room temperature for 2 hours . a 5n aqueous sodium hydroxide solution ( 40 ml ) was added to the reaction mixture , followed by extraction using ethyl acetate . the extract was sequentially washed with an aqueous saturated sodium hydrogen solution and an aqueous saturated sodium chloride solution . the organic layer was dried over magnesium sulfate and concentrated to dryness under reduced pressure . the residue was purified using silica gel column chromatography ( n - hexane : ethyl acetate = 50 : 1 → 10 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a dark brown oily substance of 5 - methylbenzofuran - 7 - ylamine ( 2 . 5 g , yield : 30 %). 5 - methylbenzofuran - 7 - ylamine ( 1 . 3 g , 8 . 8 mmol ) and 10 % palladium carbon ( 500 mg ) were added to ethanol ( 50 ml ), followed by conduction of catalytic reduction at room temperature under ordinary pressure . the catalyst was removed by celite filtration , and the obtained filtrate was condensed under reduced pressure . the residue was dissolved in dichloromethane , dried over anhydrous magnesium sulfate , and then concentrated to dryness under reduced pressure , giving a white powder of 5 - methyl - 2 , 3 - dihydrobenzofuran - 7 - ylamine ( 1 . 15 g , yield : 87 %). to a benzene solution ( 50 ml ) containing 3 - propoxynaphthalen - 2 - ylamine ( 2 . 05 g , 10 . 18 mmol ) and ethyl α -( hydroxymethylene )- 4 - methoxyphenylacetate ( 2 . 29 g , 10 . 3 mmol ) was added 350 mg of amberlyst 15 ( sigma - aldrich ). the resulting mixture was heated under reflux for 21 hours using a dean - stark trap . the reaction mixture was then cooled to room temperature , filtered to remove resin , and then the filtrate was concentrated under reduced pressure . diphenyl ether ( 2 . 2 ml ) was added to the residue , and the mixture was then heated with a mantle heater and stirred for 1 . 5 hours under reflux . the resulting reaction mixture was cooled to room temperature , and then directly purified using silica gel column chromatography ( dichloromethane : methanol = 100 : 1 → 60 : 1 ). the purified product was concentrated under reduced pressure to recrystallize the residue from ethyl acetate - n - hexane , giving a pale yellow powder of 2 -( 4 - methoxyphenyl )- 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 1 . 55 g , yield : 42 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 08 ( 3h , t , j = 7 . 3 hz ), 1 . 87 - 1 . 95 ( 2h , m ), 3 . 77 ( 3h , s ), 4 . 22 ( 2h , t , j = 6 . 5 hz ), 6 . 97 ( 2h , d , j = 8 . 8 hz ), 7 . 47 - 7 . 52 ( 3h , m ), 7 . 64 ( 2h , d , j = 8 . 8 hz ), 7 . 83 - 7 . 87 ( 1h , m ), 7 . 92 ( 1h , s ), 10 . 24 - 10 . 28 ( 1h , m ), 11 . 60 ( 1h , brs ). 3 - iodo - 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 1 . 06 g , 2 . 79 mmol ) was suspended in dimethoxyethane ( 20 ml ). furan - 3 - boron acid ( 354 mg , 3 . 16 mmol ), [ 1 , 1 ′- bis ( diphenylphosphino ) ferrocene ] dichloropalladium ( ii )- dichloromethane complex ( pdcl 2 ( dppf ). ch 2 cl 2 , 123 mg , 0 . 11 mmol ) and a 2n aqueous sodium carbonate solution ( 4 . 0 ml ) were sequentially added to the suspension . the mixture was stirred at 90 to 100 ° c . under a nitrogen atmosphere for hours . the reaction mixture was cooled to room temperature , water was added thereto , and the resulting mixture was subjected to extraction using dichloromethane . the thus - obtained organic layer was concentrated under reduced pressure , and the residue was purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 80 : 1 ). the purified product was concentrated under reduced pressure , the residue was washed with ethyl acetate and then dried , giving a pale brown powder of 2 - furan - 3 - yl - 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 430 mg , yield : 48 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 87 - 1 . 98 ( 2h , m ), 4 . 27 ( 2h , t , j = 6 . 5 hz ), 7 . 03 ( 1h , s ), 7 . 48 - 7 . 55 ( 2h , m ), 7 . 57 ( 1h , s ), 7 . 72 ( 1h , s ), 7 . 84 - 7 . 89 ( 1h , m ), 8 . 22 ( 1h , s ), 8 . 71 ( 1h , s ), 10 . 24 - 10 . 30 ( 1h , m ), 11 . 80 ( 1h , brs ). to a dmf solution ( 5 ml ) of 2 - furan - 3 - yl - 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 300 mg , 0 . 94 mmol ) was added sodium hydride ( 60 % oil base , 61 mg , 1 . 4 mmol ), and then the mixture was stirred at room temperature for 5 minutes . methyl iodide ( 181 mg , 1 . 27 mmol ) was added thereto and the resulting mixture was stirred at room temperature for 62 hours . water and ethyl acetate were added to the reaction mixture and the resulting mixture was subjected to separation . the thus - obtained organic layer was washed with water , dried over anhydrous sodium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 90 : 1 → 80 : 1 ). the purified product was concentrated under reduced pressure to recrystallize the residue from ethyl acetate - n - hexane , giving a pale gray powder of 2 - furan - 3 - yl - 4 - methyl - 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 130 mg , yield : 42 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 83 - 1 . 92 ( 2h , m ), 4 . 12 ( 2h , t , j = 6 . 4 hz ), 4 . 21 ( 3h , s ), 7 . 07 ( 1h , s ), 7 . 45 - 7 . 51 ( 2h , m ), 7 . 54 ( 1h , s ), 7 . 70 ( 1h , s ), 7 . 79 - 7 . 83 ( 1h , m ), 8 . 36 ( 1h , s ), 8 . 69 ( 1h , s ), 10 . 34 - 10 . 38 ( 1h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 87 - 2 . 01 ( 2h , m ), 4 . 27 ( 2h , t , j = 6 . 5 hz ), 7 . 12 ( 1h , dd , j = 3 . 9 hz , 5 . 1 hz ), 7 . 47 ( 1h , d , j = 4 . 7 hz ), 7 . 52 - 7 . 57 ( 2h , m ), 7 . 59 ( 1h , s ), 7 . 66 ( 1h , d , j = 3 . 7 hz ), 7 . 87 - 7 . 91 ( 1h , m ), 8 . 50 ( 1h , s ), 10 . 20 - 10 . 27 ( 1h , m ), 11 . 95 ( 1h , brs ). the above compound was prepared in the same manner as in example 3 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 84 - 1 . 92 ( 2h , m ), 4 . 12 ( 2h , t , j = 6 . 4 hz ), 4 . 23 ( 3h , s ), 7 . 09 - 7 . 13 ( 1h , m ), 7 . 46 - 7 . 55 ( 4h , m ), 7 . 66 ( 1h , d , j = 3 . 7 hz ), 7 . 80 - 7 . 84 ( 1h , m ), 8 . 63 ( 1h , s ), 10 . 32 - 10 . 36 ( 1h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 3 hz ), 1 . 90 - 1 . 98 ( 2h , m ), 4 . 27 ( 2h , t , j = 6 . 5 hz ), 7 . 49 - 7 . 58 ( 4h , m ), 7 . 63 - 7 . 66 ( 1h , m ), 7 . 85 - 8 . 00 ( 1h , m ), 8 . 24 ( 1h , s ), 8 . 34 - 8 . 36 ( 1h , m ), 10 . 23 - 10 . 29 ( 1h , m ), 11 . 71 ( 1h , brs ). the above compound was prepared in the same manner as in example 3 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 84 - 1 . 92 ( 2h , m ), 4 . 12 ( 2h , t , j = 6 . 4 hz ), 4 . 19 ( 3h , s ), 7 . 44 - 7 . 57 ( 4h , m ), 7 . 70 ( 1h , d , j = 5 . 1 hz ), 7 . 80 - 7 . 84 ( 1h , m ), 8 . 38 - 8 . 40 ( 2h , brs ), 10 . 30 - 10 . 34 ( 1h , m ). to a benzene solution ( 38 ml ) containing 3 - propoxynaphthalen - 2 - ylamine ( 600 mg , 2 . 98 mmol ) and ethyl α - acetyl - 4 - methoxyphenylacetate ( 1 . 41 g , 5 . 96 mmol ) was added 85 mg of amberlyst 15 ( sigma - aldrich ). the resulting mixture was heated under reflux for 20 hours using a dean - stark trap . the reaction mixture was cooled to room temperature , filtered to remove resin , and then the filtrate was concentrated under reduced pressure . diphenyl ether ( 2 . 8 ml ) was added to the residue , and the mixture was then heated with a mantle heater and stirred for 70 minutes under reflux . the resulting reaction mixture was cooled to room temperature , and then directly purified using silica gel column chromatography ( dichloromethane : methanol = 80 : 1 → 70 : 1 ). the purified product was concentrated under reduced pressure , giving an oily substance ( 800 mg , yield : 72 %). ethyl acetate and n - hexane were added to the thus - obtained oily substance to crystallize and then recrystallized from ethyl acetate , giving a pale yellow powder of 2 -( 4 - methoxyphenyl )- 3 - methyl - 5 - propoxy - 4h - benzo [ f ] quinolin - 1 - one ( 290 mg ). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 90 - 1 . 98 ( 2h , m ), 2 . 31 ( 3h , s ), 3 . 77 ( 3h , s ), 4 . 27 ( 2h , t , j = 6 . 8 hz ), 6 . 95 ( 2h , d , j = 8 . 6 hz ), 7 . 17 ( 2h , d , j = 8 . 6 hz ), 7 . 39 - 7 . 50 ( 2h , m ), 7 . 56 ( 1h , s ), 7 . 84 ( 1h , dd , j = 2 . 2 hz , 6 . 5 hz ), 10 . 09 - 10 . 13 ( 1h , m ), 10 . 79 ( 1h , brs ). the above compound was prepared in the same manner as in example 8 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 3 hz ), 1 . 88 - 1 . 97 ( 2h , m ), 2 . 40 ( 3h , s ), 4 . 26 ( 2h , t , j = 6 . 7 hz ), 7 . 14 ( 1h , d , j = 4 . 9 hz ), 7 . 41 - 7 . 54 ( 5h , m ), 7 . 83 ( 1h , d , j = 6 . 6 hz ), 10 . 07 - 10 . 11 ( 1h , m ), 10 . 84 ( 1h , brs ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 77 - 1 . 88 ( 2h , m ), 1 . 97 - 2 . 08 ( 2h , m ), 2 . 86 ( 2h , t , j = 7 . 5 hz ), 3 . 45 ( 2h , t , j = 7 . 0 hz ), 4 . 10 ( 2h , t , j = 6 . 5 hz ), 7 . 05 ( 1h , t , j = 3 . 8 hz ), 7 . 13 ( 1h , s ), 7 . 36 ( 1h , d , j = 5 . 1 hz ), 7 . 53 ( 1h , d , j = 3 . 6 hz ), 8 . 31 ( 1h , s ), 11 . 39 ( 1h , brs ). the above compound was prepared in the same manner as in example 3 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 4 hz ), 1 . 77 - 1 . 85 ( 2h , m ), 1 . 97 - 2 . 03 ( 2h , m ), 2 . 84 ( 2h , t , j = 7 . 6 hz ), 3 . 49 ( 2h , t , j = 7 . 1 hz ), 4 . 00 ( 2h , t , j = 6 . 4 hz ), 4 . 13 ( 3h , s ), 7 . 05 ( 1h , t , j = 3 . 8 hz ), 7 . 18 ( 1h , s ), 7 . 35 ( 1h , d , j = 4 . 7 hz ), 7 . 54 ( 1h , d , j = 3 . 3 hz ), 8 . 48 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 76 - 1 . 87 ( 2h , m ), 1 . 95 - 2 . 07 ( 2h , m ), 2 . 85 ( 2h , t , j = 7 . 5 hz ), 3 . 30 - 3 . 55 ( 2h , m ), 4 . 09 ( 2h , t , j = 6 . 5 hz ), 7 . 11 ( 1h , s ), 7 . 48 - 7 . 56 ( 2h , m ), 8 . 11 ( 1h , d , j = 6 . 2 hz ), 8 . 21 - 8 . 23 ( 1h , m ), 11 . 18 ( 1h , d , j = 5 . 8 hz ). the above compound was prepared in the same manner as in example 3 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 4 hz ), 1 . 76 - 1 . 85 ( 2h , m ), 1 . 95 - 2 . 01 ( 2h , m ), 2 . 83 ( 2h , t , j = 7 . 6 hz ), 3 . 49 ( 2h , t , j = 7 . 4 hz ), 3 . 99 ( 2h , t , j = 6 . 5 hz ), 4 . 09 ( 3h , s ), 7 . 15 ( 1h , s ), 7 . 48 - 7 . 52 ( 1h , m ), 7 . 63 - 7 . 65 ( 1h , m ), 8 . 26 - 8 . 28 ( 2h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 1 . 86 ( 2h , m ), 1 . 96 - 2 . 02 ( 2h , m ), 2 . 83 ( 2h , t , j = 7 . 5 hz ), 3 . 40 ( 2h , t , j = 7 . 3 hz ), 3 . 74 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 4 hz ), 6 . 91 ( 2h , d , j = 8 . 8 hz ), 7 . 09 ( 1h , s ), 7 . 55 ( 2h , d , j = 8 . 8 hz ), 7 . 78 ( 1h , d , j = 5 . 9 hz ), 11 . 06 ( 1h , d , j = 5 . 8 hz ). the above compound was prepared in the same manner as in example 8 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 4 hz ), 1 . 79 - 1 . 87 ( 2h , m ), 1 . 93 - 1 . 99 ( 2h , m ), 2 . 21 ( 3h , s ), 2 . 82 ( 2h , t , j = 7 . 4 hz ), 3 . 31 ( 2h , t , j = 7 . 1 hz ), 3 . 75 ( 3h , s ), 4 . 10 ( 2h , t , j = 6 . 7 hz ), 6 . 90 ( 2h , d , j = 8 . 7 hz ), 7 . 08 ( 2h , d , j = 8 . 5 hz ), 7 . 10 ( 1h , s ), 10 . 30 ( 1h , brs ). the above compound was prepared in the same manner as in example 8 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 79 - 1 . 87 ( 2h , m ), 1 . 90 - 1 . 99 ( 2h , m ), 2 . 31 ( 3h , s ), 2 . 82 ( 2h , t , j = 7 . 5 hz ), 3 . 32 ( 2h , t , j = 7 . 3 hz ), 4 . 09 ( 2h , t , j = 6 . 7 hz ), 7 . 04 - 7 . 10 ( 2h , m ), 7 . 31 - 7 . 32 ( 1h , m ), 7 . 44 - 7 . 47 ( 1h , m ), 10 . 35 ( 1h , brs ). to a dmf solution ( 6 ml ) of 8 -( 4 - methoxyphenyl )- 5 - propoxy - 1 , 2 , 3 , 6 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 9 - one ( 1 . 26 g , 3 . 60 mmol ) was added sodium hydride ( 60 % oil base , 189 mg , 4 . 33 mmol ). the mixture was stirred at room temperature for 10 minutes . to the resulting mixture was added 1 - bromo - 3 - chloropropane ( 1 . 70 g , 10 . 8 mmol ), followed by stirring at room temperature for 16 hours . water and ethyl acetate were added to the reaction mixture and the resulting reaction mixture was then subjected to separation . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution twice . after being dried over anhydrous sodium sulfate , the organic layer was concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 20 : 1 → 12 : 1 ). the purified product was concentrated under reduced pressure , giving a yellow oily substance of 6 -( 3 - chloropropyl )- 8 -( 4 - methoxyphenyl )- 5 - propoxy - 1 , 2 , 3 , 6 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 9 - one ( 365 mg , yield : 92 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , m ), 1 . 90 - 2 . 24 ( 6h , m ), 2 . 91 ( 2h , t , j = 7 . 6 hz ), 3 . 45 ( 2h , t , j = 5 . 7 hz ), 3 . 67 ( 2h , t , j = 7 . 5 hz ), 3 . 83 ( 3h , s ), 4 . 04 ( 2h , t , j = 6 . 7 hz ), 4 . 71 ( 2h , t , j = 6 . 4 hz ), 6 . 92 - 7 . 04 ( 3h , m ), 7 . 58 - 7 . 62 ( 3h , m ). a mixture containing 6 -( 3 - chloropropyl )- 8 -( 4 - methoxyphenyl )- 5 - propoxy - 1 , 2 , 3 , 6 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 9 - one ( 700 mg , 1 . 64 mmol ), morpholine ( 165 mg , 1 . 90 mmol ), potassium carbonate ( 341 mg , 2 . 47 mmol ), sodium iodide ( 295 mg , 1 . 97 mmol ) and dimethyl formamide ( 3 ml ) was stirred at 60 ° c . for 7 hours . water and ethyl acetate were added to the reaction mixture , followed by separation . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution twice and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 70 : 1 → 50 : 1 ). the purified product was concentrated under reduced pressure to recrystallize the residue from ethyl acetate - n - hexane , giving a white powder of 8 -( 4 - methoxyphenyl )- 6 -( 3 - morpholin - 4 - ylpropyl )- 5 - propoxy - 1 , 2 , 3 , 6 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 9 - one ( 295 mg , yield : 38 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 75 - 1 . 85 ( 4h , m ), 1 . 96 ( 2h , t , j = 7 . 5 hz ), 2 . 04 - 2 . 15 ( 6h , m ), 2 . 83 ( 2h , t , j = 7 . 5 hz ), 3 . 38 - 3 . 41 ( 6h , m ), 3 . 74 ( 3h , s ), 4 . 02 ( 2h , t , j = 6 . 5 hz ), 4 . 55 ( 2h , t , j = 6 . 2 hz ), 6 . 90 ( 2h , d , j = 8 . 7 hz ), 7 . 18 ( 1h , s ), 7 . 60 ( 2h , d , j = 8 . 7 hz ), 7 . 93 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 20 - 1 . 50 ( 6h , m ), 1 . 74 - 1 . 86 ( 4h , m ), 1 . 96 ( 2h , t , j = 7 . 4 hz ), 2 . 02 - 2 . 20 ( 6h , m ), 2 . 83 ( 2h , t , j = 7 . 3 hz ), 3 . 30 - 3 . 40 ( 2h , m ), 3 . 74 ( 3h , s ), 4 . 02 ( 2h , t , j = 6 . 4 hz ), 4 . 53 ( 2h , t , j = 5 . 8 hz ), 6 . 90 ( 2h , d , j = 8 . 7 hz ), 7 . 18 ( 1h , s ), 7 . 60 ( 2h , d , j = 8 . 7 hz ), 7 . 91 ( 1h , s ). the above compound was prepared in the same manner as in example 17 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , m ), 1 . 88 - 2 . 25 ( 6h , m ), 2 . 91 ( 2h , t , j = 7 . 6 hz ), 3 . 45 ( 2h , t , j = 5 . 8 hz ), 3 . 69 ( 2h , t , j = 7 . 5 hz ), 4 . 01 - 4 . 04 ( 2h , m ), 4 . 74 ( 2h , t , j = 6 . 4 hz ), 7 . 05 ( 1h , s ), 7 . 32 - 7 . 35 ( 1h , m ), 7 . 43 - 7 . 47 ( 1h , m ), 7 . 83 ( 1h , s ), 8 . 08 - 8 . 10 ( 1h , m ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 76 - 1 . 86 ( 4h , m ), 1 . 98 ( 2h , t , j = 7 . 5 hz ), 2 . 03 - 2 . 20 ( 6h , m ), 2 . 84 ( 2h , t , j = 7 . 5 hz ), 3 . 41 - 3 . 52 ( 6h , m ), 4 . 02 ( 2h , t , j = 6 . 5 hz ), 4 . 60 ( 2h , t , j = 6 . 3 hz ), 7 . 18 ( 1h , s ), 7 . 49 - 7 . 52 ( 1h , m ), 7 . 62 - 7 . 64 ( 1h , m ), 8 . 25 - 8 . 27 ( 1h , m ), 8 . 30 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 60 - 1 . 64 ( 2h , m ), 1 . 74 - 1 . 86 ( 4h , m ), 1 . 98 ( 2h , t , j = 7 . 4 hz ), 2 . 19 ( 2h , t , j = 6 . 3 hz ), 2 . 40 - 2 . 45 ( 4h , m ), 2 . 84 ( 2h , t , j = 7 . 4 hz ), 3 . 51 - 3 . 59 ( 6h , m ), 4 . 03 ( 2h , t , j = 6 . 4 hz ), 4 . 60 ( 2h , t , j = 6 . 0 hz ), 7 . 19 ( 1h , s ), 7 . 48 - 7 . 51 ( 1h , m ), 7 . 61 ( 1h , d , j = 4 . 9 hz ), 8 . 23 ( 1h , d , j = 1 . 8 hz ), 8 . 27 ( 1h , s ). to a dmf solution ( 10 ml ) of 8 -( 4 - methoxyphenyl )- 5 - propoxy - 1 , 2 , 3 , 6 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 9 - one ( 400 mg , 1 . 15 mmol ) and sodium iodide ( 343 mg , 2 . 29 mmol ) was added sodium hydride ( 60 % oil base , 74 . 9 mg , 1 . 72 mmol ), and the mixture was then stirred for 10 minutes at room temperature . to the resulting mixture was added a dmf solution ( 20 ml ) of di - tert - butyl chloromethyl phosphate ( 888 mg , 3 . 43 mmol ), and the mixture was then stirred at 40 ° c . for 4 hours . the reaction mixture was ice - cooled , ice water was added thereto , and then the reaction mixture was subjected to extraction using ethyl acetate . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution twice , dried over anhydrous sodium sulfate and then concentrated under reduced pressure . the residue was purified using medium pressure liquid chromatography ( nh silica gel , n - hexane : ethyl acetate = 100 : 0 → 0 : 100 ). the purified product was concentrated under reduced pressure , giving a white powder of di - tert - butyl 8 -( 4 - methoxyphenyl )- 9 - oxo - 5 - propoxy - 1 , 2 , 3 , 9 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 6 - ylmethyl phosphate ( 263 mg , yield : 40 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 08 - 1 . 14 ( 3h , t , j = 7 . 4 hz ), 1 . 35 ( 18h , s ), 1 . 88 - 2 . 16 ( 4h , m ), 2 . 88 - 2 . 95 ( 2h , t , j = 7 . 7 hz ), 3 . 60 - 3 . 66 ( 2h , t , j = 7 . 5 hz ), 3 . 82 ( 3h , s ), 4 . 05 - 4 . 10 ( 2h , t , j = 6 . 7 hz ), 6 . 30 - 6 . 35 ( 2h , d , j = 12 . 4 hz ), 6 . 90 - 6 . 97 ( 2h , d , j = 8 . 8 hz ), 7 . 09 ( 1h , s ), 7 . 57 - 7 . 63 ( 2h , d , j = 8 . 8 hz ), 7 . 76 ( 1h , s ). a dichloromethane solution ( 4 ml ) of di - tert - butyl 8 -( 4 - methoxyphenyl )- 9 - oxo - 5 - propoxy - 1 , 2 , 3 , 9 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 6 - ylmethyl ester ( 263 mg , 0 . 46 mmol ) was ice - cooled , trifluoroacetic acid ( 1 . 2 ml ) and dichloromethane ( 4 ml ) were added thereto under a nitrogen atmosphere and the resulting mixture was stirred at 0 ° c . for 1 hour . this mixture was concentrated under reduced pressure . the residue was subjected to vacuum drying , giving a pale yellow powder of [ 8 -( 4 - methoxyphenyl )- 9 - oxo - 5 - propoxy - 1 , 2 , 3 , 9 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 6 - ylmethyl ] monophosphate ( 147 mg , yield : 56 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 - 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 1 . 86 ( 2h , m ), 1 . 96 - 2 . 02 ( 2h , m ), 2 . 83 ( 2h , t , j = 7 . 5 hz ), 3 . 40 ( 2h , t , j = 7 . 3 hz ), 3 . 74 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 4 hz ), 6 . 25 - 6 . 30 ( 2h , d , j = 10 . 42 hz ), 6 . 92 - 6 . 95 ( 2h , m ), 7 . 13 ( 1h , s ), 7 . 59 - 7 . 63 ( 2h , d , j = 8 . 8 hz ), 7 . 76 - 7 . 79 ( 1h , d , j = 5 . 9 hz ). [ 8 -( 4 - methoxyphenyl )- 9 - oxo - 5 - propoxy - 1 , 2 , 3 , 9 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 6 - ylmethyl ] monophosphate ( 147 mg , 0 . 32 mmol ) was suspended in isopropyl alcohol ( 20 ml ), and 1n aqueous sodium hydroxide solution ( 0 . 64 ml , 0 . 64 mmol ) was then added thereto under a nitrogen atmosphere at 0 ° c . the resulting mixture was stirred for 1 hour at 0 ° c . the generated insoluble matter was separated and washed with acetone and dried , giving a white powder of [ 8 -( 4 - methoxyphenyl )- 9 - oxo - 5 - propoxy - 1 , 2 , 3 , 9 - tetrahydro - 6 - aza - cyclopenta [ a ] naphthalen - 6 - ylmethyl ] monophosphate disodium salt ( 42 mg , yield : 26 %) 1 h - nmr ( d 2 o ) δ ppm : 0 . 91 - 0 . 98 ( 3h , t , j = 7 . 8 hz ), 1 . 74 - 1 . 83 ( 2h , m ), 1 . 92 - 1 . 98 ( 2h , m ), 2 . 75 - 2 . 81 ( 2h , t , j = 7 . 6 hz ), 3 . 30 - 3 . 36 ( 2h , t , j = 7 . 2 hz ), 3 . 75 ( 3h , s ), 3 . 90 - 3 . 95 ( 2h , t , j = 6 . 7 hz ), 5 . 94 - 5 . 99 ( 2h , d , j = 9 . 5 hz ), 6 . 89 - 6 . 93 ( 2h , d , j = 8 . 8 hz ), 7 . 15 ( 1h , s ), 7 . 87 - 7 . 94 ( 2h , d , j = 8 . 8 hz ), 8 . 58 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 60 - 1 . 70 ( 4h , m ), 1 . 78 - 1 . 86 ( 2h , m ), 2 . 70 - 2 . 80 ( 2h , m ), 3 . 30 - 3 . 40 ( 2h , m ), 3 . 74 ( 3h , s ), 4 . 05 ( 2h , t , j = 6 . 4 hz ), 6 . 85 ( 1h , s ), 6 . 90 ( 2h , d , j = 8 . 7 hz ), 7 . 50 ( 2h , d , j = 8 . 7 hz ), 7 . 72 ( 1h , d , j = 5 . 1 hz ), 10 . 95 ( 1h , d , j = 4 . 7 hz ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 60 - 1 . 70 ( 4h , m ), 1 . 75 - 1 . 86 ( 2h , m ), 2 . 70 - 2 . 80 ( 2h , m ), 3 . 30 - 3 . 40 ( 2h , m ), 4 . 05 ( 2h , t , j = 6 . 4 hz ), 6 . 85 ( 1h , s ), 7 . 46 - 7 . 52 ( 2h , m ), 8 . 06 ( 1h , s ), 8 . 14 - 8 . 15 ( 1h , m ), 11 . 10 ( 1h , brs ). the above compound was prepared in the same manner as in example 8 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 98 ( 3h , t , j = 7 . 3 hz ), 1 . 60 - 1 . 70 ( 4h , m ), 1 . 78 - 1 . 87 ( 2h , m ), 2 . 17 ( 3h , s ), 2 . 70 - 2 . 80 ( 2h , m ), 3 . 20 - 3 . 30 ( 2h , m ), 3 . 74 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 7 hz ), 6 . 84 ( 1h , s ), 6 . 88 ( 2h , d , j = 8 . 7 hz ), 7 . 06 ( 2h , d , j = 8 . 5 hz ), 10 . 17 ( 1h , brs ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 06 ( 3h , t , j = 7 . 5 hz ), 1 . 74 - 1 . 95 ( 4h , m ), 2 . 72 - 2 . 75 ( 2h , t , j = 6 . 5 hz ), 3 . 75 ( 3h , s ), 4 . 00 - 4 . 10 ( 4h , m ), 6 . 87 - 6 . 93 ( 3h , m ), 7 . 46 - 7 . 52 ( 2h , d , j = 9 . 0 hz ), 7 . 65 ( 1h , s ), 10 . 70 - 10 . 90 ( 1h , brs ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 - 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 85 - 2 . 02 ( 4h , m ), 2 . 12 - 2 . 33 ( 2h , m ), 2 . 84 - 2 . 89 ( 2h , t , j = 6 . 3 hz ), 3 . 02 - 3 . 20 ( 2h , m ), 3 . 28 - 3 . 80 ( 15h , m ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 8 hz ), 4 . 28 - 4 . 31 ( 2h , t , j = 4 . 6 hz ), 4 . 75 - 4 . 95 ( 2h , m ), 7 . 00 - 7 . 03 ( 2h , d , j = 8 . 9 hz ), 7 . 30 ( 1h , s ), 7 . 63 - 7 . 66 ( 2h , d , j = 8 . 9 hz ), 8 . 48 ( 1h , s ). sodium hydride ( 60 % oil base , 80 mg , 2 . 0 mmol ) was added to a dmf solution ( 10 ml ) of 3 -( 4 - methoxyphenyl )- 10 - propoxy - 1 , 6 , 7 , 8 - tetrahydro - 5 - oxa - 1 - aza - phenanthren - 4 - one ( 600 mg , 1 . 64 mmol ), the resulting mixture was then stirred at room temperature for 5 minutes . ethyl bromoacetate ( 330 mg , 2 . 0 mmol ) was added thereto and the resulting mixture was stirred at room temperature for 16 hours . water and ethyl acetate were added to the reaction mixture , followed by separation . the thus - obtained organic layer was washed with water , dried over anhydrous sodium sulfate and then concentrated under reduced pressure . the residue was purified using medium pressure liquid chromatography ( nh silica gel , n - hexane : ethyl acetate = 100 : 0 → 0 : 100 ). the purified product was concentrated under reduced pressure , giving a colorless oily substance ethyl [ 3 -( 4 - methoxyphenyl )- 4 - oxo - 10 - propoxy - 7 , 8 - dihydro - 4h , 6h - 5 - oxa - 1 - aza - phenanthren - 1 - yl ] acetate ( 700 mg , yield : 95 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 00 - 1 . 10 ( 3h , t , j = 7 . 5 hz ), 1 . 25 - 1 . 28 ( 3h , t , j = 6 . 0 ), 1 . 75 - 1 . 90 ( 2h , m ), 2 . 02 - 2 . 43 ( 2h , m ), 2 . 80 - 2 . 90 ( 2h , m ), 3 . 85 ( 3h , s ), 3 . 86 - 3 . 88 ( 2h , m ), 4 . 10 - 4 . 13 ( 4h , m ), 5 . 10 ( 2h , s ), 6 . 75 ( 1h , s ), 6 . 85 - 6 . 90 ( 2h , d , j = 9 . 0 ), 7 . 24 ( 1h , s ), 7 . 60 - 7 . 75 ( 2h , d , j = 9 . 0 ). a 5n aqueous sodium hydroxide solution ( 10 ml ) was added to an ethanol solution ( 30 ml ) of ethyl [ 3 -( 4 - methoxyphenyl )- 4 - oxo - 10 - propoxy - 7 , 8 - dihydro - 4h , 6h - 5 - oxa - 1 - aza - phenanthren - 1 - yl ] acetate ( 700 mg , 1 . 55 mmol ) and heated for 2 hours under reflux . the mixture was cooled to room temperature and concentrated under reduced pressure . while ice - cooling the concentrate , water and concentrated hydrochloric acid were added to the residue to make it acidic . subsequently , the formed insoluble matter was separated and dried , giving a yellow powder of [ 3 -( 4 - methoxyphenyl )- 4 - oxo - 10 - propoxy - 7 , 8 - dihydro - 4h , 6h - 5 - oxa - 1 - aza - phenanthren - 1 - yl ] acetic acid ( 580 mg , yield : 88 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 - 1 . 00 ( 3h , t , j = 7 . 5 hz ), 1 . 74 - 1 . 82 ( 2h , m ), 1 . 94 - 1 . 98 ( 2h , m ), 2 . 78 - 2 . 83 ( 2h , t , j = 6 . 2 hz ), 3 . 77 ( 3h , s ), 3 . 92 - 3 . 98 ( 2h , t , j = 6 . 7 hz ), 4 . 21 - 4 . 25 ( 2h , t , j = 4 . 8 hz ), 5 . 35 ( 2h , s ), 6 . 96 - 7 . 00 ( 2h , d , j = 8 . 8 hz ), 7 . 16 ( 1h , s ), 7 . 56 - 7 . 59 ( 2h , d , j = 8 . 8 hz ), 8 . 29 ( 1h , s ). 4 -( 2 - aminoethyl ) morpholine ( 217 mg , 1 . 7 mmol ) was added to a dmf solution ( 10 ml ) of [ 3 -( 4 - methoxyphenyl )- 4 - oxo - 10 - propoxy - 7 , 8 - dihydro - 4h , 6h - 5 - oxa - 1 - aza - phenanthren - 1 - yl ] acetic acid ( 580 mg , 1 . 39 mmol ), 2 -( 7 - aza - 1h - benzotriazol - 1 - yl )- 1 , 1 , 3 , 3 - tetramethyl uronium hexafluorophosphate ( hatu , 790 mg , 2 . 1 mmol ) and triethylamine ( 5 ml ). the mixture was stirred overnight at room temperature and then concentrated under reduced pressure . water and ethyl acetate were added to the residue , followed by separation . the thus - obtained organic layer was washed with water and concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 10 : 1 ). the purified product was concentrated under reduced pressure , and the residue was recrystallized from ethyl acetate , giving a pale brown powder of 2 -[ 3 -( 4 - methoxyphenyl )- 4 - oxo - 10 - propoxy - 7 , 8 - dihydro - 4h , 6h - 5 - oxa - 1 - aza - phenanthren - 1 - yl ]- n -( 2 - morpholin - 4 - ylethyl ) acetamide ( 115 mg , yield : 16 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 - 1 . 00 ( 3h , t , j = 7 . 5 hz ), 1 . 71 - 1 . 77 ( 2h , m ), 1 . 91 - 1 . 93 ( 2h , m ), 2 . 29 - 2 . 34 ( 4h , m ), 2 . 72 - 2 . 75 ( 2h , t , j = 6 . 2 hz ), 3 . 15 - 3 . 19 ( 2h , m ), 3 . 25 - 3 . 30 ( 2h , m ), 3 . 33 - 3 . 54 ( 4h , m ), 3 . 76 ( 3h , s ), 3 . 85 - 3 . 90 ( 2h , t , j = 6 . 7 hz ), 4 . 07 - 4 . 11 ( 2h , m ), 5 . 06 ( 2h , s ), 6 . 90 - 6 . 93 ( 3h , m ), 7 . 54 - 7 . 58 ( 2h , m ), 7 . 72 ( 1h , s ), 7 . 80 - 7 . 82 ( 1h , m ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 - 1 . 12 ( 3h , t , j = 7 . 4 hz ), 1 . 36 ( 18h , s ), 1 . 88 - 1 . 96 ( 2h , m ), 2 . 01 - 2 . 10 ( 2h , m ), 3 . 82 ( 3h , s ), 3 . 98 - 4 . 03 ( 2h , t , j = 6 . 7 hz ), 4 . 28 - 4 . 32 ( 2h , t , j = 5 . 1 hz ), 6 . 25 - 6 . 31 ( 2h , d , j = 12 . 2 hz ), 6 . 85 - 6 . 93 ( 3h , m ), 7 . 60 - 7 . 66 ( 3h , m ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 74 - 1 . 95 ( 4h , m ), 2 . 72 - 2 . 75 ( 2h , t , j = 6 . 5 hz ), 3 . 75 ( 3h , s ), 4 . 00 - 4 . 10 ( 4h , m ), 6 . 20 - 6 . 24 ( 2h , d , j = 10 . 3 hz ), 6 . 92 - 7 . 10 ( 3h , m ), 7 . 53 - 7 . 57 ( 2h , m ), 7 . 86 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 91 - 0 . 97 ( 3h , t , j = 7 . 4 hz ), 1 . 72 - 1 . 86 ( 2h , m ), 1 . 90 - 1 . 94 ( 2h , m ), 2 . 70 - 2 . 75 ( 2h , t , j = 6 . 4 hz ), 3 . 74 ( 3h , s ), 3 . 91 - 3 . 97 ( 3h , t , j = 6 . 8 hz ), 4 . 11 - 4 . 15 ( 3h , t , j = 4 . 8 hz ), 5 . 94 - 5 . 98 ( 2h , d , j = 8 . 8 hz ), 6 . 89 - 6 . 93 ( 2h , d , j = 8 . 8 hz ), 7 . 03 ( 1h , s ), 7 . 37 - 7 . 41 ( 2h , d , j = 8 . 8 hz ), 7 . 97 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 03 - 1 . 10 ( 3h , t , j = 7 . 5 hz ), 1 . 84 - 2 . 02 ( 4h , m ), 3 . 52 - 3 . 58 ( 2h , t , j = 6 . 5 hz ), 3 . 81 ( 3h , s ), 4 . 02 - 4 . 07 ( 2h , t , j = 6 . 6 hz ), 4 . 16 - 4 . 19 ( 2h , t , j = 5 . 1 hz ), 6 . 58 ( 1h , s ), 6 . 91 - 6 . 95 ( 2h , d , j = 9 . 0 hz ), 7 . 51 - 7 . 55 ( 2h , d , j = 9 . 0 hz ), 7 . 61 - 7 . 64 ( 1h , d , j = 6 . 2 hz ), 8 . 86 - 8 . 88 ( 1h , d , j = 5 . 45 hz ). the above compound was prepared in the same manner as in example 31 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 01 - 1 . 07 ( 3h , t , j = 7 . 5 hz ), 1 . 23 - 1 . 29 ( 3h , t , j = 7 . 5 hz ), 1 . 79 - 1 . 85 ( 2h , m ), 1 . 95 - 1 . 98 ( 2h , m ), 3 . 49 - 3 . 54 ( 2h , t , j = 6 . 5 hz ), 3 . 83 ( 3h , s ), 3 . 91 - 3 . 96 ( 2h , t , 6 . 8 hz ), 4 . 11 - 4 . 27 ( 6h , m ), 5 . 05 ( 2h , s ), 6 . 62 ( 1h , s ), 6 . 92 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 29 ( 1h , s ), 7 . 54 - 7 . 57 ( 2h , d , j - 8 . 8 hz ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 - 1 . 00 ( 3h , t , j = 7 . 5 hz ), 1 . 72 - 1 . 86 ( 4h , m ), 3 . 11 - 3 . 33 ( 2h , m ), 3 . 76 ( 3h , s ), 3 . 90 - 3 . 95 ( 2h , t , j = 6 . 5 hz ), 4 . 08 - 4 . 11 ( 2h , m ), 5 . 17 ( 2h , s ), 6 . 70 ( 1h , s ), 6 . 90 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 53 - 7 . 60 ( 2h , d , j = 8 . 8 hz ), 8 . 54 ( 1h , s ), 12 . 6 - 12 . 9 ( 1h , brs ). the above compound was prepared in the same manner as in example 33 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 93 - 0 . 98 ( 3h , t , j = 7 . 3 hz ), 1 . 66 - 1 . 90 ( 4h , m ), 3 . 00 - 3 . 20 ( 4h , m ), 3 . 50 - 3 . 62 ( 2h , m ), 3 . 76 ( 3h , s ), 3 . 90 - 3 . 96 ( 4h , m ), 4 . 04 - 4 . 12 ( 2h , m ), 5 . 07 ( 2h , s ), 6 . 70 ( 1h , s ), 6 . 91 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 56 - 7 . 59 ( 2h , d , j = 8 . 8 hz ), 7 . 77 ( 1h , s ), 8 . 10 - 8 . 25 ( 1h , m ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 - 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 66 - 1 . 96 ( 6h , m ), 2 . 90 - 3 . 21 ( 6h , m ), 3 . 25 - 3 . 43 ( 4h , m ), 3 . 56 - 3 . 66 ( 2h , t , j = 11 . 9 hz ), 3 . 77 ( 3h , s ), 3 . 85 - 4 . 04 ( 4h , m ), 4 . 05 - 4 . 18 ( 2h , m ), 5 . 09 ( 2h , s ), 6 . 71 ( 1h , s ), 6 . 92 - 6 . 96 ( 2h , d , j = 8 . 8 hz ), 7 . 57 - 7 . 61 ( 2h , d , j = 8 . 8 hz ), 7 . 79 ( 1h , s ), 8 . 09 - 8 . 14 ( 1h , t , j = 5 . 5 hz ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 83 - 1 . 91 ( 4h , m ), 2 . 00 - 2 . 20 ( 2h , m ), 3 . 00 - 4 . 50 ( 20h , m ), 4 . 50 - 4 . 70 ( 2h , m ), 6 . 77 ( 1h , s ), 6 . 90 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 60 - 7 . 65 ( 2h , d , j = 8 . 8 hz ), 7 . 94 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 35 ( 18h , s ), 1 . 89 - 1 . 98 ( 4h , m ), 3 . 46 - 3 . 51 ( 2h , t , j = 6 . 5 hz ), 3 . 82 ( 3h , s ), 4 . 01 - 4 . 06 ( 2h , t , j = 6 . 6 hz ), 4 . 16 - 4 . 21 ( 2h , t , j = 5 . 0 hz ), 6 . 25 - 6 . 30 ( 2h , d , j = 12 . 3 hz ), 6 . 70 ( 1h , s ), 6 . 91 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 55 - 7 . 59 ( 2h , d , j = 8 . 8 hz ), 7 . 68 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 - 1 . 10 ( 3h , t , j = 7 . 5 hz ), 1 . 84 - 2 . 02 ( 4h , m ), 3 . 52 - 3 . 58 ( 2h , t , j = 6 . 5 hz ), 3 . 81 ( 3h , s ), 4 . 02 - 4 . 07 ( 2h , t , j = 6 . 6 hz ), 4 . 16 - 4 . 19 ( 2h , t , j = 5 . 1 hz ), 6 . 15 - 6 . 19 ( 2h , d , j = 10 . 8 hz ), 6 . 80 ( 1h , s ), 6 . 94 - 6 . 96 ( 2h , d , j = 9 . 0 hz ), 7 . 52 - 7 . 56 ( 2h , d , j = 9 . 0 hz ), 7 . 69 - 7 . 72 ( 1h , d , j = 6 . 2 hz ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 94 - 0 . 99 ( 2h , t , j = 7 . 4 hz ), 1 . 81 - 1 . 88 ( 2h , m ), 3 . 21 - 3 . 23 ( 2h , m ), 3 . 78 ( 3h , s ), 3 . 99 - 4 . 05 ( 2h , m ), 4 . 13 - 4 . 15 ( 2h , m ), 6 . 04 - 6 . 14 ( 2h , d , j = 8 . 8 hz ), 6 . 78 ( 1h , s ), 6 . 96 - 6 . 99 ( 2h , d , j = 8 . 8 hz ), 7 . 39 - 7 . 45 ( 2h , m ), 8 . 08 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 83 ( 2h , m ), 3 . 13 ( 2h , t , j = 8 . 8 hz ), 3 . 74 ( 3h , s ), 4 . 02 ( 2h , t , j = 6 . 5 hz ), 4 . 54 ( 2h , t , j = 8 . 9 hz ), 6 . 91 ( 2h , d , j = 8 . 7 hz ), 7 . 15 ( 1h , s ), 7 . 51 ( 2h , d , j = 8 . 7 hz ), 7 . 75 ( 1h , d , j = 5 . 9 hz ), 10 . 99 ( 1h , d , j = 5 . 9 hz ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 72 - 1 . 84 ( 2h , m ), 3 . 14 ( 2h , t , j = 8 . 9 hz ), 4 . 02 ( 2h , t , j = 6 . 5 hz ), 4 . 55 ( 2h , t , j = 8 . 9 hz ), 7 . 15 ( 1h , s ), 7 . 47 - 7 . 54 ( 2h , m ), 8 . 08 ( 1h , d , j = 6 . 3 hz ), 8 . 16 - 8 . 17 ( 1h , m ), 11 . 10 ( 1h , d , j = 6 . 1 hz ). the above compound was prepared in the same manner as in example 8 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 ( 3h , t , j = 7 . 4 hz ), 1 . 76 - 1 . 84 ( 2h , m ), 2 . 18 ( 3h , s ), 3 . 11 ( 2h , t , j = 8 . 9 hz ), 3 . 74 ( 3h , s ), 4 . 04 ( 2h , t , j = 6 . 8 hz ), 4 . 50 ( 2h , t , j = 8 . 9 hz ), 6 . 90 ( 2h , d , j = 8 . 7 hz ), 7 . 06 ( 2h , d , j = 8 . 6 hz ), 7 . 15 ( 1h , s ), 10 . 19 ( 1h , brs ). the above compound was prepared in the same manner as in example 31 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 3 hz ), 1 . 26 ( 3h , t , j = 7 . 2 hz ), 1 . 78 - 1 . 86 ( 2h , m ), 3 . 19 ( 2h , t , j = 8 . 8 hz ), 3 . 82 ( 3h , s ), 3 . 91 ( 2h , t , j = 6 . 9 hz ), 4 . 22 ( 2h , q , j = 7 . 2 hz ), 4 . 75 ( 2h , t , j = 8 . 9 hz ), 5 . 05 ( 2h , s ), 6 . 90 ( 2h , d , j = 8 . 8 hz ), 7 . 01 ( 1h , s ), 7 . 31 ( 1h , s ), 7 . 63 ( 2h , d , j = 8 . 8 hz ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 3 hz ), 1 . 26 ( 3h , t , j = 7 . 2 hz ), 1 . 78 - 1 . 86 ( 2h , m ), 3 . 19 ( 2h , t , j = 8 . 8 hz ), 3 . 82 ( 3h , s ), 3 . 91 ( 2h , t , j = 6 . 9 hz ), 4 . 22 ( 2h , q , j = 7 . 2 hz ), 4 . 75 ( 2h , t , j = 8 . 9 hz ), 5 . 05 ( 2h , s ), 6 . 90 ( 2h , d , j = 8 . 8 hz ), 7 . 01 ( 1h , s ), 7 . 31 ( 1h , s ), 7 . 63 ( 2h , d , j = 8 . 8 hz ). the above compound was prepared in the same manner as in example 33 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 92 ( 3h , t , j = 7 . 3 hz ), 1 . 67 - 1 . 76 ( 2h , m ), 2 . 28 - 2 . 33 ( 6h , m ), 3 . 08 - 3 . 17 ( 4h , m ), 3 . 47 - 3 . 51 ( 4h , m ), 3 . 75 ( 3h , s ), 3 . 86 ( 2h , t , j = 6 . 7 hz ), 4 . 53 ( 2h , t , j = 8 . 9 hz ), 5 . 06 ( 2h , s ), 6 . 90 ( 2h , d , j = 8 . 8 hz ), 7 . 19 ( 1h , s ), 7 . 54 ( 2h , d , j = 8 . 8 hz ), 7 . 74 ( 1h , s ), 7 . 83 ( 1h , t , j = 5 . 4 hz ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 74 - 1 . 82 ( 2h , m ), 2 . 30 - 2 . 33 ( 4h , m ), 2 . 54 ( 2h , t , j = 5 . 5 hz ), 3 . 14 ( 2h , t , j = 8 . 8 hz ), 3 . 42 - 3 . 45 ( 4h , m ), 3 . 74 ( 3h , s ), 3 . 97 ( 2h , t , j = 6 . 5 hz ), 4 . 50 - 4 . 61 ( 4h , m ), 6 . 92 ( 2h , d , j = 8 . 8 hz ), 7 . 25 ( 1h , s ), 7 . 56 ( 2h , d , j = 8 . 8 hz ), 7 . 81 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 - 1 . 12 ( 3h , t , j = 7 . 4 hz ), 1 . 36 ( 18h , s ), 1 . 85 - 1 . 97 ( 2h , m ), 3 . 19 - 3 . 26 ( 2h , t , j = 9 . 0 hz ), 3 . 82 ( 3h , s ), 4 . 00 - 4 . 05 ( 2h , t , j = 6 . 7 hz ), 4 . 73 - 4 . 80 ( 2h , t , j = 9 . 0 hz ), 6 . 28 - 6 . 34 ( 2h , d , j = 12 . 6 hz ), 6 . 88 - 6 . 94 ( 2h , d , j = 8 . 8 hz ), 7 . 11 ( 1h , s ), 7 . 63 - 7 . 70 ( 2h , d , j = 8 . 8 hz ), 7 . 74 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 79 - 1 . 90 ( 2h , m ), 3 . 15 - 3 . 22 ( 2h , m ), 4 . 00 - 4 . 06 ( 2h , t , j = 6 . 7 hz ), 4 . 53 - 4 . 62 ( 2h , m ), 6 . 21 - 6 . 25 ( 2h , d , j = 10 . 6 hz ), 6 . 92 - 6 . 97 ( 2h , m ), 7 . 36 ( 1h , s ), 7 . 56 - 7 . 59 ( 2h , m ), 7 . 90 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 92 - 0 . 97 ( 3h , t , j = 7 . 4 hz ), 1 . 76 - 1 . 84 ( 2h , m ), 3 . 12 - 3 . 19 ( 2h , t , j = 8 . 9 hz ), 3 . 75 ( 3h , s ), 3 . 93 - 3 . 99 ( 2h , t , j = 6 . 8 hz ), 4 . 56 - 4 . 59 ( 2h , m ), 5 . 95 - 5 . 99 ( 2h , d , j = 8 . 9 hz ), 6 . 90 - 6 . 94 ( 2h , d , j = 8 . 8 hz ), 7 . 27 ( 1h , s ), 7 . 39 - 7 . 43 ( 2h , d , j = 8 . 8 hz ), 8 . 01 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 2 . 84 ( 3h , s ), 3 . 76 ( 3h , s ), 6 . 89 - 7 . 02 ( 3h , m ), 7 . 22 ( 1h , s ), 7 . 52 - 7 . 58 ( 2h , d , j = 8 . 8 hz ), 7 . 77 ( 1h , s ), 8 . 21 ( 1h , s ), 12 . 06 ( 1h , brs ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 2 . 73 ( 3h , s ), 3 . 26 - 3 . 33 ( 2h , t , j = 8 . 8 hz ), 3 . 75 ( 3h , s ), 4 . 69 - 4 . 76 ( 2h , t , j = 8 . 8 hz ), 6 . 87 - 6 . 93 ( 3h , m ), 7 . 50 - 7 . 53 ( 2h , d , j = 8 . 9 hz ), 7 . 64 ( 1h , s ), 11 . 30 ( 1h , brs ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 39 ( 18h , s ), 2 . 86 ( 3h , s ), 3 . 26 - 3 . 33 ( 2h , t , j = 8 . 8 hz ), 3 . 83 ( 3h , s ), 4 . 66 - 4 . 73 ( 2h , t , j = 8 . 9 hz ), 6 . 21 - 6 . 26 ( 2h , d , j = 11 . 3 hz ), 6 . 92 - 6 . 99 ( 3h , m ), 7 . 52 - 7 . 56 ( 2h , d , j = 8 . 9 hz ), 7 . 66 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 2 . 75 ( 3h , s ), 3 . 26 - 3 . 33 ( 2h , t , j = 8 . 8 hz ), 3 . 75 ( 3h , s ), 4 . 69 - 4 . 76 ( 2h , t , j = 8 . 8 hz ), 6 . 15 - 6 . 19 ( 2h , d , j = 10 . 8 hz ), 6 . 90 - 6 . 97 ( 3h , m ), 7 . 52 - 7 . 58 ( 2h , d , j = 8 . 9 hz ), 7 . 64 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 2 . 57 ( 3h , s ), 3 . 06 - 3 . 13 ( 2h , t , j = 8 . 8 hz ), 3 . 72 ( 3h , s ), 4 . 50 - 4 . 58 ( 2h , m ), 5 . 84 - 5 . 88 ( 2h , d , j = 8 . 8 hz ), 6 . 84 - 6 . 87 ( 2h , d , j = 8 . 8 hz ), 6 . 93 ( 1h , s ), 7 . 27 - 7 . 31 ( 2h , d , j = 8 . 8 hz ), 7 . 75 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 - 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 80 - 2 . 00 ( 2h , m ), 2 . 33 - 2 . 39 ( 2h , t , j = 7 . 4 hz ), 3 . 70 - 3 . 80 ( 5h , m ), 4 . 04 - 4 . 09 ( 2h , t , j = 6 . 5 hz ), 6 . 85 ( 1h , s ), 6 . 91 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 53 - 7 . 56 ( 2h , d , j = 8 . 8 hz ), 7 . 72 - 7 . 75 ( 1h , d , j = 6 . 4 hz ), 9 . 94 ( 1h , s ), 11 . 02 - 11 . 25 ( 1h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 - 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 82 - 2 . 00 ( 2h , m ), 2 . 37 - 2 . 43 ( 2h , t , j = 7 . 4 hz ), 3 . 32 ( 3h , s ), 3 . 65 - 3 . 95 ( 5h , m ), 4 . 17 - 4 . 22 ( 2h , t , j = 6 . 5 hz ), 6 . 90 - 6 . 95 ( 2h , d , j = 8 . 8 hz ), 7 . 05 ( 1h , s ), 7 . 50 - 7 . 55 ( 2h , d , j = 8 . 8 hz ), 7 . 76 ( 1h , s ), 11 . 14 ( 1h , brs ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 75 ( 3h , s ), 3 . 89 ( 3h , s ), 6 . 93 ( 2h , d , j = 8 . 6 hz ), 7 . 00 ( 1h , s ), 7 . 57 ( 2h , d , j = 8 . 6 hz ), 7 . 63 - 7 . 68 ( 1h , m ), 7 . 91 ( 1h , s ), 8 . 26 ( 1h , d , j = 8 . 2 hz ), 8 . 78 ( 1h , d , j = 4 . 2 hz ), 12 . 23 ( 1h , brs ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 98 ( 3h , s ), 7 . 17 ( 1h , s ), 7 . 59 ( 1h , s ), 7 . 60 ( 1h , s ), 7 . 70 - 7 . 75 ( 1h , m ), 8 . 20 ( 1h , brs ), 8 . 33 ( 1h , d , j = 8 . 3 hz ), 8 . 50 ( 1h , s ), 8 . 81 - 8 . 83 ( 1h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 94 ( 3h , s ), 7 . 07 - 7 . 10 ( 2h , m ), 7 . 44 ( 1h , d , j = 6 . 0 hz ), 7 . 60 ( 1h , d , j = 3 . 7 hz ), 7 . 61 - 7 . 71 ( 1h , m ), 8 . 29 ( 1h , d , j = 8 . 3 hz ), 8 . 47 ( 1h , s ), 8 . 80 - 8 . 83 ( 1h , m ), 12 . 60 ( 1h , brs ). the above compound was prepared in the same manner as in example 3 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 90 ( 3h , s ), 4 . 54 ( 3h , s ), 7 . 08 - 7 . 13 ( 2h , m ), 7 . 44 ( 1h , d , j = 5 . 1 hz ), 7 . 56 - 7 . 61 ( 1h , m ), 7 . 65 ( 1h , d , j = 3 . 7 hz ), 8 . 24 ( 1h , d , j = 8 . 2 hz ), 8 . 64 ( 1h , s ), 8 . 75 - 8 . 77 ( 1h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 14 - 1 . 19 ( 3h , t , j = 7 . 4 hz ), 1 . 98 - 2 . 07 ( 2h , m ), 3 . 87 ( 3h , s ), 4 . 26 - 4 . 32 ( 2h , t , j = 6 . 6 hz ), 6 . 98 - 7 . 02 ( 2h , d , j = 8 . 7 hz ), 7 . 30 ( 1h , s ), 7 . 61 - 7 . 64 ( 2h , d , j = 6 . 6 hz ), 8 . 64 - 8 . 66 ( 1h , d , j = 6 . 0 hz ), 9 . 10 ( 1h , s ), 9 . 38 - 9 . 40 ( 1h , d , j = 4 . 8 hz ), 9 . 97 - 9 . 99 ( 1h , d , j = 5 . 9 hz ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 14 - 1 . 19 ( 3h , t , j = 7 . 4 hz ), 1 . 98 - 2 . 07 ( 2h , m ), 3 . 87 ( 3h , s ), 4 . 26 - 4 . 32 ( 2h , t , j = 6 . 6 hz ), 5 . 47 ( 2h , s ), 6 . 98 - 7 . 02 ( 2h , d , j = 8 . 7 hz ), 7 . 30 ( 1h , s ), 7 . 61 - 7 . 64 ( 2h , d , j = 6 . 6 hz ), 8 . 64 - 8 . 66 ( 1h , d , j = 6 . 0 hz ), 9 . 10 ( 1h , s ), 9 . 38 - 9 . 40 ( 1h , d , j = 4 . 8 hz ). the above compound was prepared in the same manner as in example 33 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 82 - 1 . 91 ( 2h , m ), 2 . 82 - 3 . 12 ( 8h , m ), 3 . 60 - 3 . 80 ( 4h , m ), 3 . 81 ( 3h , s ), 4 . 14 - 4 . 20 ( 2h , t , j = 6 . 8 hz ), 5 . 32 ( 2h , s ), 7 . 00 - 7 . 03 ( 2h , d , j = 7 . 8 hz ), 7 . 69 - 7 . 72 ( 2h , d , j = 7 . 8 hz ), 7 . 78 ( 1h , s ), 8 . 11 ( 1h , s ), 8 . 20 - 8 . 30 ( 1h , m ), 8 . 51 - 8 . 53 ( 1h , d , j = 6 . 1 hz ) 9 . 19 ( 1h , s ), 9 . 99 - 10 . 0 ( 1h , d , j = 6 . 1 hz ). the above compound was prepared in the same manner as in example 31 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 96 - 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 18 - 1 . 24 ( 3h , t , j = 7 . 1 hz ), 1 . 69 - 1 . 80 ( 2h , m ), 3 . 78 ( 3h , s ), 3 . 94 - 4 . 00 ( 2h , t , j = 6 . 7 hz ), 4 . 12 - 4 . 21 ( 2h , q , j = 7 . 1 hz ), 5 . 32 ( 2h , s ), 6 . 94 - 7 . 04 ( 3h , m ), 7 . 21 - 7 . 26 ( 1h , m ), 7 . 58 - 7 . 62 ( 2h , d , j = 8 . 7 hz ), 8 . 02 ( 1h , s ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 - 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 72 - 1 . 87 ( 2h , m ), 3 . 82 ( 3h , s ), 3 . 95 - 4 . 00 ( 2h , t , j = 6 . 7 hz ), 5 . 24 ( 2h , s ), 6 . 94 - 7 . 03 ( 3h , m ), 7 . 20 - 7 . 26 ( 1h , m ), 7 . 59 - 7 . 62 ( 2h , d , j = 8 . 7 hz ), 8 . 02 ( 1h , s ), 12 . 5 - 13 . 3 ( 1h , br ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 81 - 0 . 87 ( 3h , t , j = 7 . 1 hz ), 0 . 91 - 0 . 98 ( 3h , t , j = 7 . 4 hz ), 1 . 19 - 1 . 45 ( 4h , m ), 1 . 70 - 1 . 80 ( 2h , m ), 3 . 02 - 3 . 09 ( 2h , q , 6 . 3 hz ), 3 . 76 ( 3h , s ), 3 . 90 - 3 . 95 ( 2h , t , j = 6 . 8 hz ), 5 . 13 ( 2h , s ), 6 . 90 - 6 . 98 ( 3h , m ), 7 . 15 - 7 . 20 ( 1h , m ), 7 . 56 - 7 . 60 ( 2h , d , j = 8 . 7 hz ), 7 . 90 ( 1h , s ), 7 . 97 - 8 . 01 ( 1h , t , j = 5 . 5 hz ). to a dmf solution ( 2 ml ) of [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] acetic acid ( 800 mg , 2 . 07 mmol ) were sequentially added a dmf solution ( 1 ml ) of 4 -( 2 - aminoethyl ) morpholine ( 273 mg ), triethylamine ( 506 mg , 5 . 0 mmol ), diethylphosphorocyanidate ( depc , 405 mg , 2 . 48 mmol ) and dmf ( 1 ml ) while ice - cooling , followed by stirring at room temperature for 23 hours . water was added to the reaction mixture and then subjected to extraction using ethyl acetate . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution twice , dried over anhydrous sodium sulfate and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 30 : 1 → 15 : 1 ). the purified product was concentrated under reduced pressure , and the residue was recrystallized from ethyl acetate , giving a white powder of 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ]- n -( 2 - morpholin - 4 - ylethyl ) acetamide ( 789 mg , yield : 77 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 95 ( 3h , t , j = 7 . 3 hz ), 1 . 71 - 1 . 80 ( 2h , m ), 2 . 30 - 2 . 34 ( 6h , m ), 3 . 18 ( 2h , q , j = 6 . 5 hz ), 3 . 49 - 3 . 53 ( 4h , m ), 3 . 76 ( 3h , s ), 3 . 93 ( 2h , t , j = 6 . 8 hz ), 5 . 14 ( 2h , s ), 6 . 92 - 6 . 99 ( 3h , m ), 7 . 18 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 8 hz ), 7 . 90 - 7 . 95 ( 2h , m ). sodium hydride ( 60 % oil base , 61 mg , 1 . 4 mmol ) was added to a dmf solution ( 2 ml ) of 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ]- n -( 2 - morpholin - 4 - ylethyl ) acetamide ( 580 mg , 1 . 16 mmol ), and the resulting mixture was stirred at room temperature for 5 minutes . methyl iodide ( 230 mg , 1 . 62 mmol ) was added thereto , and the thus - obtained mixture was stirred at room temperature for 15 hours . water and ethyl acetate were added to the reaction mixture , followed by separation . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 30 : 1 → 15 : 1 ). the purified product was concentrated under reduced pressure , and the residue was recrystallized from ethyl acetate , giving a white powder of 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ]- n - methyl - n -( 2 - morpholin - 4 - ylethyl ) acetamide ( 440 mg , yield : 74 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 ( 3h , t , j = 7 . 3 hz ), 1 . 64 - 1 . 72 ( 2h , m ), 2 . 33 - 2 . 38 ( 4h , m ), 2 . 43 - 2 . 50 ( 2h , m ), 2 . 85 ( 1h , s ), 2 . 99 ( 2h , s ), 3 . 37 ( 2h , t , j = 6 . 8 hz ), 3 . 44 - 3 . 48 ( 4h , m ), 3 . 75 ( 3h , s ), 3 . 89 ( 2h , t , j = 6 . 7 hz ), 5 . 43 ( 2h , s ), 6 . 89 - 6 . 97 ( 3h , m ), 7 . 12 - 7 . 17 ( 1h , m ), 7 . 53 - 7 . 57 ( 2h , m ), 7 . 83 ( 1h , s ). the above compound was prepared in the same manner as in example 73 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 95 ( 3h , t , j = 7 . 3 hz ), 1 . 52 - 1 . 57 ( 2h , m ), 1 . 71 - 1 . 79 ( 2h , m ), 2 . 21 - 2 . 29 ( 6h , m ), 3 . 09 ( 2h , q , j = 5 . 8 hz ), 3 . 49 - 3 . 54 ( 4h , m ), 3 . 76 ( 3h , s ), 3 . 93 ( 2h , t , j = 6 . 8 hz ), 5 . 12 ( 2h , s ), 6 . 92 - 6 . 99 ( 3h , m ), 7 . 18 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 8 hz ), 7 . 90 ( 1h , s ), 8 . 00 ( 1h , t , j = 5 . 4 hz ). the above compound was prepared in the same manner as in example 74 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 92 - 0 . 98 ( 3h , m ), 1 . 65 - 1 . 71 ( 4h , m ), 2 . 21 - 2 . 36 ( 6h , m ), 2 . 82 ( 1h , s ), 2 . 98 ( 2h , s ), 3 . 20 - 3 . 30 ( 2h , m ), 3 . 48 - 3 . 58 ( 4h , m ), 3 . 76 ( 3h , s ), 3 . 90 ( 2h , t , j = 6 . 8 hz ), 5 . 43 - 5 . 45 ( 2h , m ), 6 . 90 - 6 . 98 ( 3h , m ), 7 . 13 - 7 . 18 ( 1h , m ), 7 . 54 - 7 . 59 ( 2h , m ), 7 . 86 ( 1h , s ). the above compound was prepared in the same manner as in example 73 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 95 ( 3h , t , j = 7 . 3 hz ), 1 . 40 - 1 . 49 ( 2h , m ), 1 . 67 - 1 . 84 ( 4h , m ), 1 . 91 - 2 . 00 ( 2h , m ), 2 . 14 ( 3h , s ), 2 . 69 - 2 . 73 ( 2h , m ), 3 . 55 - 3 . 75 ( 1h , m ), 3 . 75 ( 3h , s ), 3 . 93 ( 2h , t , j = 6 . 7 hz ), 5 . 14 ( 2h , s ), 6 . 90 - 6 . 98 ( 3h , m ), 7 . 16 ( 1h , dd , j = 4 . 4 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 6 hz ), 7 . 90 ( 1h , s ), 8 . 03 ( 1h , d , j = 7 . 3 hz ). the above compound was prepared in the same manner as in example 73 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 03 ( 3h , t , j = 7 . 3 hz ), 1 . 31 - 1 . 38 ( 2h , m ), 1 . 41 ( 9h , s ), 1 . 80 - 1 . 86 ( 4h , m ), 2 . 70 - 3 . 00 ( 2h , m ), 3 . 79 ( 3h , s ), 3 . 88 - 4 . 13 ( 5h , m ), 4 . 94 ( 2h , s ), 6 . 55 ( 1h , brs ), 6 . 77 - 6 . 92 ( 4h , m ), 7 . 31 ( 1h , s ), 7 . 46 ( 2h , d , j = 8 . 8 hz ). a 4n hydrochloric acid ethyl acetate solution ( 25 ml ) was added to an ethanol solution ( 12 ml ) of tert - butyl 4 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] acetylamino } piperidine - 1 - carboxylate ( 820 mg , 1 . 44 mmol ), followed by stirring at room temperature for 28 hours . the resulting mixture was concentrated under reduced pressure . after adding an aqueous sodium bicarbonate solution to the residue to adjust the ph to 8 , the residue was washed with ethyl acetate . a 2n aqueous sodium hydroxide solution was added to the water layer to adjust its ph to 11 , followed by extraction using dichloromethane . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution and dried over anhydrous magnesium sulfate , and then concentrated under reduced pressure . the residue was recrystallized from ethanol - ethyl acetate , giving a white powder of 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ]- n - piperidin - 4 - ylacetamide ( 185 mg , yield : 27 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 ( 3h , t , j = 7 . 3 hz ), 1 . 22 - 1 . 33 ( 2h , m ), 1 . 62 - 1 . 81 ( 4h , m ), 2 . 36 - 2 . 45 ( 2h , m ), 2 . 84 - 2 . 89 ( 2h , m ), 3 . 55 - 3 . 75 ( 2h , m ), 3 . 75 ( 3h , s ), 3 . 92 ( 2h , t , j = 6 . 7 hz ), 5 . 13 ( 2h , s ), 6 . 90 - 6 . 98 ( 3h , m ), 7 . 16 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 56 ( 2h , d , j = 8 . 6 hz ), 7 . 88 ( 1h , s ), 8 . 01 ( 1h , d , j = 7 . 5 hz ). the above compound was prepared in the same manner as in example 31 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 06 - 1 . 12 ( 3h , t , j = 7 . 13 ), 1 . 80 - 2 . 02 ( 4h , m ), 2 . 24 - 2 . 30 ( 2h , t , j = 7 . 4 hz ), 3 . 77 ( 3h , s ), 3 . 92 - 4 . 00 ( 2h , q , j = 7 . 1 hz ), 4 . 03 - 4 . 09 ( 2h , t , j = 6 . 6 hz ), 4 . 54 - 4 . 60 ( 2h , t , j = 6 . 87 hz ), 6 . 93 - 7 . 04 ( 3h , m ), 7 . 24 - 7 . 29 ( 1h , m ), 7 . 60 - 7 . 63 ( 2h , d , j = 8 . 6 hz ), 7 . 97 ( 1h , s ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 2 . 00 ( 4h , m ), 2 . 16 - 2 . 22 ( 2h , t , j = 7 . 4 hz ), 3 . 78 ( 3h , s ), 4 . 04 - 4 . 09 ( 2h , t , j = 6 . 6 hz ), 4 . 54 - 4 . 60 ( 2h , t , j = 7 . 0 hz ), 6 . 93 - 7 . 04 ( 3h , m ), 7 . 24 - 7 . 30 ( 1h , m ), 7 . 60 - 7 . 64 ( 2h , d , j = 8 . 8 hz ), 7 . 97 ( 1h , s ), 11 . 80 - 12 . 20 ( 1h , br ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 78 - 0 . 84 ( 3h , t , j = 7 . 1 hz ), 0 . 99 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 10 - 1 . 42 ( 4h , m ), 1 . 75 - 2 . 01 ( 6h , m ), 2 . 92 - 2 . 97 ( 2h , m ), 3 . 77 ( 3h , s ), 4 . 03 - 4 . 08 ( 2h , t , j = 6 . 6 hz ), 4 . 53 - 4 . 58 ( 2h , t , j = 6 . 2 hz ), 6 . 92 - 7 . 03 ( 3h , m ), 7 . 23 - 7 . 28 ( 1h , m ), 7 . 60 - 7 . 63 ( 2h , t , j = 8 . 6 hz ), 7 . 70 - 7 . 75 ( 1h , m ), 7 . 93 ( 1h , s ). the above compound was prepared in the same manner as in example 17 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 - 1 . 12 ( 3h , m ), 1 . 85 - 1 . 96 ( 2h , m ), 2 . 30 - 2 . 35 ( 2h , m ), 3 . 33 ( 2h , t , j = 6 . 1 hz ), 3 . 83 ( 3h , s ), 3 . 96 - 4 . 05 ( 2h , m ), 4 . 69 ( 2h , t , j = 6 . 5 hz ), 6 . 85 - 7 . 03 ( 4h , m ), 7 . 59 - 7 . 64 ( 3h , m ). the above compound was prepared in the same manner as in example 17 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 - 1 . 13 ( 3h , m ), 1 . 87 - 1 . 96 ( 2h , m ), 2 . 22 - 2 . 27 ( 2h , m ), 3 . 49 ( 2h , t , j = 5 . 8 hz ), 3 . 83 ( 3h , s ), 3 . 96 - 4 . 05 ( 2h , m ), 4 . 70 ( 2h , t , j = 6 . 5 hz ), 6 . 86 - 7 . 02 ( 4h , m ), 7 . 59 - 7 . 64 ( 3h , m ). the above compound was prepared in the same manner as in example 18 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 73 - 1 . 87 ( 4h , m ), 2 . 07 - 2 . 20 ( 6h , m ), 3 . 36 - 3 . 39 ( 4h , m ), 3 . 74 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 5 hz ), 4 . 56 ( 2h , t , j = 6 . 3 hz ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 21 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 57 ( 2h , d , j = 8 . 7 hz ), 7 . 98 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 81 ( 6h , t , j = 7 . 0 hz ), 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 75 - 1 . 87 ( 4h , m ), 2 . 22 - 2 . 38 ( 6h , m ), 3 . 75 ( 3h , s ), 4 . 03 ( 2h , t , j = 6 . 6 hz ), 4 . 54 ( 2h , t , j = 6 . 7 hz ), 6 . 91 - 7 . 01 ( 3h , m ), 7 . 23 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 59 ( 2h , d , j = 8 . 8 hz ), 7 . 96 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 78 - 1 . 86 ( 4h , m ), 1 . 96 ( 3h , s ), 2 . 04 - 2 . 14 ( 10h , m ), 3 . 75 ( 3h , s ), 4 . 02 ( 2h , t , j = 6 . 5 hz ), 4 . 55 ( 2h , t , j = 6 . 2 hz ), 6 . 90 - 7 . 01 ( 3h , m ), 7 . 23 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 8 hz ), 7 . 97 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 20 - 1 . 40 ( 6h , m ), 1 . 73 - 1 . 84 ( 4h , m ), 2 . 02 - 2 . 10 ( 6h , m ), 3 . 74 ( 3h , s ), 4 . 00 ( 2h , t , j = 6 . 4 hz ), 4 . 53 ( 2h , t , j = 6 . 2 hz ), 6 . 89 - 7 . 00 ( 3h , m ), 7 . 20 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 57 ( 2h , d , j = 8 . 6 hz ), 7 . 95 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 80 - 1 . 00 ( 6h , m ), 1 . 70 - 1 . 80 ( 4h , m ), 2 . 00 - 2 . 20 ( 12h , m ), 3 . 75 ( 3h , s ), 4 . 00 - 4 . 06 ( 2h , m ), 4 . 54 - 4 . 59 ( 2h , m ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 20 - 7 . 26 ( 1h , m ), 7 . 55 - 7 . 60 ( 2h , m ), 7 . 98 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 3 hz ), 1 . 79 - 1 . 94 ( 4h , m ), 3 . 08 - 3 . 14 ( 2h , m ), 3 . 68 - 3 . 83 ( 5h , m ), 4 . 05 ( 2h , t , j = 6 . 7 hz ), 4 . 19 - 4 . 43 ( 3h , m ), 4 . 54 - 4 . 60 ( 2h , m ), 6 . 23 ( 1h , brs ), 6 . 92 - 7 . 04 ( 3h , m ), 7 . 27 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 61 ( 2h , d , j = 8 . 6 hz ), 8 . 00 ( 1h , s ), 10 . 30 ( 1h , brs ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 79 - 1 . 89 ( 4h , m ), 2 . 14 - 2 . 27 ( 6h , m ), 3 . 20 - 3 . 30 ( 4h , m ), 3 . 74 ( 3h , s ), 4 . 03 ( 2h , t , j = 6 . 5 hz ), 4 . 60 ( 2h , t , j = 6 . 0 hz ), 6 . 58 ( 1h , dd , j = 5 . 0 hz , 6 . 9 hz ), 6 . 69 ( 1h , d , j = 8 . 6 hz ), 6 . 90 - 7 . 02 ( 3h , m ), 7 . 23 ( 1h , dd , j = 4 . 4 hz , 9 . 0 hz ), 7 . 40 - 7 . 50 ( 1h , m ), 7 . 58 - 7 . 61 ( 2h , m ), 8 . 02 - 8 . 06 ( 2h , m ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 12 - 1 . 20 ( 2h , m ), 1 . 50 - 1 . 55 ( 2h , m ), 1 . 68 - 1 . 86 ( 6h , m ), 1 . 90 - 2 . 11 ( 3h , m ), 2 . 30 - 2 . 33 ( 4h , m ), 2 . 62 - 2 . 67 ( 2h , m ), 3 . 48 - 3 . 51 ( 4h , m ), 3 . 75 ( 3h , s ), 4 . 03 ( 2h , t , j = 6 . 5 hz ), 4 . 56 ( 2h , t , j = 5 . 9 hz ), 6 . 90 - 7 . 01 ( 3h , m ), 7 . 23 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 60 ( 2h , d , j = 8 . 8 hz ), 7 . 99 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 81 - 1 . 89 ( 2h , m ), 2 . 00 - 2 . 25 ( 2h , m ), 2 . 80 - 2 . 97 ( 2h , m ), 3 . 25 ( 3h , s ), 3 . 20 - 3 . 40 ( 4h , m ), 3 . 60 - 3 . 65 ( 8h , m ), 3 . 75 ( 3h , s ), 4 . 06 ( 2h , t , j = 6 . 7 hz ), 4 . 60 ( 2h , t , j = 6 . 3 hz ), 6 . 91 - 7 . 04 ( 3h , m ), 7 . 26 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 61 ( 2h , d , j = 8 . 8 hz ), 8 . 03 ( 1h , s ). sodium hydride ( 60 % oil base , 800 mg , 18 . 3 mmol ) was added to a dmf solution ( 25 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 5 . 0 g , 15 . 2 mmol ). the mixture was stirred for 30 minutes at room temperature . n - bromopropyl phthalimide ( 4 . 48 g , 16 . 7 mmol ) was added to the mixture and stirred at room temperature for 30 minutes and at 50 ° c . for 5 hours . the reaction mixture was ice - cooled and water ( 20 ml ) and ethyl acetate were added thereto , followed by stirring for 2 hours . the generated insoluble matter was separated , washed with water , and then dried , giving a pale yellow powder of 2 -{ 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1yl ] propyl } isoindole - 1 , 3 - dione ( 4 . 63 g , yield : 59 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 ( 3h , t , j = 7 . 3 hz ), 1 . 74 - 1 . 83 ( 2h , m ), 2 . 03 ( 2h , t , j = 7 . 4 hz ), 3 . 62 ( 2h , t , j = 6 . 6 hz ), 3 . 76 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 7 hz ), 4 . 61 ( 2h , t , j = 7 . 5 hz ), 6 . 91 - 7 . 02 ( 3h , m ), 7 . 25 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 8 hz ), 7 . 78 - 7 . 86 ( 4h , m ), 8 . 06 ( 1h , s ). hydrazine hydrate ( 0 . 62 ml , 12 . 8 mmol ) was added to an ethanol solution ( 60 ml ) of 2 -{ 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propyl } isoindole - 1 , 3 - dione ( 2 . 0 g , 3 . 88 mmol ) and heated under reflux for 4 hours . the resulting mixture was concentrated under reduced pressure , a 5n aqueous sodium hydroxide solution was added to the thus - obtained residue , and then the resulting mixture was subjected to extraction using dichloromethane . the thus - obtained organic layer was sequentially washed with water and an aqueous saturated sodium chloride solution , dried over anhydrous magnesium sulfate , and then concentrated under reduced pressure , giving a yellow oily 1 -( 3 - aminopropyl )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 1 . 4 g , yield : 94 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 09 ( 3h , t , j = 7 . 3 hz ), 1 . 23 ( 2h , brs ), 1 . 84 - 1 . 95 ( 4h , m ), 2 . 69 ( 2h , t , j = 6 . 8 hz ), 3 . 82 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 7 hz ), 4 . 61 ( 2h , t , j = 6 . 9 hz ), 6 . 83 - 7 . 02 ( 4h , m ), 7 . 59 - 7 . 65 ( 3h , m ). a dichloromethane solution ( 6 ml ) of 1 -( 3 - aminopropyl )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 645 mg , 1 . 67 mmol ) was ice - cooled . triethylamine ( 253 mg , 2 . 5 mmol ) and chloroacetyl chloride ( 207 mg , 1 . 83 mmol ) were added to the solution and stirred at room temperature for 2 hours . water was added to the reaction mixture , followed by extraction using dichloromethane . the thus - obtained organic layer was condensed , and the residue was then purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 4 : 1 → 2 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a white powder of 2 - chloro - n -{ 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propyl } acetamide ( 372 mg , yield : 48 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 3 hz ), 1 . 86 - 2 . 09 ( 4h , m ), 3 . 33 ( 2h , q , j = 6 . 9 hz ), 3 . 83 ( 3h , s ), 4 . 01 ( 2h , s ), 4 . 04 ( 2h , t , j = 6 . 8 hz ), 4 . 56 ( 2h , t , j = 6 . 9 hz ), 6 . 66 ( 1h , brs ), 6 . 86 - 6 . 96 ( 3h , m ), 7 . 03 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 52 ( 1h , s ), 7 . 61 ( 2h , d , j = 8 . 8 hz ). 2 - chloro - n -{ 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propyl } acetamide ( 370 mg , 0 . 8 mmol ) was suspended in acetonitrile ( 12 ml ). 1 -( 2 - methoxyethyl ) piperazine ( 138 mg , 0 . 96 mmol ), triethylamine ( 162 mg , 1 . 6 mmol ) and acetonitrile ( 2 ml ) were added to the suspension , and stirred at 70 to 80 ° c . for 6 hours . the resulting mixture was concentrated under reduced pressure , and the residue was subjected to extraction using ethyl acetate . the extract was then sequentially washed with water , an aqueous saturated sodium chloride solution , and an aqueous saturated sodium bicarbonate solution . the washed product was concentrated under reduced pressure , and the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 30 : 1 → 10 : 1 ). the purified product was concentrated under reduced pressure , and the residue was then dissolved in ethyl acetate ( 5 ml ). a 4n hydrogen chloride ethyl acetate solution ( 0 . 19 ml ) was added thereto and stirred , and then the mixture was concentrated to dryness under reduced pressure , giving a pale yellow amorphous solid of n -{ 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propyl }- 2 -[ 4 -( 2 - methoxyethyl ) piperazin - 1 - yl ] acetamide hydrochloride ( 200 mg ). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 3 hz ), 1 . 78 - 1 . 89 ( 4h , m ), 2 . 50 - 3 . 00 ( 4h , m ), 2 . 96 - 3 . 20 ( 8h , m ), 3 . 25 ( 3h , s ), 3 . 62 - 3 . 66 ( 4h , m ), 3 . 75 ( 3h , s ), 3 . 98 - 4 . 04 ( 2h , m ), 4 . 56 ( 2h , t , j = 6 . 4 hz ), 6 . 91 - 7 . 02 ( 3h , m ), 7 . 24 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 60 ( 2h , d , j = 8 . 8 hz ), 8 . 00 ( 1h , s ), 8 . 07 ( 1h , brs ). the above compound was prepared in the same manner as in example 17 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 - 1 . 13 ( 3h , m ), 1 . 70 - 2 . 00 ( 6h , m ), 3 . 39 ( 2h , t , j = 6 . 3 hz ), 3 . 83 ( 3h , s ), 4 . 03 ( 2h , t , j = 6 . 7 hz ), 4 . 53 ( 2h , t , j = 6 . 8 hz ), 6 . 86 - 7 . 03 ( 4h , m ), 7 . 49 ( 1h , s ), 7 . 57 - 7 . 63 ( 2h , m ). the above compound was prepared in the same manner as in example 18 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 98 ( 3h , t , j = 7 . 3 hz ), 1 . 27 - 1 . 35 ( 2h , m ), 1 . 62 - 1 . 82 ( 4h , m ), 2 . 13 - 2 . 19 ( 6h , m ), 3 . 44 - 3 . 47 ( 4h , m ), 3 . 73 ( 3h , s ), 3 . 98 ( 2h , t , j = 6 . 5 hz ), 4 . 49 ( 2h , t , j = 6 . 8 hz ), 6 . 89 - 6 . 99 ( 3h , m ), 7 . 19 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 57 ( 2h , d , j = 8 . 6 hz ), 7 . 95 ( 1h , s ). the above compound was prepared in the same manner as in example 18 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 27 - 1 . 32 ( 2h , m ), 1 . 62 - 1 . 65 ( 2h , m ), 1 . 79 ( 2h , q , j = 6 . 9 hz ), 2 . 07 ( 3h , s ), 2 . 11 - 2 . 21 ( 10h , m ), 3 . 74 ( 3h , s ), 4 . 00 ( 2h , t , j = 6 . 5 hz ), 4 . 49 ( 2h , t , j = 6 . 8 hz ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 21 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 6 hz ), 7 . 96 ( 1h , s ). the above compound was prepared in the same manner as in example 94 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 96 ( 3h , t , j = 7 . 3 hz ), 1 . 50 - 1 . 80 ( 6h , m ), 3 . 57 ( 2h , t , j = 6 . 3 hz ), 3 . 76 ( 3h , s ), 3 . 97 ( 2h , t , j = 6 . 7 hz ), 4 . 49 ( 2h , t , j = 6 . 8 hz ), 6 . 88 - 6 . 95 ( 3h , m ), 7 . 18 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 60 ( 2h , d , j = 8 . 7 hz ), 7 . 80 - 7 . 90 ( 4h , m ), 8 . 01 ( 1h , s ). the above compound was prepared in the same manner as in example 95 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 3 hz ), 1 . 36 - 1 . 60 ( 4h , m ), 1 . 75 - 1 . 95 ( 4h , m ), 2 . 69 ( 2h , t , j = 6 . 9 hz ), 3 . 82 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 6 hz ), 4 . 50 ( 2h , t , j = 7 . 3 hz ), 6 . 83 - 7 . 02 ( 4h , m ), 7 . 50 ( 1h , s ), 7 . 60 ( 2h , d , j = 8 . 5 hz ). the above compound was prepared in the same manner as in example 94 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 08 ( 3h , t , j = 7 . 3 hz ), 1 . 20 - 1 . 77 ( 8h , m ), 1 . 83 - 1 . 94 ( 2h , m ), 3 . 65 ( 2h , t , j = 6 . 9 hz ), 3 . 82 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 5 hz ), 4 . 46 ( 2h , t , j = 7 . 3 hz ), 6 . 83 - 7 . 04 ( 4h , m ), 7 . 49 ( 1h , s ), 7 . 61 ( 2h , d , j = 8 . 7 hz ), 7 . 68 - 7 . 83 ( 4h , m ). the above compound was prepared in the same manner as in example 95 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 3 hz ), 1 . 30 - 1 . 80 ( 10h , m ), 1 . 87 - 1 . 95 ( 2h , m ), 2 . 65 ( 2h , t , j = 6 . 4 hz ), 3 . 83 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 6 hz ), 4 . 47 ( 2h , t , j = 7 . 5 hz ), 6 . 88 - 7 . 03 ( 4h , m ), 7 . 50 ( 1h , s ), 7 . 62 ( 2h , d , j = 8 . 7 hz ). the above compound was prepared in the same manner as in example 17 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 81 - 2 . 01 ( 2h , m ), 3 . 83 ( 3h , s ), 3 . 84 - 3 . 89 ( 2h , t , j = 6 . 3 hz ), 4 . 00 - 4 . 05 ( 2h , t , j = 6 . 7 hz ), 4 . 74 - 4 . 79 ( 2h , t , j = 6 . 3 hz ), 6 . 89 - 7 . 04 ( 4h , m ), 7 . 54 ( 1h , s ), 7 . 59 - 7 . 62 ( 2h , d , j = 8 . 8 hz ). potassium carbonate ( 2 . 1 g , 15 . 2 mmol ) and 4 -( 2 - chloroethyl ) morpholine hydrochloride ( 1 . 36 g , 7 . 31 mmol ) were added to an n - methylpyrrolidone ( nmp ) solution ( 5 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 1 . 0 g , 3 . 05 mmol ) and then stirred at 50 to 60 ° c . for 45 hours . water and ethyl acetate were added to the reaction mixture , followed by separation . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution twice , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 50 : 1 → 30 : 1 ). the purified product was concentrated under reduced pressure , and the residue was recrystallized from ethyl acetate , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 1 -( 2 - morpholin - 4 - ylethyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 1 . 01 g , yield : 75 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 3 hz ), 1 . 78 - 1 . 87 ( 2h , m ), 2 . 33 - 2 . 36 ( 4h , m ), 2 . 59 ( 2h , t , j = 5 . 6 hz ), 3 . 43 - 3 . 47 ( 4h , m ), 3 . 77 ( 3h , s ), 4 . 05 ( 2h , t , j = 6 . 5 hz ), 4 . 66 ( 2h , t , j = 5 . 7 hz ), 6 . 94 - 7 . 02 ( 3h , m ), 7 . 25 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 60 ( 2h , d , j = 8 . 8 hz ), 7 . 95 ( 1h , s ). the above compound was prepared in the same manner as in example 94 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 3 hz ), 1 . 85 - 2 . 01 ( 2h , m ), 3 . 76 ( 3h , s ), 4 . 03 - 4 . 12 ( 4h , m ), 4 . 84 ( 2h , t , j = 5 . 6 hz ), 6 . 84 - 6 . 89 ( 3h , m ), 6 . 92 - 7 . 00 ( 1h , m ), 7 . 56 ( 2h , d , j = 8 . 6 hz ), 7 . 68 - 7 . 79 ( 5h , m ). the above compound was prepared in the same manner as in example 95 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 3 hz ), 1 . 36 ( 2h , brs ), 1 . 84 - 1 . 95 ( 2h , m ), 3 . 10 ( 2h , t , j = 6 . 0 hz ), 3 . 82 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 7 hz ), 4 . 54 ( 2h , t , j = 6 . 1 hz ), 6 . 84 - 7 . 02 ( 4h , m ), 7 . 60 - 7 . 64 ( 3h , m ). a dmf solution ( 0 . 5 ml ) of n -( tert - butoxycarbonyl )- l - serine ( 174 mg , 0 . 85 mmol ), triethylamine ( 198 mg , 1 . 96 mmol ), diethyl phosphorocyanidate ( depc , 176 mg , 0 . 97 mmol ) and dmf ( 0 . 5 ml ) were sequentially added to a dmf solution ( 1 ml ) of 1 -( 2 - aminoethyl )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 300 mg , 0 . 81 mmol ) while ice - cooling , and stirred at room temperature for 20 hours . water was added to the reaction mixture and then subjected to extraction using ethyl acetate . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution twice . the washed product was dried over anhydrous sodium sulfate and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 40 : 1 → 30 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a white amorphous solid of tert - butyl (( s )- 1 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethylcarbamoyl }- 2 - hydroxyethyl ) carbamate ( 338 mg , yield : 75 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 09 ( 3h , t , j = 7 . 3 hz ), 1 . 38 ( 9h , s ), 1 . 87 - 1 . 95 ( 2h , m ), 3 . 08 ( 1h , brs ), 3 . 45 - 3 . 60 ( 3h , m ), 3 . 69 - 3 . 79 ( 1h , m ), 3 . 76 ( 3h , s ), 3 . 99 ( 2h , t , j = 6 . 8 hz ), 4 . 34 ( 1h , brs ), 4 . 64 ( 2h , brs ), 5 . 87 ( 1h , d , j = 7 . 9 hz ), 6 . 56 ( 1h , dd , j = 8 . 9 hz , 11 . 7 hz ), 6 . 73 ( 2h , d , j = 8 . 7 hz ), 6 . 91 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 36 ( 2h , d , j = 8 . 7 hz ), 7 . 46 ( 1h , s ), 8 . 26 ( 1h , brs ). the above compound was prepared in the same manner as in example 109 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 0 . 90 - 1 . 05 ( 4h , m ), 1 . 12 ( 3h , t , j = 7 . 3 hz ), 1 . 37 ( 9h , s ), 1 . 41 ( 9h , s ), 1 . 48 - 1 . 60 ( 2h , m ), 1 . 87 - 1 . 99 ( 2h , m ), 2 . 80 - 2 . 90 ( 2h , m ), 3 . 40 - 3 . 50 ( 1h , m ), 3 . 80 ( 3h , s ), 3 . 91 - 4 . 24 ( 5h , m ), 4 . 53 ( 1h , brs ), 5 . 27 - 5 . 33 ( 1h , m ), 5 . 75 - 5 . 78 ( 1h , m ), 6 . 43 - 6 . 52 ( 1h , m ), 6 . 84 - 6 . 90 ( 3h , m ), 7 . 39 - 7 . 48 ( 3h , m ), 8 . 09 ( 1h , brs ). the above compound was prepared in the same manner as in example 109 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 3 hz ), 1 . 39 ( 9h , s ), 1 . 85 - 2 . 01 ( 2h , m ), 2 . 72 - 2 . 90 ( 2h , m ), 3 . 50 - 3 . 60 ( 1h , m ), 3 . 76 ( 3h , s ), 3 . 77 - 3 . 86 ( 1h , m ), 4 . 02 ( 2h , t , j = 6 . 7 hz ), 4 . 30 - 4 . 43 ( 2h , m ), 4 . 82 - 4 . 88 ( 1h , m ), 5 . 82 ( 1h , brs ), 6 . 57 ( 1h , s ), 6 . 72 - 6 . 84 ( 3h , m ), 6 . 94 - 6 . 99 ( 1h , m ), 7 . 08 ( 1h , s ), 7 . 37 - 7 . 45 ( 3h , m ), 8 . 05 ( 1h , brs ). the above compound was prepared in the same manner as in example 96 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 12 ( 3h , t , j = 7 . 3 hz ), 1 . 90 - 1 . 98 ( 2h , m ), 3 . 64 - 3 . 70 ( 2h , m ), 3 . 83 ( 3h , s ), 3 . 98 ( 2h , s ), 4 . 03 ( 2h , t , j = 6 . 6 hz ), 4 . 72 - 4 . 76 ( 2h , m ), 6 . 51 ( 1h , dd , j = 9 . 0 hz , 11 . 7 hz ), 6 . 78 ( 2h , d , j = 8 . 8 hz ), 6 . 89 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 25 - 7 . 32 ( 3h , m ), 8 . 54 ( 1h , brs ). the above compound was prepared in the same manner as in example 97 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 3 hz ), 1 . 75 - 1 . 96 ( 7h , m ), 2 . 50 - 2 . 80 ( 2h , m ), 2 . 85 - 3 . 25 ( 10h , m ), 3 . 76 ( 3h , s ), 3 . 80 - 3 . 95 ( 4h , m ), 4 . 04 ( 2h , t , j = 6 . 5 hz ), 4 . 69 ( 2h , brs ), 6 . 93 - 7 . 02 ( 3h , m ), 7 . 25 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 64 ( 2h , d , j = 8 . 8 hz ), 7 . 87 ( 1h , s ), 8 . 69 ( 1h , brs ). the above compound was prepared in the same manner as in example 97 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 98 ( 3h , t , j = 7 . 3 hz ), 1 . 76 - 1 . 85 ( 2h , m ), 2 . 95 - 3 . 05 ( 4h , m ), 3 . 25 ( 3h , s ), 3 . 10 - 3 . 30 ( 2h , m ), 3 . 39 - 3 . 64 ( 10h , m ), 3 . 75 ( 3h , s ), 4 . 02 ( 2h , t , j = 6 . 5 hz ), 4 . 68 ( 2h , brs ), 6 . 91 - 7 . 01 ( 3h , m ), 7 . 23 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 59 ( 2h , d , j = 8 . 7 hz ), 7 . 86 ( 1h , s ), 8 . 57 ( 1h , t , j = 5 . 4 hz ). a 4n hydrogen chloride ethyl acetate solution ( 5 ml ) was added to an ethanol solution ( 5 ml ) of tert - butyl (( s )- 1 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethylcarbamoyl }- 2 - hydroxyethyl ) carbamate ( 330 mg , 0 . 6 mmol ) and stirred at room temperature for 14 hours . the resulting mixture was concentrated under reduced pressure . water was added to the residue , which was then washed with ethyl acetate . a 2n aqueous sodium hydroxide solution ( 6 ml ) was added to the water layer to adjust its ph to 11 , followed by extraction with dichloromethane . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution , dried over anhydrous magnesium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 20 : 1 → 15 : 1 ). the purified product was concentrated under reduced pressure , the residue was dissolved in ethanol ( 3 ml ) and ethyl acetate ( 3 ml ), and a 4n hydrogen chloride ethylacetate solution ( 0 . 1 ml ) was then added thereto . the mixture was stirred and concentrated to dryness under reduced pressure , and recrystallized from ethyl acetate , giving a white powder of ( s )- 2 - amino - n -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethyl }- 3 - hydroxypropionamide hydrochloride ( 145 mg , yield : 50 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 3 hz ), 1 . 76 - 1 . 88 ( 2h , m ), 3 . 23 - 3 . 50 ( 5h , m ), 3 . 75 ( 3h , s ), 4 . 05 ( 2h , t , j = 6 . 5 hz ), 4 . 53 - 4 . 73 ( 2h , m ), 5 . 40 - 5 . 42 ( 1h , m ), 6 . 91 - 7 . 03 ( 3h , m ), 7 . 26 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 58 ( 2h , d , j = 8 . 7 hz ), 7 . 80 ( 1h , s ), 8 . 00 ( 2h , brs ), 8 . 58 ( 1h , t , j = 5 . 2 hz ). the above compound was prepared in the same manner as in example 115 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 00 - 1 . 50 ( 6h , m ), 1 . 77 - 1 . 86 ( 2h , m ), 2 . 57 ( 2h , t , j = 7 . 2 hz ), 3 . 32 - 3 . 44 ( 3h , m ), 3 . 50 - 3 . 70 ( 4h , m ), 3 . 74 ( 3h , s ), 4 . 00 - 4 . 05 ( 2h , m ), 4 . 53 - 4 . 82 ( 2h , m ), 6 . 91 - 7 . 03 ( 3h , m ), 7 . 24 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 60 ( 2h , d , j = 8 . 7 hz ), 7 . 86 ( 1h , s ), 8 . 61 ( 1h , brs ). the above compound was prepared in the same manner as in example 115 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 3 hz ), 1 . 78 - 1 . 86 ( 2h , m ), 2 . 26 ( 1h , dd , j = 9 . 3 hz , 14 . 5 hz ), 2 . 65 ( 1h , dd , j = 3 . 8 hz , 14 . 5 hz ), 3 . 26 ( 1h , dd , j = 3 . 8 hz , 9 . 3 hz ), 3 . 30 - 3 . 55 ( 4h , m ), 3 . 73 ( 3h , s ), 3 . 98 - 4 . 05 ( 2h , m ), 4 . 64 ( 2h , brs ), 6 . 61 ( 1h , s ), 6 . 87 - 7 . 01 ( 3h , m ), 7 . 22 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 48 ( 1h , s ), 7 . 57 ( 2h , d , j = 8 . 7 hz ), 7 . 79 ( 1h , s ), 8 . 13 ( 1h , brs ). the above compound was prepared in the same manner as in example 3 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 09 - 1 . 15 ( 3h , t , j = 7 . 4 hz ), 1 . 82 - 2 . 03 ( 2h , m ), 2 . 38 - 2 . 64 ( 2h , m ), 3 . 85 ( 3h , s ), 4 . 02 - 4 . 07 ( 2h , t , j = 6 . 7 hz ), 4 . 55 - 4 . 61 ( 2h , t , j = 7 . 2 hz ), 4 . 96 - 5 . 15 ( 2h , m ), 5 . 60 - 5 . 89 ( 1h , m ), 6 . 79 - 7 . 08 ( 4h , m ), 7 . 49 ( 1h , s ), 7 . 61 - 7 . 64 ( 2h , d , j = 8 . 8 hz ). a dioxane ( 30 ml )- water ( 10 ml ) solution of 1 - but - 3 - enyl - 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 1 . 2 g , 3 . 15 mmol ) was prepared . a 2 . 6 - lutidine ( 0 . 674 g , 6 . 29 mmol ), 4 % osmic acid solution ( 1 ml ) and sodium periodate ( 2 . 69 g , 12 . 6 mmol ) were added to the solution , and stirred at room temperature for 30 minutes . water was added to the reaction mixture , then the mixture was extracted with dichloromethane , washed with water , and then dried over anhydrous sodium sulfate . the dried product was concentrated under reduced pressure , and the residue was then purified using silica gel column chromatography ( n - hexane : ethyl acetate = 100 : 0 → 0 : 100 ). the purified product was concentrated to dryness under reduced pressure , giving a pale yellow powder of 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propionaldehyde ( 1 . 0 g , yield : 83 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 - 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 94 ( 2h , m ), 3 . 04 - 3 . 92 ( 2h , t , j = 6 . 6 hz ), 3 . 83 ( 3h , s ), 3 . 99 - 4 . 04 ( 2h , t , j = 6 . 8 hz ), 4 . 76 - 4 . 81 ( 2h , t , j = 6 . 6 hz ), 6 . 82 - 7 . 06 ( 4h , m ), 7 . 49 - 7 . 68 ( 3h , m ), 9 . 81 ( 1h , s ). 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propionaldehyde ( 1 . 0 g , 2 . 61 mmol ) was dissolved in water ( 10 ml ), tert - butyl alcohol ( 20 ml ) and dichloromethane ( 20 ml ). sodium chlorite ( 3 . 2 g , 35 . 4 mmol ), 2 - methyl - 2 - butene ( 19 . 86 gm , 283 mmol ) and sodium - dihydrogenphosphate dihydrate ( 2 g , 2 . 61 mmol ) were added to the resulting solution , and the solution was stirred at room temperature for 1 hour . water was added to the reaction mixture , the mixture was extracted with dichloromethane , and then washed with water and dried over anhydrous sodium sulfate . the dried product was concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 50 : 50 → 0 : 100 ). the purified product was concentrated to dryness under reduced pressure , giving a pale yellow powder of 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propionic acid ( 710 mg , yield : 68 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 96 - 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 62 - 1 . 91 ( 2h , m ), 2 . 75 - 2 . 80 ( 2h , t , j = 6 . 9 hz ), 3 . 76 ( 3h , s ), 4 . 01 - 4 . 07 ( 2h , t , j = 6 . 6 hz ), 4 . 69 - 4 . 75 ( 2h , t , j = 7 . 0 hz ), 6 . 90 - 7 . 03 ( 3h , m ), 7 . 22 - 7 . 29 ( 1h , m ), 7 . 59 - 7 . 63 ( 2h , d , j = 8 . 8 hz ), 8 . 03 ( 1h , s ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 25 - 1 . 50 ( 2h , m ), 1 . 75 - 1 . 90 ( 2h , m ), 2 . 20 - 2 . 45 ( 2h , m ), 2 . 50 - 3 . 00 ( 15h , m ), 3 . 78 ( 3h , s ), 3 . 98 - 4 . 05 ( 2h , m ), 4 . 75 - 5 . 00 ( 2h , m ), 6 . 94 - 7 . 05 ( 3h , m ), 7 . 26 - 7 . 40 ( 1h , m ), 7 . 58 - 7 . 62 ( 2h , d , j = 8 . 7 hz ), 7 . 88 - 7 . 92 ( 2h , m ). 1 -( 2 - hydroxyethyl )- 4 - methylpiperazine ( 199 mg , 1 . 38 mmol ), dicyclohexylcarbodiimide ( 310 mg , 1 . 50 mmol ) and 4 - dimethylaminopyridine ( 168 mg , 1 . 38 mmol ) were added to a dmf solution ( 10 ml ) of 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propionic acid ( 500 mg , 1 . 25 mmol ) and stirred overnight at room temperature . water was added to the reaction mixture , the mixture was extracted with dichloromethane and washed with water and then dried over anhydrous sodium sulfate . the dried product was concentrated under reduced pressure , and the resulting residue was purified using silica gel column chromatography ( ethyl acetate → dichloromethane : methanol = 10 : 1 ). the residue was dissolved in ethyl acetate and a 4n hydrogen chloride ethylacetate solution was added thereto and stirred . the mixture was concentrated to dryness under reduced pressure , giving a pale yellow powder of 2 -( 4 - methyl piperazin - 1 - yl ) ethyl 3 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] propionate dihydrochloride ( 110 mg , yield : 17 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 69 - 1 . 88 ( 2h , m ), 2 . 78 ( 3h , s ), 2 . 87 - 3 . 04 ( 2h , m ), 3 . 10 - 3 . 60 ( 10h , m ), 3 . 77 ( 3h , s ), 4 . 01 - 4 . 11 ( 2h , t , j = 6 . 8 hz ), 4 . 27 - 4 . 44 ( 2h , m ), 4 . 67 - 4 . 94 ( 2h , m ), 6 . 76 - 7 . 09 ( 3h , m ), 7 . 16 - 7 . 33 ( 1h , m ), 7 . 58 - 7 . 63 ( 2h , d , j = 8 . 8 hz ), 8 . 07 ( 1h , s ). the above compound was prepared in the same manner as in example 122 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 - 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 65 - 1 . 88 ( 2h , m ), 2 . 68 ( 3h , s ), 2 . 70 ( 3h , s ), 2 . 93 - 3 . 10 ( 2h , m ), 3 . 11 - 3 . 29 ( 4h , m ), 3 . 76 ( 3h , s ), 4 . 04 - 4 . 09 ( 2h , t , j = 6 . 6 hz ), 4 . 68 - 4 . 94 ( 2h , m ), 6 . 90 - 7 . 06 ( 3h , m ), 7 . 26 - 7 . 31 ( 1h , m ), 7 . 61 - 7 . 64 ( 2h , d , j = 8 . 7 hz ), 8 . 00 ( 1h , s ), 10 . 41 - 10 . 92 ( 1h , br ). the above compound was prepared in the same manner as in example 17 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 09 - 1 . 15 ( 3h , t , j = 7 . 4 hz ), 1 . 82 - 2 . 03 ( 2h , m ), 3 . 67 - 3 . 72 ( 2h , t , j = 6 . 8 hz ), 3 . 84 ( 3h , s ), 4 . 01 - 4 . 07 ( 2h , t , j = 6 . 8 hz ), 4 . 79 - 4 . 85 ( 2h , t , j = 6 . 8 hz ), 6 . 88 - 7 . 06 ( 4h , m ), 7 . 53 ( 1h , s ), 7 . 58 - 7 . 63 ( 2h , m ). 1 -( 2 - chloroethyl )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 3 . 5 g , 8 . 98 mmol ), methyl 3 - mercaptopropionate ( 1 . 19 g , 9 . 88 mmol ), and sodium iodide ( 1 . 48 g , 9 . 88 mmol ) were added to dmf ( 30 ml ) and stirred at 80 ° c . for 5 hours . water and ethyl acetate were added to the reaction mixture , followed by separation . the thus - obtained organic layer was washed with water , dried over anhydrous magnesium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane ). the purified product was concentrated to dryness under reduced pressure , giving a pale yellow powder of methyl 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethylsulfanyl } propionate ( 3 . 2 g , yield : 75 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 2 . 65 - 2 . 80 ( 2h , m ), 2 . 54 - 2 . 60 ( 2h , t , j = 7 . 2 hz ), 2 . 70 - 2 . 76 ( 2h , t , j = 7 . 2 hz ), 2 . 88 - 2 . 93 ( 2h , t , j = 6 . 9 hz ), 3 . 56 ( 3h , s ), 3 . 78 ( 3h , s ), 4 . 03 - 4 . 09 ( 2h , t , j = 6 . 6 hz ), 4 . 68 - 4 . 74 ( 2h , t , j = 6 . 9 hz ), 6 . 85 - 7 . 08 ( 3h , m ), 7 . 25 - 7 . 30 ( 1h , m ), 7 . 52 - 7 . 67 ( 2h , m ), 8 . 06 ( 1h , s ). lithium hydroxide mono - hydrate ( 31 mg , 0 . 74 mmol ) and water ( 5 ml ) were added to an acetonitrile solution ( 10 ml ) of methyl 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethylsulfanyl } propionate ( 175 mg , 0 . 37 mmol ), and the mixture was stirred at room temperature for 2 hours . the reaction mixture was washed with ethyl acetate , and then 2n hydrochloric acid was added to the water layer to make the mixture acidic . the generated insoluble matter was separated , washed with water and then dried , giving a white powder of 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethylsulfanyl } propionic acid ( 140 mg , yield : 82 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 96 - 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 70 - 1 . 90 ( 2h , m ), 2 . 42 - 2 . 47 ( 2h , t , j = 7 . 0 hz ), 2 . 64 - 2 . 70 ( 2h , t , j = 7 . 0 hz ), 2 . 85 - 2 . 90 ( 2h , t , j = 6 . 8 hz ), 3 . 74 ( 3h , s ), 3 . 99 - 4 . 04 ( 2h , t , j = 6 . 6 hz ), 4 . 65 - 4 . 70 ( 2h , t , j = 6 . 8 hz ), 6 . 91 - 7 . 02 ( 3h , m ), 7 . 20 - 7 . 26 ( 1h , m ), 7 . 55 - 7 . 60 ( 2h , m ), 8 . 01 ( 1h , s ), 11 . 35 - 12 . 84 ( 1h , br ). 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethylsulfanyl } propionic acid ( 2 . 26 g , 4 . 92 mmol ) was dissolved in a mixed solvent of dichloromethane ( 100 ml ) and methanol ( 20 ml ), m - chloroperbenzoic acid ( mcpba , purity : 70 %, 2 . 55 g , 10 . 33 mmol ) was added thereto , and the mixture was then stirred at room temperature for 1 hour . the resulting reaction mixture was ice - cooled . an aqueous saturated sodium hydrogen sulfite solution ( 50 ml ) was added to the reaction mixture , followed by extraction with dichloromethane . the thus - obtained organic layer was washed with water and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 100 : 0 → 100 : 10 ). the purified product was concentrated under reduced pressure and subjected to recrystallization from ethyl acetate - n - hexane , giving a pale yellow powder of 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethanesulfonyl } propionic acid ( 2 . 2 g , yield : 91 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 - 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 73 - 1 . 96 ( 2h , m ), 2 . 64 - 2 . 70 ( 2h , t , j = 7 . 7 hz ), 3 . 37 - 3 . 43 ( 2h , t , j = 7 . 7 hz ), 3 . 66 - 3 . 72 ( 2h , t , j = 6 . 7 hz ), 3 . 77 ( 3h , s ), 4 . 05 - 4 . 11 ( 2h , t , j = 6 . 8 hz ), 4 . 94 - 4 . 99 ( 2h , t , j = 6 . 7 hz ), 6 . 93 - 7 . 06 ( 3h , m ), 7 . 27 - 7 . 30 ( 1h , m ), 7 . 59 - 7 . 63 ( 2h , m ), 8 . 02 ( 1h , s ). the above compound was prepared in the same manner as in example 127 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 84 - 2 . 03 ( 2h , m ), 2 . 84 - 2 . 89 ( 2h , t , j = 7 . 0 hz ), 3 . 27 - 3 . 33 ( 2h , t , j = 7 . 0 hz ), 3 . 51 - 3 . 57 ( 2h , t , j = 6 . 9 hz ), 3 . 70 ( 3h , s ), 3 . 83 ( 3h , s ), 4 . 05 - 4 . 09 ( 2h , t , j = 6 . 8 hz ), 4 . 95 - 5 . 00 ( 2h , t , j = 6 . 9 hz ), 6 . 86 - 6 . 94 ( 3h , m ), 7 . 01 - 7 . 08 ( 1h , m ), 7 . 58 - 7 . 64 ( 2h , m ), 7 . 66 ( 1h , s ). the above compound was prepared in the same manner as in example 125 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 60 - 1 . 75 ( 2h , m ), 1 . 84 - 2 . 03 ( 2h , m ), 2 . 40 - 2 . 60 ( 2h , m ), 2 . 84 - 2 . 89 ( 2h , m ), 3 . 60 - 3 . 75 ( 2h , m ), 3 . 70 ( 3h , s ), 4 . 05 - 4 . 09 ( 2h , t , j = 6 . 8 hz ), 4 . 62 - 4 . 80 ( 2h , m ), 6 . 86 - 6 . 94 ( 3h , m ), 7 . 01 - 7 . 08 ( 1h , m ), 7 . 58 - 7 . 64 ( 2h , m ), 7 . 66 ( 1h , s ). the above compound was prepared in the same manner as in example 127 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 - 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 66 - 1 . 94 ( 4h , m ), 3 . 38 - 3 . 53 ( 2h , m ), 3 . 56 - 3 . 71 ( 2h , m ), 3 . 77 ( 3h , s ), 4 . 03 - 4 . 14 ( 4h , m ), 4 . 67 - 4 . 70 ( 1h , t , j = 5 . 1 hz ), 4 . 93 - 4 . 99 ( 2h , t , j = 6 . 7 hz ), 6 . 93 - 7 . 06 ( 3h , m ), 7 . 26 - 7 . 33 ( 1h , m ), 7 . 59 - 7 . 62 ( 2h , m ), 8 . 01 ( 1h , s ). o - iodoxybenzoic acid ( ibx , 1 . 9 g , 6 . 78 mmol ) was added to a dimethyl sulfoxide ( dmso ) solution ( 3 ml ) of 5 - fluoro - 1 -[ 2 -( 3 - hydroxypropane - 1 - sulfonyl ) ethyl ]- 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 2 . 7 g , 5 . 65 mmol ) and stirred overnight at room temperature . water and ethyl acetate were added to the reaction mixture . subsequently , insoluble matter was filtered off , and the filtrate was then separated . the thus - obtained organic layer was washed with water and concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( n - hexane : ethyl acetate = 2 : 1 → 0 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a white powder of 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethanesulfonyl } propionaldehyde ( 1 . 8 g , yield : 67 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 - 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 82 - 2 . 03 ( 2h , m ), 2 . 80 - 3 . 01 ( 2h , m ), 3 . 45 - 3 . 50 ( 2h , m ), 3 . 60 - 3 . 70 ( 2h , m ), 3 . 78 ( 3h , s ), 4 . 03 - 4 . 09 ( 2h , t , j = 6 . 8 hz ), 4 . 90 - 5 . 10 ( 2h , m ), 6 . 93 - 7 . 06 ( 3h , m ), 7 . 26 - 7 . 33 ( 1h , m ), 7 . 59 - 7 . 62 ( 2h , m ), 8 . 01 ( 1h , s ), 9 . 67 ( 1h , s ). the above compound was prepared in the same manner as in example 125 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 69 - 1 . 94 ( 2h , m ), 2 . 69 ( 3h , s ), 2 . 71 ( 3h , s ), 2 . 85 - 3 . 04 ( 4h , m ), 3 . 11 - 3 . 28 ( 2h , m ), 3 . 76 ( 3h , s ), 4 . 03 - 4 . 08 ( 2h , t , j = 6 . 8 hz ), 4 . 64 - 4 . 87 ( 2h , m ), 6 . 73 - 7 . 09 ( 3h , m ), 7 . 12 - 7 . 34 ( 1h , m ), 7 . 63 - 7 . 67 ( 2h , d , j = 8 . 8 hz ), 8 . 14 ( 1h , s ), 10 . 62 - 11 . 04 ( 1h , br ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 - 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 1 . 96 ( 2h , m ), 2 . 25 ( 3h , s ), 2 . 29 - 2 . 45 ( 4h , m ), 2 . 75 - 2 . 80 ( 2h , t , j = 7 . 4 hz ), 3 . 30 - 3 . 50 ( 6h , m ), 3 . 65 - 3 . 70 ( 2h , t , j = 6 . 7 hz ), 4 . 05 - 4 . 11 ( 2h , t , j = 6 . 7 hz ), 4 . 95 - 5 . 00 ( 2h , t , j = 6 . 7 hz ), 6 . 91 - 7 . 06 ( 3h , m ), 7 . 27 - 7 . 32 ( 1h , m ), 7 . 60 - 7 . 64 ( 2h , d , j = 8 . 8 hz ), 8 . 03 ( 1h , s ). n - methylpiperazine ( 0 . 455 mg , 4 . 54 mmol ) was added to a methanol solution ( 20 ml ) of 3 -{ 2 -[ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] ethanesulfonyl } propionaldehyde ( 1 . 8 g , 3 . 79 mmol ) while ice - cooling , and then the resulting mixture was stirred at room temperature for 1 hour . sodium cyanoborohydride ( 0 . 238 g , 3 . 79 mmol ) and acetic acid ( 2 ml ) were added to the resulting mixture and stirred at room temperature for 3 hours . water was added to the reaction mixture , then the mixture was subjected to extraction using ethyl acetate . the extract was washed with an aqueous saturated sodium bicarbonate solution and concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 100 : 0 → 10 : 1 ). the purified product was concentrated under reduced pressure , and a 4n hydrogen chloride ethylacetate solution was added to an ethyl acetate solution of the residue . the thus - generated insoluble matter was separated , giving a yellow powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 1 -{ 2 -[ 3 -( 4 - methylpiperazin - 1 - yl ) propane - 1 - sulfonyl ] ethyl }- 8 - propoxy - 1h - quinolin - 4 - one dihydrochloride ( 360 mg , yield : 15 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 98 - 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 1 . 96 ( 2h , m ), 2 . 12 - 2 . 34 ( 2h , m ), 2 . 80 ( 3h , s ), 3 . 00 - 3 . 75 ( 14h , m ), 3 . 77 ( 3h , s ), 4 . 06 - 4 . 12 ( 2h , t , j = 6 . 7 hz ), 4 . 98 - 5 . 03 ( 2h , t , j = 6 . 4 hz ), 6 . 94 - 7 . 07 ( 3h , m ), 7 . 28 - 7 . 33 ( 1h , m ), 7 . 61 - 7 . 64 ( 2h , d , j = 8 . 8 hz ), 8 . 05 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 77 ( 3h , s ), 3 . 87 - 3 . 90 ( 2h , t , j = 4 . 3 hz ), 4 . 35 - 4 . 38 ( 2h , t , j = 4 . 3 hz ), 4 . 58 ( 2h , s ), 6 . 80 - 7 . 00 ( 3h , m ), 7 . 10 - 7 . 32 ( 6h , m ), 7 . 54 - 7 . 57 ( 2h , m ), 7 . 79 - 7 . 82 ( 1h , d , j = 6 . 2 hz ), 11 . 49 ( 1h , d , j = 5 . 2 hz ). 20 % palladium hydroxide / carbon ( 5 . 0 g ) was added to an ethanol solution ( 50 ml ) of 8 -( 2 - benzyloxyethoxy )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 1h - quinolin - 4 - one ( 6 . 3 g , 15 . 0 mmol ), followed by hydrogen substitution . the mixture was stirred at room temperature for 4 hours . after completion of the reaction , the catalyst was removed and the mixture was concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 100 : 0 → 20 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a pale yellow powder of 5 - fluoro - 8 -( 2 - hydroxyethoxy )- 3 -( 4 - methoxyphenyl )- 1h - quinolin - 4 - one ( 5 . 2 g , yield : 99 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 77 ( 3h , s ), 3 . 79 - 3 . 83 ( 2h , t , j = 4 . 7 hz ), 4 . 12 - 4 . 16 ( 2h , t , j = 4 . 7 hz ), 6 . 84 - 6 . 96 ( 3h , m ), 7 . 12 - 7 . 17 ( 1h , m ), 7 . 53 - 7 . 57 ( 2h , d , j = 8 . 8 hz ), 7 . 85 ( 1h , s ). the above compound was prepared in the same manner as in example 120 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 80 ( 3h , s ), 4 . 92 ( 2h , s ), 6 . 85 - 6 . 92 ( 3h , m ), 7 . 11 - 7 . 16 ( 1h , m ), 7 . 53 - 7 . 57 ( 2h , d , j = 8 . 8 hz ), 7 . 80 - 7 . 82 ( 1h , d , j = 6 . 2 hz ), 11 . 46 - 11 . 49 ( 1h , d , j = 6 . 0 hz ), 13 . 10 - 13 . 30 ( 1h , br ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 84 - 0 . 90 ( 7 . 2 hz ), 1 . 10 - 1 . 60 ( 4h , m ), 3 . 15 - 3 . 23 ( 2h , q , j = 6 . 5 hz ), 3 . 76 ( 3h , s ), 4 . 66 ( 2h , s ), 6 . 87 - 6 . 96 ( 3h , m ), 7 . 11 - 7 . 16 ( 1h , m ), 7 . 55 - 7 . 59 ( 2h , d , j = 8 . 5 hz ), 8 . 31 - 8 . 35 ( 1h , t , 5 . 8 hz ), 11 . 68 ( 1h , brs ). the above compound was prepared in the same manner as in example 33 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 2 . 40 - 2 . 50 ( 2h , m ), 3 . 10 - 3 . 14 ( 2h , m ), 4 . 45 ( 2h , s ), 3 . 28 - 3 . 54 ( 4h , m ), 3 . 75 ( 3h , s ), 3 . 80 - 4 . 21 ( 4h , m ), 6 . 84 - 6 . 95 ( 3h , m ), 7 . 10 - 7 . 15 ( 1h , m ), 7 . 51 - 7 . 54 ( 2h , d , j = 8 . 8 hz ), 8 . 20 - 8 . 50 ( 1h , m ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 22 - 1 . 27 ( 3h , t , j = 7 . 1 hz ), 2 . 16 - 2 . 26 ( 2h , m ), 2 . 54 - 2 . 59 ( 2h , t , j = 6 . 6 hz ), 3 . 81 ( 3h , s ), 4 . 10 - 4 . 20 ( 4h , m ), 6 . 75 - 6 . 94 ( 4h , m ), 7 . 55 - 7 . 72 ( 2h , m ), 7 . 72 - 7 . 75 ( 1h , d , j = 6 . 1 hz ), 9 . 49 - 9 . 51 ( 1h , d , j = 5 . 2 hz ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 89 - 2 . 01 ( 2h , m ), 2 . 42 - 2 . 45 ( 2h , m ), 3 . 69 ( 3h , s ), 4 . 05 - 4 . 10 ( 2h , t , j = 6 . 1 hz ), 6 . 76 - 6 . 89 ( 3h , m ), 7 . 02 - 7 . 07 ( 1h , m ), 7 . 45 - 7 . 49 ( 2h , d , j = 8 . 5 hz ), 7 . 71 - 7 . 73 ( 1h , d , j = 5 . 4 hz ), 11 . 21 - 11 . 23 ( 1h , d , j = 4 . 9 hz ), 11 . 6 - 12 . 5 ( 1h , br ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 79 - 0 . 86 ( 3h , t , j = 7 . 1 hz ), 1 . 15 - 1 . 40 ( 4h , m ), 2 . 00 - 2 . 10 ( 2h , m ), 2 . 29 - 2 . 35 ( 2h , t , j = 7 . 3 hz ), 2 . 99 - 3 . 10 ( 2h , m ), 3 . 76 ( 3h , s ), 4 . 10 - 4 . 15 ( 2h , t , j = 6 . 2 hz ), 6 . 84 - 6 . 95 ( 3h , m ), 7 . 10 - 7 . 16 ( 1h , m ), 7 . 52 - 7 . 56 ( 2h , t , j = 8 . 6 hz ), 7 . 70 - 7 . 85 ( 2h , m ), 11 . 27 ( 1h , brs ). the above compound was prepared in the same manner as in example 33 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 2 . 02 - 2 . 07 ( 2h , m ), 2 . 40 - 2 . 43 ( 2h , m ), 2 . 94 - 3 . 26 ( 6h , m ), 3 . 28 - 3 . 54 ( 4h , m ), 3 . 75 ( 3h , s ), 3 . 80 - 4 . 21 ( 4h , m ), 6 . 84 - 6 . 95 ( 3h , m ), 7 . 10 - 7 . 15 ( 1h , m ), 7 . 51 - 7 . 54 ( 2h , d , j = 8 . 8 hz ), 8 . 20 - 8 . 50 ( 1h , m ), 10 . 60 - 11 . 10 ( 1h , br ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 03 - 1 . 09 ( 3h , t , j = 7 . 4 hz ), 1 . 80 - 1 . 91 ( 2h , m ), 3 . 81 - 3 . 85 ( 2h , m ), 4 . 03 - 4 . 08 ( 2h , t , j = 6 . 6 hz ), 4 . 63 ( 2h , s ), 6 . 79 - 6 . 93 ( 4h , m ), 7 . 30 - 7 . 37 ( 5h , m ), 7 . 53 - 7 . 57 ( 2h , m ), 7 . 69 - 7 . 72 ( 1h , d , j = 6 . 1 hz ), 9 . 05 - 9 . 08 ( 1h , d , j = 5 . 7 hz ). the above compound was prepared in the same manner as in example 136 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 06 - 1 . 09 ( 3h , t , j = 7 . 4 hz ), 1 . 81 - 1 . 90 ( 2h , m ), 3 . 70 - 3 . 75 ( 2h , m ), 3 . 99 - 4 . 03 ( 2h , m ), 4 . 09 - 4 . 14 ( 2h , t , j = 6 . 4 hz ), 4 . 80 - 4 . 93 ( 1h , m ), 6 . 86 - 6 . 97 ( 3h , m ), 7 . 13 - 7 . 18 ( 1h , m ), 7 . 53 - 7 . 57 ( 2h , d , j = 8 . 7 hz ), 7 . 79 - 7 . 87 ( 1h , m ), 11 . 0 - 11 . 5 ( 1h , m ). ethyl [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] acetate ( 4 . 0 g , 9 . 6 mmol ) was dissolved in dichloromethane ( 20 ml ). a 1m - boron tribromide dichloromethane solution ( 35 ml , 35 mmol ) was added dropwise to the dissolution at − 10 ° c . after stirring at the same temperature for 2 hours , water was added to the reaction mixture , followed by extraction with dichloromethane . the thus - obtained organic layer was concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 50 : 1 → 15 : 1 ). the purified product was concentrated to dryness under reduced pressure , giving a yellow powder of ethyl [ 5 - fluoro - 3 -( 4 - hydroxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] acetate ( 2 . 7 g , yield : 57 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 97 ( 3h , t , j = 7 . 3 hz ), 1 . 19 ( 3h , t , j = 7 . 1 hz ), 1 . 69 - 1 . 77 ( 2h , m ), 3 . 95 ( 2h , t , j = 6 . 6 hz ), 4 . 14 ( 2h , q , j = 7 . 1 hz ), 5 . 29 ( 2h , s ), 6 . 76 ( 2h , d , j = 8 . 7 hz ), 6 . 97 ( 1h , dd , j = 9 . 0 hz , 11 . 7 hz ), 7 . 21 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 45 ( 2h , d , j = 8 . 7 hz ), 7 . 95 ( 1h , s ), 9 . 41 ( 1h , s ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 98 ( 3h , t , j = 7 . 4 hz ), 1 . 73 - 1 . 82 ( 2h , m ), 3 . 95 ( 2h , t , j = 6 . 6 hz ), 5 . 21 ( 2h , s ), 6 . 76 ( 2h , d , j = 8 . 7 hz ), 6 . 96 ( 1h , dd , j = 9 . 0 hz , 11 . 6 hz ), 7 . 20 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 45 ( 2h , d , j = 8 . 7 hz ), 7 . 95 ( 1h , s ), 9 . 40 ( 1h , s ), 12 . 50 ( 1h , brs ). 4 -( 2 - aminoethyl ) morpholine ( 184 mg , 1 . 41 mmol ), 1 -( 3 - dimethylaminopropyl )- 3 - ethylcarbodiimide hydrochloride ( wsc , 295 mg , 1 . 54 mmol ) and 1 - hydroxybenzotriazole ( hobt , 215 mg , 1 . 41 mmol ) were added to a dmf solution ( 7 ml ) of [ 5 - fluoro - 3 -( 4 - hydroxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ] acetic acid ( 500 mg , 1 . 34 mmol ) and then the mixture was stirred at room temperature for 23 hours . water and triethylamine were added to the reaction mixture to make the reaction mixture basic , followed by extraction using ethyl acetate . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 30 : 1 → 10 : 1 ). the purified product was concentrated under reduced pressure , and the residue was recrystallized from ethyl acetate , giving a white powder of 2 -[ 5 - fluoro - 3 -( 4 - hydroxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ]- n -( 2 - morpholin - 4 - ylethyl ) acetamide ( 157 mg , yield : 24 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 94 ( 3h , t , j = 7 . 3 hz ), 1 . 70 - 1 . 78 ( 2h , m ), 2 . 29 - 2 . 33 ( 6h , m ), 3 . 17 ( 2h , q , j = 6 . 3 hz ), 3 . 44 - 3 . 52 ( 4h , m ), 3 . 92 ( 2h , t , j = 6 . 8 hz ), 5 . 12 ( 2h , s ), 6 . 75 ( 2h , d , j = 8 . 7 hz ), 6 . 94 ( 1h , dd , j = 8 . 9 hz , 11 . 6 hz ), 7 . 16 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 44 ( 2h , d , j = 8 . 6 hz ), 7 . 83 ( 1h , s ), 7 . 91 ( 1h , t , j = 5 . 4 hz ), 9 . 50 ( 1h , s ). potassium carbonate ( 129 mg , 0 . 93 mmol ) and ethyl bromoacetate ( 114 mg , 0 . 68 mmol ) were added to a dmf solution ( 4 ml ) of 2 -[ 5 - fluoro - 3 -( 4 - hydroxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl ]- n -( 2 - morpholin - 4 - ylethyl ) acetamide ( 300 mg , 0 . 62 mmol ), followed by stirring at room temperature for 87 hours . water and ethyl acetate were added to the reaction mixture and the reaction mixture was then subjected to separation . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 50 : 1 → 20 : 1 ). the purified product was concentrated under reduced pressure , giving a pale yellow oily substance of ethyl [( 4 -{ 5 - fluoro - 1 -[( 2 - morpholin - 4 - ylethylcarbamoyl ) methyl ]- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinolin - 3 - yl } phenoxy ) acetate ( 306 mg , yield : 87 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 3 hz ), 1 . 30 ( 3h , t , j = 7 . 1 hz ), 1 . 79 - 1 . 88 ( 2h , m ), 2 . 30 - 2 . 43 ( 6h , m ), 3 . 35 ( 2h , q , j = 6 . 0 hz ), 3 . 48 - 3 . 52 ( 4h , m ), 3 . 91 ( 2h , t , j = 6 . 9 hz ), 4 . 26 ( 2h , q , j = 7 . 1 hz ), 4 . 59 ( 2h , s ), 5 . 00 ( 2h , s ), 6 . 76 - 6 . 96 ( 5h , m ), 7 . 37 ( 1h , s ), 7 . 51 ( 2h , d , j = 8 . 8 hz ). ethyl ( 4 -{ 5 - fluoro - 1 -[( 2 - morpholin - 4 - yl - ethylcarbamoyl ) methyl ]- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinolin - 3 - yl } phenoxy ) acetate ( 300 mg ) was added to a 7n ammonia - methanol solution ( 15 ml ) and then stirred at 70 ° c . for 43 hours . the mixture was cooled to room temperature and concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 50 : 1 → 9 : 1 → ethyl acetate : methanol = 10 : 1 ). the purified product was concentrated under reduced pressure , and the residue was recrystallized from ethyl acetate - n - hexane , giving a pale yellow powder of 2 -( 4 -{ 5 - fluoro - 1 -[( 2 - morpholin - 4 - yl - ethylcarbamoyl ) methyl ]- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinolin - 3 - yl } phenoxy ) acetamide ( 100 mg , yield : 35 %) 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 95 ( 3h , t , j = 7 . 3 hz ), 1 . 72 - 1 . 81 ( 2h , m ), 2 . 32 - 2 . 34 ( 6h , m ), 3 . 18 ( 2h , q , j = 6 . 5 hz ), 3 . 50 - 3 . 54 ( 4h , m ), 3 . 94 ( 2h , t , j = 6 . 8 hz ), 4 . 43 ( 2h , s ), 5 . 14 ( 2h , s ), 6 . 92 - 7 . 00 ( 3h , m ), 7 . 19 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 39 ( 1h , s ), 7 . 53 ( 1h , s ), 7 . 59 ( 2h , d , j = 8 . 8 hz ), 7 . 91 - 7 . 93 ( 2h , brs ). the above compound was prepared in the same manner as in example 149 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 3 hz ), 1 . 27 ( 3h , t , j = 7 . 1 hz ), 1 . 53 - 1 . 74 ( 6h , m ), 1 . 80 - 1 . 88 ( 2h , m ), 3 . 50 - 3 . 60 ( 1h , m ), 3 . 83 - 3 . 91 ( 2h , m ), 3 . 95 ( 2h , t , j = 6 . 8 hz ), 4 . 03 - 4 . 08 ( 1h , m ), 4 . 16 - 4 . 28 ( 4h , m ), 4 . 72 ( 1h , brs ), 5 . 10 ( 2h , s ), 6 . 84 - 7 . 00 ( 4h , m ), 7 . 35 ( 1h , s ), 7 . 58 ( 2h , d , j = 8 . 8 hz ). 2n hydrochloric acid ( 6 . 3 ml ) was added to an ethanol solution ( 20 ml ) of ethyl ( 5 - fluoro - 4 - oxo - 8 - propoxy - 3 -{ 4 -[ 2 -( tetrahydropyran - 2 - yloxy ) ethoxy ] phenyl }- 4h - quinolin - 1 - yl ) acetate ( 840 mg , 1 . 59 mmol ) and stirred at 50 ° c . for 2 hours . the resulting mixture was cooled to room temperature and then concentrated under reduced pressure . ethyl acetate and water were added to the residue , followed by separation . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 30 : 1 → 15 : 1 ). the purified product was concentrated under reduced pressure , giving a pale yellow oily substance of ethyl { 5 - fluoro - 3 -[ 4 -( 2 - hydroxyethoxy ) phenyl ]- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - yl } acetate ( 627 mg , yield : 89 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 3 hz ), 1 . 27 ( 3h , t , j = 7 . 1 hz ), 1 . 79 - 1 . 88 ( 3h , m ), 3 . 92 - 3 . 98 ( 4h , m ), 4 . 08 - 4 . 12 ( 2h , m ), 4 . 24 ( 2h , q , j = 7 . 1 hz ), 5 . 10 ( 2h , s ), 6 . 84 - 7 . 00 ( 4h , m ), 7 . 35 ( 1h , s ), 7 . 58 ( 2h , d , j = 8 . 8 hz ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 98 ( 3h , t , j = 7 . 3 hz ), 1 . 71 - 1 . 85 ( 2h , m ), 3 . 72 ( 2h , m ), 3 . 93 - 4 . 02 ( 4h , m ), 4 . 87 ( 1h , brs ), 5 . 22 ( 2h , s ), 6 . 93 - 7 . 02 ( 3h , m ), 7 . 22 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 57 ( 2h , d , j = 8 . 8 hz ), 8 . 00 ( 1h , s ), 12 . 50 ( 1h , brs ). the above compound was prepared in the same manner as in example 148 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 95 ( 3h , t , j = 7 . 3 hz ), 1 . 72 - 1 . 79 ( 2h , m ), 2 . 30 - 2 . 40 ( 6h , m ), 3 . 18 ( 2h , q , j = 5 . 9 hz ), 3 . 50 - 3 . 53 ( 4h , m ), 3 . 69 - 3 . 74 ( 2h , m ), 3 . 91 - 4 . 00 ( 4h , m ), 4 . 91 ( 1h , t , j = 5 . 4 hz ), 5 . 14 ( 2h , s ), 6 . 92 - 6 . 98 ( 3h , m ), 7 . 18 ( 1h , dd , j = 4 . 4 hz , 9 . 0 hz ), 7 . 57 ( 2h , d , j = 8 . 6 hz ), 7 . 90 - 7 . 93 ( 2h , brs ). the above compound was prepared in the same manner as in example 1 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 25 - 1 . 31 ( 3h , t , j = 7 . 1 hz ), 1 . 87 - 1 . 98 ( 2h , m ), 2 . 10 - 2 . 17 ( 2h , m ), 2 . 51 - 2 . 57 ( 2h , t , j = 7 . 3 hz ), 4 . 00 - 4 . 21 ( 6h , m ), 6 . 83 - 6 . 93 ( 4h , m ), 7 . 55 - 7 . 59 ( 2h , d , j = 8 . 4 hz ), 7 . 72 - 7 . 75 ( 1h , d , j = 6 . 1 hz ), 8 . 93 ( 1h , brs ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 93 - 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 69 - 1 . 91 ( 4h , m ), 2 . 28 - 2 . 34 ( 2h , t , j = 7 . 3 hz ), 3 . 89 - 3 . 94 ( 2h , t , j = 6 . 4 hz ), 4 . 00 - 4 . 05 ( 2h , t , j = 6 . 4 hz ), 6 . 67 - 6 . 87 ( 3h , m ), 7 . 03 - 7 . 08 ( 1h , m ), 7 . 43 - 7 . 47 ( 2h , d , j = 8 . 7 hz ), 7 . 71 - 7 . 73 ( 1h , d , j = 6 . 3 hz ), 11 . 18 - 11 . 20 ( 1h , d , j = 6 . 0 hz ), 11 . 5 - 12 . 2 ( 1h , br ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 81 - 0 . 87 ( 3h , t , j = 7 . 3 hz ), 1 . 01 - 1 . 08 ( 3h , t , j = 7 . 4 hz ), 1 . 20 - 1 . 40 ( 4h , m ), 1 . 80 - 1 . 95 ( 4h , m ), 2 . 19 - 2 . 25 ( 2h , t , j = 7 . 4 hz ), 3 . 00 - 3 . 40 ( 2h , m ), 3 . 93 - 3 . 99 ( 2h , t , j = 6 . 3 hz ), 4 . 07 - 4 . 13 ( 2h , t , j = 6 . 4 hz ), 6 . 84 - 6 . 93 ( 3h , m ), 7 . 11 - 7 . 16 ( 1h , m ), 7 . 51 - 7 . 54 ( 2h , d , j = 8 . 5 hz ), 7 . 82 ( 2h , m ), 11 . 24 ( 1h , brs ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 - 1 . 09 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 1 . 92 ( 2h , m ), 4 . 09 - 4 . 14 ( 2h , t , j = 6 . 4 hz ), 4 . 70 ( 2h , s ), 6 . 86 - 6 . 97 ( 3h , m ), 7 . 13 - 7 . 18 ( 1h , m ), 7 . 51 - 7 . 56 ( 2h , m ), 7 . 80 - 7 . 83 ( 1h , d , j = 6 . 3 hz ), 11 . 27 - 11 . 29 ( 1h , d , j = 6 . 0 hz ), 12 . 99 ( 1h , brs ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 83 - 0 . 88 ( 3h , t , j = 7 . 2 hz ), 1 . 02 - 1 . 08 ( 3h , t , j = 7 . 4 hz ), 1 . 23 - 1 . 50 ( 4h , m ), 1 . 80 - 1 . 88 ( 2h , m ), 3 . 08 - 3 . 16 ( 2h , m ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 4 hz ), 4 . 47 ( 2h , s ), 6 . 85 - 6 . 97 ( 3h , m ), 7 . 12 - 7 . 17 ( 1h , m ), 7 . 53 - 7 . 56 ( 2h , d , j = 8 . 8 hz ), 7 . 80 ( 1h , s ), 8 . 03 - 8 . 08 ( 1h , t , j = 5 . 5 hz ), 11 . 24 ( 1h , brs ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 3 hz ), 1 . 86 - 2 . 00 ( 2h , m ), 4 . 12 ( 2h , t , j = 6 . 6 hz ), 6 . 85 - 6 . 98 ( 2h , m ), 7 . 84 - 7 . 93 ( 5h , m ), 8 . 90 ( 1h , brs ), 10 . 02 ( 1h , s ). the above compound was prepared in the same manner as in example 106 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 01 ( 3h , t , j = 7 . 3 hz ), 1 . 74 - 1 . 86 ( 2h , m ), 2 . 32 - 2 . 35 ( 4h , m ), 2 . 59 ( 2h , t , j = 5 . 4 hz ), 3 . 51 - 3 . 54 ( 4h , m ), 4 . 04 ( 2h , t , j = 6 . 5 hz ), 4 . 50 ( 2h , d , j = 4 . 5 hz ), 4 . 66 ( 2h , d , j = 5 . 4 hz ), 5 . 22 ( 1h , brs ), 6 . 99 ( 1h , dd , j = 8 . 9 hz , 11 . 6 hz ), 7 . 22 - 7 . 33 ( 3h , m ), 7 . 61 ( 2h , d , j = 8 . 2 hz ), 7 . 97 ( 1h , s ). the above compound was prepared in the same manner as in example 73 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 3 hz ), 1 . 75 - 1 . 89 ( 2h , m ), 2 . 38 - 2 . 50 ( 6h , m ), 3 . 38 ( 2h , q , j = 6 . 3 hz ), 3 . 53 - 3 . 61 ( 4h , m ), 4 . 08 ( 2h , t , j = 6 . 4 hz ), 6 . 92 ( 1h , dd , j = 8 . 7 hz , 12 . 0 hz ), 7 . 15 ( 1h , dd , j = 3 . 9 hz , 8 . 8 hz ), 7 . 71 ( 2h , d , j = 8 . 5 hz ), 7 . 89 ( 2h , d , j = 8 . 5 hz ), 7 . 94 ( 1h , s ), 8 . 41 ( 1h , t , j = 5 . 5 hz ), 11 . 46 ( 1h , brs ). the above compound was prepared in the same manner as in example 73 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 3 hz ), 1 . 30 - 1 . 38 ( 2h , m ), 1 . 75 - 1 . 89 ( 4h , m ), 2 . 34 - 2 . 49 ( 4h , m ), 2 . 79 - 3 . 02 ( 2h , m ), 3 . 61 - 3 . 69 ( 6h , m ), 4 . 08 ( 2h , t , j = 6 . 4 hz ), 4 . 42 ( 1h , brs ), 6 . 92 ( 1h , dd , j = 8 . 8 hz , 12 . 0 hz ), 7 . 15 ( 1h , dd , j = 3 . 9 hz , 8 . 8 hz ), 7 . 37 ( 2h , d , j = 8 . 2 hz ), 7 . 67 ( 2h , d , j = 8 . 2 hz ), 7 . 92 ( 1h , s ), 11 . 45 ( 1h , brs ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 - 1 . 16 ( 3h , t , j = 7 . 4 hz ), 1 . 86 - 2 . 00 ( 2h , m ), 3 . 86 ( 3h , s ), 4 . 02 - 4 . 07 ( 2h , t , j = 6 . 5 hz ), 6 . 72 - 6 . 91 ( 1h , m ), 6 . 92 - 7 . 05 ( 3h , m ), 7 . 31 - 7 . 43 ( 2h , m ), 9 . 25 ( 1h , brs ), 9 . 77 ( 1h , s ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 - 1 . 16 ( 3h , t , j = 7 . 4 hz ), 1 . 85 - 2 . 05 ( 2h , m ), 3 . 70 ( 3h , s ), 3 . 85 ( 3h , s ), 4 . 10 - 4 . 15 ( 2h , t , j = 6 . 5 hz ), 6 . 75 - 6 . 99 ( 4h , m ), 7 . 12 - 7 . 22 ( 2h , m ), 9 . 36 ( 1h , brs ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 - 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 69 - 1 . 92 ( 2h , m ), 3 . 76 ( 3h , s ), 4 . 10 - 4 . 15 ( 2h , t , j = 6 . 5 hz ), 6 . 88 - 6 . 97 ( 3h , m ), 7 . 12 - 7 . 23 ( 3h , m ), 10 . 78 ( 1h , brs ), 13 . 00 - 15 . 00 ( 1h , br ). ethanolamine ( 10 ml ) was added to methyl 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinoline - 2 - carboxylic acid ( 3 . 2 g , 7 . 78 mmol ) and stirred at 100 ° c . for 3 hours . the mixture was cooled to room temperature and purified using silica gel column chromatography ( dichloromethane : methanol = 100 : 0 → 20 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a pale yellow amorphous solid of 2 - hydroxyethyl 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinoline - 2 - carboamide ( 3 . 0 g , yield : 93 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 69 - 1 . 95 ( 2h , m ), 2 . 92 - 3 . 17 ( 4h , m ), 3 . 76 ( 3h , s ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 6 hz ), 4 . 32 - 4 . 57 ( 1h , m ), 6 . 86 - 6 . 93 ( 3h , m ), 7 . 15 - 7 . 21 ( 3h , m ), 8 . 13 - 8 . 33 ( 1h , m ), 11 . 09 ( 1h , brs ). triphenyl phosphine ( 2 . 47 g , 9 . 8 mmol ) and carbon tetrachloride ( 1 . 4 g , 9 . 1 mmol ) were added to a thf solution ( 30 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydro - quinoline - 2 - carboxy -( 2 - hydroxyethyl ) amide ( 3 . 0 g , 7 . 24 mmol ) and heated under reflux for 2 hours . the mixture was cooled to room temperature , and water was then added thereto , followed by extraction with dichloromethane . the thus - obtained organic layer was washed with water , dried over anhydrous sodium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 100 : 0 → 20 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinoline - 2 - carboxy -( 2 - chloroethyl ) amide ( 1 . 8 g , yield : 58 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 - 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 89 ( 2h , m ), 3 . 20 - 3 . 30 ( 4h , m ), 3 . 75 ( 3h , s ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 6 hz ), 6 . 86 - 6 . 95 ( 3h , m ), 7 . 16 - 7 . 21 ( 3h , m ), 8 . 64 - 8 . 69 ( 1h , t , j = 5 . 4 hz ), 11 . 14 ( 1h , s ). the above compound was prepared in the same manner as in example 167 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 100 - 1 . 10 ( 3h , m ), 1 . 83 - 1 . 95 ( 2h , m ), 3 . 42 - 3 . 54 ( 5h , m ), 3 . 60 - 3 . 65 ( 2h , m ), 3 . 80 ( 1 . 2h , s ), 3 . 82 ( 1 . 8h , s ), 3 . 99 - 4 . 00 ( 0 . 8h , t , j = 6 . 6 hz ), 4 . 06 - 4 . 12 ( 1 . 2h , t , j = 6 . 6 hz ), 6 . 75 - 6 . 96 ( 4h , m ), 7 . 32 - 7 . 45 ( 2h , m ), 8 . 89 ( 0 . 6h , brs ), 9 . 31 ( 0 . 4h , brs ). n - methylpiperazine ( 276 mg , 2 . 76 mmol ), sodium iodide ( 440 mg , 2 . 9 mmol ) and potassium carbonate ( 572 mg , 4 . 14 mmol ) were added to a dmf solution ( 8 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinoline - 2 - carboxy -( 2 - chloroethyl ) amide ( 600 mg , 1 . 38 mmol ) and stirred overnight at 80 ° c . the mixture was cooled to room temperature , and water was then added thereto , followed by extraction using chloroform . the thus - obtained organic layer was concentrated under reduced pressure , and the residue was then purified using medium pressure liquid chromatography ( nh silica gel , dichloromethane : methanol = 100 : 0 → 10 : 1 ). the purified product was concentrated under reduced pressure , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydro - quinoline - 2 - carboxy -[ 2 -( 4 - methylpiperazin - 1 - yl ) ethyl ] amide ( 100 mg , yield : 14 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 - 1 . 16 ( 3h , t , j = 7 . 4 hz ), 1 . 90 - 1 . 99 ( 2h , m ), 2 . 21 - 2 . 80 ( 13h , m ), 3 . 28 - 3 . 35 ( 2h , m ), 3 . 85 ( 3h , s ), 4 . 08 - 4 . 14 ( 2h , t , j = 6 . 5 hz ), 6 . 25 - 6 . 50 ( 1h , brs ), 6 . 79 - 7 . 05 ( 4h , m ), 7 . 28 - 7 . 32 ( 2h , m ), 9 . 77 - 10 . 1 ( 1h , br ). the above compound was prepared in the same manner as in example 170 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 - 1 . 16 ( 3h , t , j = 7 . 4 hz ), 1 . 88 - 2 . 00 ( 2h , m ), 2 . 17 - 2 . 25 ( 6h , m ), 3 . 29 - 3 . 35 ( 2h , m ), 3 . 54 - 3 . 58 ( 4h , m ), 3 . 84 ( 3h , s ), 4 . 08 - 4 . 14 ( 2h , t , j = 6 . 4 hz ), 6 . 35 - 6 . 50 ( 1h , m ), 6 . 79 - 7 . 05 ( 4h , m ), 7 . 28 - 7 . 34 ( 2h , m ), 9 . 96 ( 1h , s ). the above compound was prepared in the same manner as in example 134 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 07 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 83 - 1 . 92 ( 2h , m ), 2 . 32 ( 3h , s ), 2 . 61 - 2 . 65 ( 2h , t , j = 5 . 5 hz ), 3 . 75 - 3 . 80 ( 2h , m ), 3 . 82 ( 3h , s ), 4 . 04 - 4 . 12 ( 3h , m ), 6 . 72 - 6 . 94 ( 4h , m ), 7 . 13 - 7 . 17 ( 2h , m ), 10 . 03 ( 1h , brs ). 1 -( 2 - pyridyl ) piperazine ( 551 mg , 3 . 38 mmol ) was added to a 1 , 2 - dichloromethane solution ( 20 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinoline - 2 - carbaldehyde ( 800 mg , 2 . 25 mmol ) and stirred at room temperature for 1 hour . sodium triacetoxyborohydride ( 670 mg , 3 . 16 mmol ) was added to the resulting mixture and stirred at room temperature for 4 hours . dichloromethane was added to the resulting reaction mixture , washed with water , and then the mixture was dried over sodium sulfate . thereafter , the solvent was removed under reduced pressure . the residue was then purified using nh silica gel column chromatography ( dichloromethane : ethyl acetate = 1 : 1 ). the solvent was removed under reduced pressure and the residue was recrystallized from ethyl acetate - n - hexane , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 2 -( 4 - pyridin - 2 - yl - piperazin - 1 - ylmethyl )- 1h - quinolin - 4 - one ( 400 mg , yield : 35 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 - 1 . 13 ( 3h , t , j = 7 . 4 hz ), 1 . 84 - 1 . 93 ( 2h , m ), 2 . 63 - 2 . 67 ( 4h , m ), 3 . 50 - 3 . 65 ( 6h , m ), 3 . 89 ( 3h , s ), 4 . 06 - 4 . 11 ( 2h , t , j = 6 . 3 hz ), 6 . 93 - 6 . 68 ( 2h , m ), 6 . 76 - 6 . 98 ( 4h , m ), 7 . 16 - 7 . 20 ( 2h , d , j = 8 . 8 hz ), 7 . 45 - 7 . 56 ( 1h , m ), 8 . 18 - 8 . 21 ( 1h , m ), 10 . 0 - 10 . 2 ( 1h , brs ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 - 1 . 11 ( 3h , t , j = 7 . 4 hz ), 1 . 81 - 1 . 95 ( 2h , m ), 2 . 66 - 2 . 70 ( 4h , m ), 3 . 38 - 3 . 42 ( 4h , m ), 3 . 56 ( 2h , s ), 3 . 83 ( 3h , s ), 4 . 06 - 4 . 11 ( 2h , t , j = 6 . 3 hz ), 6 . 66 - 6 . 69 ( 2h , d , j = 5 . 3 hz ), 6 . 76 - 6 . 97 ( 4h , m ), 7 . 15 - 7 . 19 ( 2h , d , j = 7 . 5 hz ), 8 . 28 - 8 . 30 ( 2h , d , j = 5 . 3 hz ), 9 . 90 - 10 . 2 ( 1h , brs ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 - 1 . 12 ( 3h , t , j = 7 . 3 hz ), 1 . 85 - 1 . 93 ( 2h , m ), 2 . 39 ( 3h , s ), 2 . 62 - 2 . 64 ( 4h , m ), 3 . 53 ( 2h , s ), 3 . 55 - 3 . 70 ( 4h , m ), 3 . 83 ( 3h , s ), 4 . 05 - 4 . 10 ( 2h , t , j = 6 . 4 hz ), 6 . 41 - 6 . 44 ( 1h , d , j = 8 . 4 hz ), 6 . 50 - 6 . 53 ( 1h , d , j = 7 . 3 hz ), 6 . 75 - 6 . 96 ( 4h , m ), 7 . 16 - 7 . 20 ( 2h , d , j = 8 . 8 hz ), 7 . 37 - 7 . 41 ( 1h , m ), 10 . 2 ( 1h , s ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 - 1 . 11 ( 3h , t , j = 7 . 4 hz ), 1 . 81 - 1 . 95 ( 2h , m ), 2 . 46 ( 3h , s ), 2 . 60 - 2 . 70 ( 4h , m ), 3 . 30 - 3 . 40 ( 4h , m ), 3 . 54 ( 2h , s ), 3 . 82 ( 3h , s ), 4 . 05 - 4 . 10 ( 2h , t , j = 6 . 3 hz ), 6 . 45 - 6 . 55 ( 2h , m ), 6 . 74 - 6 . 95 ( 4h , m ), 7 . 13 - 7 . 17 ( 2h , d , j = 8 . 7 hz ), 8 . 17 - 8 . 19 ( 1h , d , j = 5 . 9 hz ), 10 . 04 ( 1h , s ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 13 - 1 . 20 ( 3h , t , j = 7 . 4 hz ), 1 . 50 - 1 . 70 ( 2h , m ), 2 . 30 - 2 . 60 ( 3h , m ), 2 . 70 - 2 . 90 ( 6h , m ), 3 . 40 - 3 . 77 ( 4h , m ), 3 . 83 ( 3h , s ), 4 . 11 - 4 . 16 ( 2h , t , j = 6 . 3 hz ), 6 . 76 - 6 . 96 ( 4h , m ), 7 . 08 - 7 . 12 ( 2h , d , j = 8 . 7 hz ), 9 . 60 ( 1h , s ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 - 1 . 17 ( 3h , t , j = 7 . 4 hz ), 1 . 87 - 2 . 15 ( 3h , m ), 2 . 39 - 2 . 42 ( 4h , m ), 2 . 46 - 2 . 51 ( 2h , t , j = 5 . 7 hz ), 2 . 64 - 2 . 68 ( 2h , t , j = 5 . 7 hz ), 3 . 65 - 3 . 68 ( 4h , t , j = 4 . 6 hz ), 3 . 74 ( 2h , s ), 3 . 83 ( 3h , s ), 4 . 07 - 4 . 12 ( 2h , t , j = 6 . 3 hz ), 6 . 74 - 6 . 96 ( 4h , m ), 7 . 16 - 7 . 20 ( 2h , m ), 10 . 35 ( 1h , s ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 - 1 . 17 ( 3h , t , j = 7 . 4 hz ), 1 . 86 - 2 . 00 ( 2h , m ), 2 . 30 - 2 . 42 ( 7h , m ), 2 . 46 - 2 . 52 ( 2h , m ), 2 . 58 - 2 . 64 ( 2h , m ), 3 . 52 ( 2h , s ), 3 . 52 - 3 . 63 ( 4h , t , j = 4 . 6 hz ), 3 . 83 ( 3h , s ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 3 hz ), 6 . 75 - 6 . 96 ( 4h , m ), 7 . 13 - 7 . 18 ( 2h , d , j = 8 . 7 hz ), 10 . 11 ( 1h , s ). the above compound was prepared in the same manner as in example 168 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 100 - 1 . 10 ( 3h , m ), 1 . 83 - 1 . 95 ( 2h , m ), 2 . 26 ( 3h , s ), 2 . 64 ( 2h , m ), 3 . 03 ( 2h , s ), 3 . 48 2h , m ), 3 . 82 ( 3h , s ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 6 hz ), 6 . 75 - 6 . 96 ( 4h , m ), 7 . 32 - 7 . 45 ( 2h , m ), 8 . 89 ( 0 . 6h , brs ), 9 . 31 ( 0 . 4h , brs ). a dichloromethane solution ( 30 ml ) of methyl 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 1 , 4 - dihydroquinoline - 2 - carboxylate ( 5 . 0 g , 13 mmol ) was cooled to − 78 ° c ., and hydrogenated diisobutylaluminium ( dibal - h , 1m toluene solution , 30 ml ) was added thereto dropwise under a nitrogen atmosphere . after completion of the addition , the mixture was stirred at the same temperature for 3 hours . the reaction mixture was heated to room temperature , and 5n sodium hydroxide was added thereto , followed by extraction with dichloromethane . the thus - obtained organic layer was washed with water , dried over sodium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 10 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a yellow amorphous solid of 5 - fluoro - 2 - hydroxymethyl - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 4 . 8 g , yield : 85 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 04 - 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 83 - 1 . 92 ( 2h , m ), 3 . 75 ( 3h , s ), 4 . 02 - 4 . 07 ( 2h , t , j = 6 . 5 hz ), 4 . 39 ( 2h , s ), 4 . 67 ( 1h , brs ), 6 . 71 - 6 . 83 ( 4h , m ), 6 . 95 - 6 . 98 ( 2h , m ), 9 . 82 ( 1h , s ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 09 - 1 . 14 ( 3h , t , j = 7 . 4 hz ), 1 . 78 - 1 . 94 ( 2h , m ), 2 . 32 - 2 . 47 ( 4h , m ), 3 . 47 ( 2h , s ), 3 . 55 - 3 . 68 ( 4h , m ), 3 . 77 ( 3h , s ), 4 . 12 - 4 . 16 ( 2h , t , j = 6 . 2 hz ), 6 . 79 - 7 . 00 ( 3h , m ), 7 . 06 - 7 . 14 ( 2h , m ), 7 . 15 - 7 . 25 ( 1h , m ), 10 . 21 ( 1h , brs ). the above compound was prepared in the same manner as in example 173 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 18 - 1 . 24 ( 3h , t , j = 7 . 4 hz ), 1 . 86 - 2 . 08 ( 2h , m ), 2 . 31 ( 3h , s ), 2 . 36 - 2 . 79 ( 8h , m ), 3 . 49 ( 2h , s ), 3 . 84 ( 3h , s ), 4 . 08 - 4 . 13 ( 2h , t , j = 6 . 2 hz ), 6 . 68 - 7 . 00 ( 4h , m ), 7 . 11 - 7 . 22 ( 2h , m ), 10 . 21 ( 1h , brs ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 99 ( 3h , t , j = 7 . 3 hz ), 1 . 65 - 1 . 71 ( 2h , m ), 1 . 79 - 1 . 87 ( 2h , m ), 2 . 09 ( 2h , t , j = 7 . 4 hz ), 2 . 57 ( 2h , t , j = 7 . 0 hz ), 3 . 76 ( 3h , s ), 4 . 13 ( 2h , t , j = 6 . 6 hz ), 6 . 81 - 6 . 94 ( 3h , m ), 7 . 06 ( 2h , d , j = 8 . 7 hz ), 7 . 14 ( 1h , dd , j = 4 . 0 hz , 8 . 8 hz ), 10 . 40 ( 1h , brs ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 82 ( 3h , t , j = 6 . 9 hz ), 1 . 00 ( 3h , t , j = 7 . 3 hz ), 1 . 19 - 1 . 30 ( 4h , m ), 1 . 64 - 1 . 70 ( 2h , m ), 1 . 84 ( 2h , q , j = 6 . 9 hz ), 1 . 98 - 2 . 03 ( 2h , m ), 2 . 48 - 2 . 56 ( 2h , m ), 2 . 94 - 2 . 99 ( 2h , m ), 3 . 75 ( 3h , s ), 4 . 10 ( 2h , t , j = 6 . 4 hz ), 6 . 81 - 6 . 93 ( 3h , m ), 7 . 05 - 7 . 15 ( 3h , m ), 7 . 82 ( 1h , t , j = 5 . 0 hz ), 10 . 97 ( 1h , brs ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 2 . 00 ( 2h , m ), 4 . 14 ( 2h , t , j = 6 . 4 hz ), 6 . 99 ( 1h , dd , j = 8 . 8 , 12 . 0 hz ), 7 . 23 ( 1h , dd , j = 3 . 9 , 8 . 8 hz ), 8 . 12 ( 1h , s ), 9 . 08 ( 2h , s ), 9 . 10 ( 1h , s ), 11 . 68 ( 1h , s ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 95 ( 2h , m ), 3 . 87 ( 3h , s ), 4 . 11 ( 2h , t , j = 6 . 4 hz ), 6 . 90 ( 1h , dd , j = 8 . 7 , 12 . 0 hz ), 7 . 13 ( 1h , dd , j = 3 . 9 , 8 . 7 hz ), 7 . 95 ( 1h , s ), 8 . 08 ( 1h , d , j = 5 . 4 hz ), 8 . 37 ( 1h , s ), 11 . 36 ( 1h , d , j = 5 . 4 hz ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 4 hz ), 1 . 36 ( 18h , s ), 1 . 85 - 2 . 05 ( 2h , m ), 3 . 83 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 6 hz ), 6 . 32 ( 2h , d , j = 13 . 0 hz ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 07 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 63 ( 2h , d , j = 8 . 9 hz ), 7 . 79 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 4 hz ), 1 . 37 ( 18h , s ), 1 . 85 - 2 . 05 ( 2h , m ), 4 . 08 ( 2h , t , j = 6 . 6 hz ), 6 . 30 ( 2h , d , j = 12 . 6 hz ), 6 . 99 ( 1h , dd , j = 9 . 0 , 10 . 7 hz ), 7 . 13 ( 1h , dd , j = 4 . 4 , 9 . 0 hz ), 7 . 27 ( 1h , dd , j = 2 . 1 , 8 . 3 hz ), 7 . 37 ( 1h , d , j = 8 . 3 hz ), 7 . 47 ( 1h , d , j = 2 . 1 hz ), 7 . 75 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 37 ( 18h , s ), 1 . 54 ( 3h , t , j = 7 . 0 hz ), 3 . 76 ( 3h , s ), 3 . 83 ( 3h , s ), 4 . 18 ( 2h , q , j = 7 . 0 hz ), 6 . 28 ( 2h , d , j = 11 . 9 hz ), 6 . 50 - 6 . 60 ( 2h , m ), 6 . 93 ( 1h , dd , j = 9 . 0 , 10 . 9 hz ), 7 . 07 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 34 ( 1h , d , j = 9 . 0 hz ), 7 . 72 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 5 hz ), 1 . 36 ( 18h , s ), 1 . 42 ( 3h , t , j = 7 . 0 hz ), 1 . 85 - 2 . 05 ( 2h , m ), 4 . 00 - 4 . 15 ( 4h , m ), 6 . 32 ( 2h , d , j = 13 . 0 hz ), 6 . 80 - 7 . 00 ( 3h , m ), 7 . 08 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 61 ( 2h , t , j = 8 . 9 hz ), 7 . 78 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 02 - 1 . 90 ( 28h , m ), 2 . 50 - 2 . 75 ( 1h , m ), 2 . 78 ( 3h , s ), 3 . 84 ( 3h , s ), 5 . 97 ( 1h , dd , j = 9 . 4 , 10 . 7 hz ), 6 . 80 - 7 . 05 ( 3h , m ), 7 . 42 ( 1h , dd , j = 5 . 1 , 8 . 8 hz ), 7 . 51 ( 1h , dd , j = 9 . 4 , 12 . 1 hz ), 7 . 64 ( 2h , d , j = 8 . 8 hz ), 7 . 71 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 5 hz ), 1 . 36 ( 18h , s ), 1 . 85 - 2 . 05 ( 2h , m ), 3 . 82 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 6 hz ), 6 . 30 ( 2h , d , j = 12 . 6 hz ), 6 . 60 - 6 . 80 ( 2h , m ), 6 . 96 ( 1h , dd , j = 9 . 0 , 10 . 8 hz ), 7 . 10 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 51 ( 1h , t , j = 8 . 4 hz ), 7 . 79 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 0 . 35 - 0 . 50 ( 2h , m ), 0 . 60 - 0 . 75 ( 2h , m ), 1 . 25 - 1 . 45 ( 19h , m ), 3 . 83 ( 3h , s ), 3 . 95 ( 2h , d , j = 7 . 1 hz ), 6 . 40 ( 2h , d , j = 13 . 1 hz ), 6 . 85 - 7 . 00 ( 3h , m ), 7 . 04 ( 1h , dd , j = 4 . 6 , 9 . 0 hz ), 7 . 63 ( 2h , d , j = 8 . 9 hz ), 7 . 79 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 36 ( 18h , s ), 1 . 55 ( 3h , t , j = 7 . 0 hz ), 3 . 83 ( 3h , s ), 4 . 19 ( 2h , q , j = 7 . 0 hz ), 6 . 33 ( 2h , d , j = 12 . 8 hz ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 08 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 63 ( 2h , d , j = 8 . 8 hz ), 7 . 77 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 36 ( 18h , s ), 1 . 85 - 2 . 10 ( 4h , m ), 2 . 15 - 2 . 30 ( 2h , m ), 2 . 85 - 3 . 00 ( 1h , m ), 3 . 83 ( 3h , s ), 4 . 07 ( 2h , d , j = 7 . 0 hz ), 6 . 30 ( 2h , d , j = 13 . 2 hz ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 07 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 63 ( 2h , d , j = 8 . 9 hz ), 7 . 79 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 12 ( 3h , t , j = 7 . 4 hz ), 1 . 36 ( 18h , s ), 1 . 90 - 2 . 05 ( 2h , m ), 3 . 83 ( 3h , s ), 4 . 06 ( 2h , t , j = 6 . 6 hz ), 6 . 28 ( 2h , d , j = 13 . 2 hz ), 6 . 94 ( 2h , d , j = 8 . 9 hz ), 7 . 02 ( 1h , dd , j = 6 . 8 , 11 . 6 hz ), 7 . 62 ( 2h , d , j = 8 . 9 hz ), 7 . 78 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 11 ( 3h , t , j = 7 . 5 hz ), 1 . 37 ( 18h , s ), 1 . 85 - 2 . 00 ( 2h , m ), 3 . 93 ( 3h , s ), 4 . 06 ( 2h , t , j = 6 . 6 hz ), 6 . 34 ( 2h , d , j = 13 . 1 hz ), 6 . 94 ( 1h , dd , j = 9 . 0 , 11 . 1 hz ), 7 . 06 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 81 ( 1h , s ), 8 . 01 ( 1h , s ), 8 . 38 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 13 ( 3h , t , j = 7 . 5 hz ), 1 . 36 ( 18h , s ), 1 . 90 - 2 . 10 ( 2h , m ), 4 . 10 ( 2h , t , j = 6 . 6 hz ), 6 . 36 ( 2h , d , j = 13 . 8 hz ), 7 . 01 ( 1h , dd , j = 9 . 0 , 10 . 9 hz ), 7 . 16 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 96 ( 1h , s ), 9 . 08 ( 2h , s ), 9 . 15 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 02 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 90 ( 2h , m ), 3 . 77 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 5 hz ), 6 . 26 ( 2h , d , j = 11 . 2 hz ), 6 . 96 ( 2h , d , j = 8 . 9 hz ), 7 . 06 ( 1h , dd , j = 9 . 1 , 11 . 6 hz ), 7 . 33 ( 1h , dd , j = 4 . 5 , 9 . 1 hz ), 7 . 58 ( 2h , d , j = 8 . 9 hz ), 8 . 00 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 80 - 1 . 95 ( 2h , m ), 4 . 10 ( 2h , t , j = 6 . 5 hz ), 6 . 24 ( 2h , d , j = 11 . 2 hz ), 7 . 13 ( 1h , dd , j = 9 . 0 , 11 . 4 hz ), 7 . 40 ( 1h , dd , j = 4 . 6 , 9 . 0 hz ), 7 . 42 ( 1h , d , j = 8 . 2 hz ), 7 . 52 ( 1h , dd , j = 2 . 1 , 8 . 2 hz ), 7 . 69 ( 1h , d , j = 2 . 1 hz ), 7 . 97 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 45 ( 3h , t , j = 6 . 9 hz ), 3 . 69 ( 3h , s ), 3 . 80 ( 3h , s ), 4 . 19 ( 2h , q , j = 6 . 9 hz ), 6 . 20 ( 2h , d , j = 9 . 7 hz ), 6 . 56 ( 1h , dd , j = 2 . 4 , 8 . 2 hz ), 6 . 61 ( 1h , d , j = 2 . 4 hz ), 7 . 07 ( 1h , dd , j = 9 . 0 , 11 . 5 hz ), 7 . 16 ( 1h , d , j = 8 . 2 hz ), 7 . 35 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 80 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 4 hz ), 1 . 35 ( 3h , t , j = 7 . 0 hz ), 1 . 75 - 1 . 95 ( 2h , m ), 4 . 00 - 4 . 15 ( 4h , m ), 6 . 28 ( 2h , d , j = 11 . 2 hz ), 6 . 96 ( 2h , d , j = 8 . 8 hz ), 7 . 08 ( 1h , dd , j = 9 . 0 , 11 . 6 hz ), 7 . 35 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 59 ( 2h , d , j = 8 . 8 hz ), 8 . 03 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 95 ( 2h , m ), 3 . 81 ( 3h , s ), 4 . 09 ( 2h , d , j = 6 . 9 hz ), 6 . 24 ( 2h , d , j = 10 . 9 hz ), 6 . 75 - 7 . 00 ( 2h , m ), 7 . 11 ( 1h , dd , j = 9 . 0 , 11 . 4 hz ), 7 . 24 - 7 . 50 ( 2h , m ), 7 . 95 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 35 - 0 . 45 ( 2h , m ), 0 . 55 - 0 . 70 ( 2h , m ), 1 . 30 - 1 . 45 ( 1h , m ), 3 . 79 ( 3h , s ), 3 . 99 ( 2h , d , j = 7 . 2 hz ), 6 . 36 ( 2h , d , j = 11 . 2 hz ), 6 . 98 ( 2h , d , j = 8 . 9 hz ), 7 . 07 ( 1h , dd , j = 9 . 0 , 11 . 6 hz ), 7 . 33 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 60 ( 2h , d , j = 8 . 9 hz ), 8 . 03 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 45 ( 3h , t , j = 6 . 9 hz ), 3 . 79 ( 3h , s ), 4 . 19 ( 2h , q , j = 6 . 9 hz ), 6 . 28 ( 2h , d , j = 10 . 8 hz ), 6 . 98 ( 2h , d , j = 8 . 9 hz ), 7 . 08 ( 1h , dd , j = 9 . 0 , 11 . 6 hz ), 7 . 36 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 60 ( 2h , d , j = 8 . 9 hz ), 8 . 03 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 60 - 2 . 20 ( 6h , m ), 2 . 70 - 2 . 95 ( 1h , m ), 3 . 79 ( 3h , s ), 4 . 11 ( 2h , d , j = 6 . 9 hz ), 6 . 25 ( 2h , d , j = 11 . 5 hz ), 6 . 97 ( 2h , d , j = 8 . 9 hz ), 7 . 08 ( 1h , dd , j = 9 . 0 , 11 . 5 hz ), 7 . 35 ( 1h , dd , j = 4 . 5 , 9 . hz ), 7 . 60 ( 2h , d , j = 8 . 9 hz ), 8 . 02 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 705 - 2 . 00 ( 2h , m ), 3 . 78 ( 3h , s ), 4 . 12 ( 2h , t , j = 6 . 5 hz ), 6 . 25 ( 2h , d , j = 11 . 5 hz ), 6 . 98 ( 2h , d , j = 8 . 8 hz ), 7 . 50 - 7 . 70 ( 3h , m ), 8 . 07 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 75 - 2 . 00 ( 10h , m ), 3 . 79 ( 3h , s ), 3 . 83 ( 3h , s ), 3 . 90 - 4 . 60 ( 1h , m ), 5 . 85 ( 1h , d , j = 9 . 5 hz ), 6 . 48 ( 1h , d , j = 9 . 5 hz ), 7 . 00 ( 2h , d , j = 8 . 9 hz ), 7 . 33 ( 1h , dd , j = 8 . 6 , 11 . 6 hz ), 7 . 52 ( 2h , d , j = 8 . 9 hz ), 8 . 16 ( 1h , dd , j = 3 . 2 , 8 . 6 hz ), 8 . 22 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 04 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 95 ( 2h , m ), 3 . 80 - 4 . 15 ( 5h , m ), 6 . 29 ( 2h , d , j = 10 . 5 hz ), 7 . 07 ( 1h , dd , j = 9 . 0 , 11 . 6 hz ), 7 . 32 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 87 ( 1h , s ), 8 . 31 ( 1h , s ), 8 . 32 ( 1h , s ). the above compound was prepared in the same manner as in example 24 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 05 ( 3h , t , j = 6 . 6 hz ), 1 . 75 - 1 . 95 ( 2h , m ), 4 . 11 ( 2h , t , j = 6 . 5 hz ), 6 . 32 ( 2h , d , j = 12 . 0 hz ), 7 . 17 ( 1h , dd , j = 9 . 1 , 11 . 4 hz ), 7 . 43 ( 1h , dd , j = 4 . 5 , 9 . 1 hz ), 8 . 39 ( 1h , s ), 9 . 10 ( 2h , s ), 9 . 13 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 97 ( 3h , t , j = 7 . 4 hz ), 1 . 75 - 1 . 85 ( 2h , m ), 3 . 76 ( 3h , s ), 4 . 00 ( 2h , t , j = 6 . 7 hz ), 6 . 04 ( 2h , d , j = 9 . 1 hz ), 6 . 90 - 7 . 05 ( 3h , m ), 7 . 18 ( 1h , dd , j = 4 . 6 , 9 . 1 hz ), 7 . 42 ( 2h , d , j = 8 . 7 hz ), 8 . 14 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 96 ( 3h , t , j = 7 . 5 hz ), 1 . 75 - 1 . 95 ( 2h , m ), 4 . 07 ( 2h , t , j = 6 . 7 hz ), 6 . 08 ( 2h , d , j = 8 . 8 hz ), 7 . 05 ( 1h , dd , j = 9 . 1 , 12 . 2 hz ), 7 . 30 ( 1h , dd , j = 4 . 7 , 9 . 1 hz ), 7 . 32 - 7 . 40 ( 2h , m ), 7 . 50 - 7 . 55 ( 1h , m ), 8 . 21 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 1 . 40 ( 3h , t , j = 7 . 0 hz ), 3 . 66 ( 3h , s ), 3 . 77 ( 3h , s ), 4 . 16 ( 2h , q , j = 7 . 0 hz ), 6 . 03 ( 2h , d , j = 8 . 2 hz ), 6 . 55 - 6 . 65 ( 2h , m ), 7 . 02 ( 1h , dd , j = 9 . 0 , 12 . 3 hz ), 7 . 17 ( 1h , d , j = 9 . 0 hz ), 7 . 28 ( 1h , dd , j = 4 . 7 , 9 . 0 hz ), 8 . 09 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 93 ( 3h , t , j = 7 . 5 hz ), 1 . 27 ( 3h , t , j = 7 . 0 hz ), 1 . 70 - 1 . 90 ( 2h , m ), 3 . 95 - 4 . 10 ( 4h , m ), 6 . 03 ( 2h , d , j = 8 . 9 hz ), 6 . 90 - 7 . 05 ( 3h , m ), 7 . 20 ( 1h , dd , j = 4 . 6 , 9 . 1 hz ), 7 . 40 ( 2h , d , j = 8 . 7 hz ), 8 . 15 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 57 ( 3h , t , j = 7 . 4 hz ), 1 . 70 - 1 . 85 ( 2h , m ), 3 . 69 ( 3h , s ), 3 . 96 ( 2h , d , j = 6 . 7 hz ), 5 . 98 ( 2h , d , j = 8 . 9 hz ), 6 . 65 - 6 . 75 ( 2h , m ), 6 . 95 ( 1h , dd , j = 8 . 4 , 12 . 2 hz ), 7 . 15 - 7 . 30 ( 2h , m ), 8 . 12 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 20 - 0 . 35 ( 2h , m ), 0 . 40 - 0 . 60 ( 2h , m ), 1 . 20 - 1 . 45 ( 1h , m ), 3 . 73 ( 3h , s ), 3 . 90 ( 2h , d , j = 7 . 3 hz ), 6 . 09 ( 2h , d , j = 9 . 2 hz ), 6 . 80 - 7 . 05 ( 3h , m ), 7 . 21 ( 1h , dd , j = 4 . 7 , 9 . 0 hz ), 7 . 40 ( 2h , d , j = 8 . 8 hz ), 8 . 15 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 1 . 38 ( 3h , t , j = 7 . 0 hz ), 3 . 73 ( 3h , s ), 4 . 10 ( 2h , q , j = 7 . 0 hz ), 6 . 01 ( 2h , d , j = 8 . 4 hz ), 6 . 90 - 7 . 05 ( 3h , m ), 7 . 19 ( 1h , dd , j = 4 . 6 , 8 . 9 hz ), 7 . 40 ( 2h , d , j = 8 . 8 hz ), 8 . 13 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 1 . 63 - 2 . 10 ( 6h , m ), 2 . 75 - 3 . 00 ( 1h , m ), 3 . 72 ( 3h , s ), 4 . 00 ( 2h , d , j = 7 . 2 hz ), 5 . 99 ( 2h , d , j = 9 . 8 hz ), 6 . 90 - 7 . 05 ( 3h , m ), 7 . 17 ( 1h , dd , j = 4 . 7 , 9 . 1 hz ), 7 . 40 ( 2h , d , j = 8 . 7 hz ), 8 . 14 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 94 ( 3h , d , j = 7 . 5 hz ), 1 . 70 - 1 . 95 ( 2h , m ), 3 . 73 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 5 hz ), 6 . 02 ( 2h , d , j = 9 . 1 hz ), 6 . 90 - 7 . 50 ( 5h , m ), 8 . 16 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 60 - 1 . 75 ( 10h , m ), 2 . 40 - 2 . 60 ( 1h , m ), 2 . 66 ( 3h , s ), 3 . 73 ( 3h , s ), 5 . 80 ( 1h , dd , j = 7 . 7 , 7 . 8 hz ), 6 . 80 - 7 . 05 ( 4h , m ), 7 . 35 - 7 . 55 ( 3h , m ), 8 . 18 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 94 ( 3h , d , j = 7 . 5 hz ), 1 . 70 - 1 . 90 ( 2h , m ), 3 . 79 ( 3h , s ), 3 . 93 ( 2h , t , j = 6 . 7 hz ), 5 . 99 ( 2h , d , j = 9 . 1 hz ), 6 . 92 ( 1h , dd , j = 9 . 0 , 12 . 3 hz ), 7 . 08 ( 1h , dd , j = 4 . 7 , 9 . 0 hz ), 7 . 86 ( 1h , s ), 8 . 02 ( 1h , s ), 8 . 30 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 96 ( 3h , d , j = 7 . 4 hz ), 1 . 70 - 1 . 95 ( 2h , m ), 4 . 06 ( 2h , t , j = 6 . 7 hz ), 6 . 10 ( 2h , d , j = 9 . 6 hz ), 7 . 05 ( 1h , dd , j = 8 . 9 , 12 . 1 hz ), 7 . 29 ( 1h , dd , j = 4 . 4 , 8 . 9 hz ), 8 . 41 ( 1h , s ), 8 . 94 ( 2h , s ), 8 . 96 ( 1h , s ). the above compound was prepared in the same manner as in example 31 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 23 - 1 . 29 ( 3h , t , j = 7 . 1 hz ), 1 . 70 - 1 . 78 ( 2h , m ), 1 . 91 - 2 . 15 ( 6h , m ), 2 . 52 - 2 . 87 ( 2h , m ), 3 . 14 - 3 . 44 ( 2h , m ), 4 . 00 - 4 . 08 ( 2h , q , j = 6 . 1 hz ), 4 . 59 - 4 . 64 ( 2h , t , j = 6 . 9 hz ), 6 . 87 - 7 . 03 ( 3h , m ), 7 . 14 - 7 . 37 ( 1h , m ), 7 . 51 ( 1h , s ), 7 . 55 - 7 . 73 ( 2h , m ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 63 - 1 . 81 ( 2h , m ), 1 . 87 - 2 . 14 ( 6h , m ), 2 . 57 - 2 . 81 ( 2h , m ), 3 . 14 - 3 . 39 ( 2h , m ), 3 . 81 ( 3h , s ), 4 . 61 - 4 . 66 ( 2h , t , j = 6 . 8 hz ), 6 . 84 - 7 . 01 ( 3h , m ), 7 . 25 - 7 . 30 ( 1h , m ), 7 . 52 - 7 . 63 ( 3h , m ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 0 . 82 - 0 . 88 ( 3h , t , j = 7 . 1 hz ), 1 . 21 - 1 . 31 ( 4h , m ), 1 . 74 - 1 . 77 ( 2h , m ), 1 . 89 - 2 . 10 ( 2h , m ), 2 . 60 - 2 . 80 ( 2h , m ), 3 . 04 - 3 . 12 ( 2h , m ), 3 . 20 - 3 . 45 ( 2h , m ), 3 . 82 ( 3h , s ), 4 . 58 - 4 . 63 ( 2h , m ), 5 . 20 - 5 . 30 ( 1h , m ), 6 . 88 - 6 . 94 ( 2h , m ), 7 . 23 - 7 . 28 ( 1h , m ), 7 . 52 ( 1h , s ), 7 . 61 - 7 . 67 ( 2h , m ). the above compound was prepared in the same manner as in example 32 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 80 - 2 . 00 ( 6h , m ), 2 . 33 - 2 . 39 ( 2h , t , j = 7 . 2 hz ), 3 . 00 - 3 . 05 ( 4h , m ), 3 . 96 - 4 . 01 ( 2h , t , j = 6 . 4 hz ), 6 . 84 - 6 . 93 ( 3h , m ), 7 . 32 - 7 . 37 ( 1h , m ), 7 . 50 - 7 . 53 ( 2h , d , j = 8 . 7 hz ), 7 . 79 ( 1h , s ), 10 . 95 ( 1h , s ), 11 . 80 - 12 . 20 ( 1h , brs ). the above compound was prepared in the same manner as in example 33 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 81 - 0 . 87 ( 3h , t , j = 7 . 0 hz ), 1 . 19 - 1 . 40 ( 4h , m ), 1 . 85 - 1 . 95 ( 6h , m ), 2 . 19 - 2 . 25 ( 2h , t , j = 7 . 2 hz ), 2 . 97 - 3 . 10 ( 6h , m ), 3 . 93 - 3 . 98 ( 2h , t , j = 6 . 3 hz ), 6 . 85 - 6 . 93 ( 3h , m ), 7 . 34 - 7 . 39 ( 1h , m ), 7 . 51 - 7 . 54 ( 2h , d , j = 8 . 3 hz ), 7 . 75 - 7 . 83 ( 2h , m ), 10 . 97 ( 1h , brs ). sodium iodide ( 1 . 4 g , 0 . 9 mmol ) and sodium hydride ( 60 % oil base , 220 mg , 5 . 5 mmol ) were added to a dmf solution ( 15 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 1 . 0 g , 3 . 0 mmol ) and stirred at room temperature for 10 minutes . chloromethyl ( tert - butoxycarbonylmethylamino ) acetate ( 2 . 52 g , 10 . 6 mmol ) was added to the reaction mixture while ice - cooling , and then the mixture was stirred at room temperature for 3 hours . an aqueous sodium bicarbonate solution was added to the reaction mixture and then the mixture was subjected to extraction using ethyl acetate . the thus - obtained organic layer was dried over sodium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( n - hexane : ethyl acetate = 2 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a pale yellow amorphous solid of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ( tert - butoxycarbonyl methylamino ) acetate ( 290 mg , yield : 18 %). 1 h - nmr ( cdcl 3 ) δ ppm : 100 - 1 . 15 ( 3h , m ), 1 . 29 - 1 . 44 ( 9h , s ), 1 . 85 - 2 . 00 ( 2h , m ), 2 . 88 - 2 . 90 ( 3h , s ), 3 . 84 ( 3h , s ), 3 . 90 - 4 . 15 ( 4h , m ), 6 . 46 - 6 . 51 ( 2h , s ), 6 . 90 - 7 . 15 ( 4h , m ), 7 . 59 ( 2h , d , j = 8 . 6 hz ), 7 . 74 - 7 . 79 ( 1h , s ). a 4n hydrogen chloride ethylacetate solution ( 1 ml ) was added to an ethyl acetate solution ( 2 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ( tert - butoxycarbonylmethylamino ) acetate ( 100 mg , 0 . 19 mmol ) and stirred at room temperature for 3 hours . the deposited insoluble matter was collected by filtration , washed with acetone , and then dried , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl methylaminoacetate hydrochloride ( 78 . 3 mg , yield : 88 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 ( 3h , t , j = 7 . 4 hz ), 1 . 80 - 1 . 90 ( 2h , m ), 2 . 45 - 2 . 60 ( 3h , m ), 3 . 79 ( 3h , s ), 4 . 07 ( 2h , s ), 4 . 10 ( 2h , t , j = 6 . 6 hz ), 6 . 61 ( 2h , s ), 6 . 99 ( 2h , d , j = 8 . 9 hz ), 7 . 11 ( 1h , dd , j = 9 . 1 , 11 . 5 hz ), 7 . 39 ( 1h , dd , j = 4 . 5 , 9 . 1 hz ), 7 . 60 ( 2h , d , j = 8 . 9 hz ), 8 . 17 ( 1h , s ), 9 . 14 ( 2h , br ). the above compound was prepared in the same manner as in example 106 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 77 - 1 . 88 ( 6h , m ), 2 . 31 - 2 . 34 ( 4h , m ), 2 . 58 ( 2h , t , j = 5 . 4 hz ), 3 . 37 - 3 . 44 ( 8h , m ), 4 . 04 ( 2h , t , j = 6 . 5 hz ), 4 . 67 ( 2h , d , j = 5 . 4 hz ), 7 . 01 ( 1h , dd , j = 9 . 0 hz , 11 . 6 hz ), 7 . 27 ( 1h , dd , j = 4 . 5 hz , 9 . 0 hz ), 7 . 52 ( 2h , d , j = 8 . 3 hz ), 7 . 72 ( 2h , d , j = 8 . 3 hz ), 8 . 05 ( 1h , s ). a 4n hydrogen chloride ethylacetate solution ( 2 ml ) was added to an ethyl acetate solution ( 3 ml ) of di - tert - butyl 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl phosphate ( 300 mg , 0 . 55 mmol ) while ice - cooling and the mixture was stirred at room temperature for 2 hours . the deposited insoluble matter was collected by filtration and dried , giving a white powder of 1 - chloromethyl - 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 18 mg , yield : 92 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 13 ( 3h , t , j = 7 . 5 hz ), 1 . 70 - 2 . 10 ( 2h , m ), 3 . 84 ( 3h , s ), 4 . 11 ( 2h , t , j = 6 . 6 hz ), 6 . 40 ( 2h , s ), 6 . 90 - 7 . 05 ( 3h , m ), 7 . 12 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 51 ( 1h , s ), 8 . 59 ( 2h , d , j = 8 . 8 hz ). benzyloxyacetyl chloride ( 1 . 9 ml , 3 equivalent weight ) was added to a dichloromethane solution ( 50 ml ) of 4 -( tert - butyldimethylsilyloxy )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - quinolin ( 1 . 5 g , 3 . 4 mmol ) while ice - cooling and the mixture was stirred overnight at room temperature . an aqueous sodium bicarbonate solution was added to the reaction mixture , followed by extraction using ethyl acetate . the thus - obtained organic layer was dried over sodium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( n - hexane : ethyl acetate = 2 : 1 ). the purified product was concentrated under reduced pressure , giving a colorless oily substance of 1 -( 2 - benzyloxyacetyl )- 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 250 mg , yield : 15 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 70 - 1 . 90 ( 2h , m ), 3 . 84 ( 3h , s ), 3 . 95 ( 2h , t , j = 6 . 4 hz ), 4 . 38 ( 2h , s ), 4 . 52 ( 2h , s ), 6 . 94 ( 2h , d , j = 8 . 8 hz ), 6 . 95 - 7 . 40 ( 7h , m ), 7 . 57 ( 2h , d , j = 8 . 8 hz ), 7 . 92 ( 1h , s ). the above compound was prepared in the same manner as in example 233 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 05 ( 3h , t , j = 7 . 5 hz ), 1 . 80 - 2 . 00 ( 2h , m ), 2 . 41 ( 3h , s ), 3 . 83 ( 3h , s ), 4 . 02 ( 2h , t , j = 5 . 7 hz ), 6 . 95 ( 2h , d , j = 8 . 9 hz ), 7 . 00 - 7 . 15 ( 2h , m ), 7 . 59 ( 2h , d , j = 8 . 9 hz ), 8 . 02 ( 1h , s ). the above compound was prepared in the same manner as in example 233 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 0 . 95 - 1 . 15 ( 3h , m ), 1 . 70 - 2 . 05 ( 2h , m ), 3 . 80 - 4 . 20 ( 7h , m ), 6 . 50 - 8 . 00 ( 7h , m ). the above compound was prepared in the same manner as in example 229 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 80 - 2 . 00 ( 2h , m ), 3 . 84 ( 3h , s ), 4 . 08 ( 2h , t , j = 6 . 7 hz ), 5 . 11 ( 2h , s ), 6 . 62 ( 2h , s ), 6 . 90 - 7 . 15 ( 6h , m ), 7 . 30 - 7 . 45 ( 5h , m ), 7 . 62 ( 2h , d , j = 8 . 9 hz ), 7 . 84 ( 1h , s ), 7 . 94 ( 2h , d , j = 8 . 9 hz ). 10 % palladium / carbon ( 260 mg ) was added to a thf ( 30 ml ) and ethanol ( 15 ml ) solution of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 - benzyloxybenzoate ( 2 . 6 g , 4 . 6 mmol ). the mixture was subjected to hydrogen substitution and stirred at room temperature for 3 hours . after completion of the reaction , the catalyst was removed by conducting filtration using celite , and the mixture was concentrated to dryness under reduced pressure , giving a pale yellow powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 - hydroxybenzoate ( 2 . 22 g , yield : quantitative ). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 80 - 2 . 00 ( 2h , m ), 3 . 81 ( 3h , s ), 4 . 08 ( 2h , t , j = 6 . 7 hz ), 6 . 63 ( 2h , s ), 6 . 42 ( 2h , d , j = 8 . 8 hz ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 10 ( 1h , dd , j = 4 . 4 , 9 . 0 hz ), 7 . 22 ( 1h , br ), 7 . 58 ( 2h , d , j = 8 . 8 hz ), 7 . 83 ( 2h , d , j = 8 . 8 hz ), 7 . 88 ( 1h , s ). 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 - hydroxybenzoate ( 2 . 2 g , 4 . 6 mmol ) was suspended in acetone ( 50 ml ). tetrasol ( 420 mg ) and di - tert - butyl diisopropyl phosphoramidite ( 1 . 9 ml ) were added thereto and the resulting suspension was stirred at room temperature for 2 hours . the reaction mixture was ice - cooled , and an aqueous 30 % hydrogen peroxide solution ( 2 . 9 ml ) was added thereto , followed by stirring at the same temperature for 2 hours . an aqueous sodium thiosulphate solution and an aqueous sodium bicarbonate solution were added to the reaction mixture . the resulting mixture was stirred and then concentrated under reduced pressure . water was added to the residue , followed by extraction using ethyl acetate . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution , dried over sodium sulfate , and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( n - hexane : ethyl acetate = 100 : 1 → 2 : 1 ). the purified material was concentrated to dryness under reduced pressure , giving a white amorphous solid of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 -( di - tert - butoxyphosphono ) benzoate ( 2 . 51 g , yield : 81 %). 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 ( 3h , t , j = 7 . 4 hz ), 1 . 50 ( 18h , s ), 1 . 80 - 2 . 00 ( 2h , m ), 3 . 84 ( 3h , s ), 4 . 08 ( 2h , t , j = 6 . 7 hz ), 6 . 63 ( 2h , s ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 10 ( 1h , dd , j = 4 . 4 , 9 . 0 hz ), 7 . 26 ( 2h , d , j = 8 . 5 hz ), 7 . 62 ( 2h , d , j = 8 . 7 hz ), 7 . 83 ( 1h , s ), 7 . 97 ( 2h , d , j = 8 . 5 hz ). trifluoro - acetic acid ( 2 ml ) was added to a dichloromethane solution ( 10 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 -( di - tert - butoxy - phosphono ) benzoate ( 500 mg ) while ice - cooling , and then the mixture was stirred at the same temperature for 1 hour . the resulting mixture was concentrated under reduced pressure at a bath temperature of not higher than 30 ° c . the residue was recrystallized from ethyl acetate - n - hexane , giving a pale yellow powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 - phosphonoxybenzoate ( 406 . 7 mg , yield : 98 %). 1 h - nmr ( dmso - d 6 ) δ ppm : 0 . 93 ( 3h , t , j = 7 . 4 hz ), 1 . 60 - 1 . 85 ( 2h , m ), 3 . 79 ( 3h , s ), 4 . 06 ( 2h , t , j = 6 . 5 hz ), 6 . 64 ( 2h , s ), 6 . 98 ( 2h , d , j = 8 . 8 hz ), 7 . 09 ( 1h , dd , j = 9 . 1 , 11 . 5 hz ), 7 . 27 ( 2h , d , j = 8 . 7 hz ), 7 . 37 ( 1h , dd , j = 4 . 4 , 9 . 1 hz ), 7 . 62 ( 2h , d , j = 8 . 8 hz ), 7 . 92 ( 2h , d , j = 8 . 7 hz ), 8 . 38 ( 1h , s ). 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 - phosphonoxybenzoate ( 397 mg ) was suspended in isopropyl alcohol ( 10 ml ) while ice - cooling . a 1n aqueous sodium hydroxide solution ( 1 . 5 ml ) was added thereto and the suspension was stirred at the same temperature for 1 hour . the deposited insoluble matter was collected by filtration and recrystallized from acetone - water , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl 4 - phosphonoxybenzoate disodium salt ( 338 . 6 mg ). 1 h - nmr ( d 2 o ) δ ppm : 0 . 81 ( 3h , t , j = 7 . 4 hz ), 1 . 50 - 2 . 00 ( 2h , m ), 3 . 60 ( 3h , s ), 3 . 89 ( 2h , t , j = 6 . 7 hz ), 6 . 30 ( 2h , s ), 6 . 68 ( 2h , d , j = 8 . 7 hz ), 6 . 92 ( 1h , dd , j = 9 . 1 , 12 . 1 hz ), 7 . 05 - 7 . 20 ( 5h , m ), 7 . 75 ( 2h , d , j = 8 . 9 hz ), 7 . 79 ( 1h , s ). the above compound was prepared in the same manner as in example 229 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 06 ( 3h , t , j = 7 . 5 hz ), 1 . 75 - 2 . 00 ( 2h , m ), 3 . 84 ( 3h , s ), 4 . 00 ( 2h , t , j = 6 . 6 hz ), 4 . 44 ( 2h , s ), 5 . 92 ( 2h , s ), 6 . 90 - 7 . 40 ( 9h , m ), 7 . 59 ( 2h , d , j = 8 . 8 hz ), 7 . 76 ( 1h , s ). 1 - bromo - 2 , 3 , 4 , 6 - tetra - o - acetyl - α - d - glucopyranosyl ( 17 . 0 g , 41 . 3 mmol ), benzyltri - n - butylammonium bromide ( 1 . 3 g , 4 . 16 mmol ), potassium carbonate ( 14 . 37 g , 104 mmol ) and water ( 0 . 45 ml ) were sequentially added in this order to a chloroform solution ( 90 ml ) of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1h - quinolin - 4 - one ( 6 . 75 g , 20 . 6 mmol ). chloroform ( 27 ml ) was added to the resulting reaction mixture and the mixture was then stirred at room temperature for 39 hours . 2n hydrochloric acid ( 80 ml ) was added to the thus - obtained mixture while ice - cooling , followed by extraction with dichloromethan . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : ethyl acetate = 30 : 1 → 4 : 1 ). the purified product was concentrated under reduced pressure . the residue was dissolved in ethanol ( 100 ml ), and an aqueous solution ( 8 . 16 ml ) of potassium hydroxide ( 5 . 44 g ) was added thereto , followed by stirring at room temperature for 3 hours . the resulting reaction mixture was concentrated under reduced pressure . 2n hydrochloric acid ( 20 . 4 ml ) was added to the residue , and extraction was conducted using ethyl acetate . the thus - obtained organic layer was washed with an aqueous saturated sodium chloride solution and then concentrated under reduced pressure . the residue was purified using silica gel column chromatography ( dichloromethane : methanol = 50 : 1 → 20 : 1 → ethyl acetate : methanol = 30 : 1 ). the purified product was concentrated under reduced pressure , and the residue was then recrystallized from ethyl acetate , giving a white powder of 5 - fluoro - 3 -( 4 - methoxyphenyl )- 8 - propoxy - 1 -(( 2r , 3r , 4s , 5s , 6r )- 3 , 4 , 5 - trihydroxy - 6 - hydroxymethyltetrahydropyran - 2 - yl )- 1h - quinolin - 4 - one ( 0 . 38 g ). 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 ( 3h , t , j = 7 . 3 hz ), 1 . 79 - 1 . 88 ( 2h , m ), 3 . 24 - 3 . 41 ( 3h , m ), 3 . 54 - 3 . 70 ( 3h , m ), 3 . 76 ( 3h , s ), 3 . 96 - 4 . 11 ( 2h , m ), 4 . 69 ( 1h , t , j = 5 . 5 hz ), 5 . 14 - 5 . 16 ( 2h , m ), 5 . 33 ( 1h , d , j = 5 . 4 hz ), 6 . 51 ( 1h , d , j = 8 . 9 hz ), 6 . 94 - 7 . 05 ( 3h , m ), 7 . 29 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 54 ( 2h , d , j = 8 . 8 hz ), 7 . 99 ( 1h , s ). the above compound was prepared in the same manner as in example 242 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 03 ( 3h , t , j = 7 . 3 hz ), 1 . 81 - 1 . 89 ( 2h , m ), 3 . 30 - 3 . 40 ( 1h , m ), 3 . 57 - 3 . 58 ( 3h , m ), 3 . 71 - 3 . 75 ( 2h , m ), 3 . 77 ( 3h , s ), 3 . 96 - 4 . 12 ( 2h , m ), 4 . 67 - 4 . 76 ( 2h , m ), 4 . 91 ( 1h , d , j = 5 . 7 hz ), 5 . 17 ( 1h , d , j = 5 . 4 hz ), 6 . 43 ( 1h , d , j = 8 . 8 hz ), 6 . 96 - 7 . 05 ( 3h , m ), 7 . 28 ( 1h , dd , j = 4 . 5 hz , 9 . 1 hz ), 7 . 52 ( 2h , d , j = 8 . 8 hz ), 8 . 05 ( 1h , s ). the above compound was prepared in the same manner as in example 23 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 09 ( 3h , t , j = 7 . 4 hz ), 1 . 44 ( 18h , s ), 1 . 80 - 2 . 00 ( 2h , m ), 3 . 84 ( 3h , s ), 4 . 06 ( 2h , t , j = 6 . 7 hz ), 4 . 53 ( 2h , d , j = 8 . 9 hz ), 6 . 51 ( 2h , s ), 6 . 90 - 7 . 00 ( 3h , m ), 7 . 08 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 59 ( 2h , d , j = 8 . 9 hz ), 7 . 73 ( 1h , s ). the above compound was prepared in the same manner as in example 239 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , d , j = 7 . 4 hz ), 1 . 65 - 1 . 90 ( 2h , m ), 3 . 79 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 6 hz ), 4 . 45 ( 2h , d , j = 9 . 0 hz ), 6 . 49 ( 2h , s ), 6 . 98 ( 2h , d , j = 8 . 9 hz ), 7 . 09 ( 1h , dd , j = 9 . 1 , 11 . 5 hz ), 7 . 36 ( 1h , dd , j = 4 . 4 , 9 . 1 hz ), 7 . 59 ( 2h , d , j = 8 . 9 hz ), 8 . 16 ( 1h , s ). the above compound was prepared in the same manner as in example 25 using appropriate starting material . 1 h - nmr ( d 2 o ) δ ppm : 0 . 84 ( 3h , d , j = 7 . 4 hz ), 1 . 55 - 1 . 70 ( 2h , m ), 3 . 61 ( 3h , s ), 3 . 86 ( 2h , t , j = 6 . 6 hz ), 4 . 25 ( 2h , d , j = 6 . 9 hz ), 6 . 26 ( 2h , s ), 6 . 73 ( 2h , d , j = 8 . 7 hz ), 6 . 88 ( 1h , dd , j = 9 . 2 , 12 . 1 hz ), 7 . 08 ( 1h , dd , j = 4 . 5 , 9 . 2 hz ), 7 . 18 ( 2h , d , j = 8 . 7 hz ), 7 . 78 ( 1h , s ). the above compound was prepared in the same manner as in example 229 using appropriate starting material . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 10 ( 3h , t , j = 7 . 4 hz ), 1 . 20 - 1 . 75 ( 24h , m ), 1 . 80 - 2 . 00 ( 2h , m ), 2 . 85 - 3 . 10 ( 2h , m ), 3 . 84 ( 3h , s ), 4 . 07 ( 2h , t , j = 6 . 6 hz ), 4 . 15 - 4 . 30 ( 1h , m ), 4 . 45 - 4 . 65 ( 1h , m ), 5 . 00 - 5 . 25 ( 1h , m ), 6 . 48 ( 2h , s ), 6 . 90 - 7 . 05 ( 3h , m ), 7 . 10 ( 1h , dd , j = 4 . 5 , 9 . 0 hz ), 7 . 59 ( 2h , d , j = 8 . 8 hz ), 7 . 74 ( 1h , s ). the above compound was prepared in the same manner as in example 229 using appropriate starting materials . 1 h - nmr ( cdcl 3 ) δ ppm : 1 . 08 ( 3h , t , j = 7 . 3 hz ), 1 . 12 ( 3h , t , j = 7 . 3 hz ), 1 . 79 ( 3h , d , j = 6 . 7 hz ), 1 . 90 - 2 . 00 ( 2h , m ), 2 . 30 ( 1h , q , j = 7 . 3 hz ), 2 . 33 ( 1h , q , j = 7 . 3 hz ), 3 . 85 ( 3h , s ), 4 . 00 ( 1h , td , j = 6 . 7 , 8 . 9 hz ), 4 . 12 ( 1h , td , j = 6 . 7 , 8 . 9 hz ), 6 . 80 - 7 . 10 ( 5h , m ), 7 . 66 ( 2h , d , j = 8 . 8 hz ), 8 . 29 ( 1h , s ). the above compound was prepared in the same manner as in example 1 using appropriate starting material . 1 h - nmr ( dmso - d 6 ) δ ppm : 3 . 76 ( 3h , s ), 3 . 83 ( 3h , s ), 6 . 65 ( 1h , d , j = 13 . 6 hz ), 6 . 76 ( 1h , s ), 6 . 92 ( 2h , d , j = 8 . 8 hz ), 7 . 54 ( 2h , d , j = 8 . 8 hz ), 7 . 90 ( 1h , d , j = 5 . 8 hz ), 11 . 75 ( 1h , brs ). the above compound was prepared in the same manner as in example 3 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 33 ( 3h , t , j = 6 . 9 hz ), 3 . 75 ( 3h , s ), 3 . 89 ( 3h , s ), 4 . 27 ( 2h , q , j = 7 . 0 hz ), 6 . 74 ( 1h , d , j = 13 . 7 hz ), 6 . 82 ( 1h , s ), 6 . 92 ( 2h , d , j = 8 . 7 hz ), 7 . 55 ( 2h , d , j = 8 . 7 hz ), 8 . 04 ( 1h , s ). the above compound was prepared in the same manner as in example 2 using appropriate starting materials . 1 h - nmr ( dmso - d 6 ) δ ppm : 1 . 00 ( 3h , t , j = 7 . 4 hz ), 1 . 06 ( 3h , t , j = 7 . 1 hz ), 1 . 67 - 1 . 88 ( 4h , m ), 2 . 16 ( 2h , t , j = 7 . 4 hz ), 2 . 58 ( 2h , t , j = 7 . 0 hz ), 3 . 76 ( 3h , s ), 3 . 90 ( 2h , q , j = 7 . 1 hz ), 4 . 14 ( 2h , t , j = 6 . 6 hz ), 6 . 81 - 6 . 94 ( 3h , m ), 7 . 06 ( 2h , d , j = 8 . 6 hz ), 7 . 15 ( 1h , dd , j = 4 . 0 hz , 8 . 8 hz ), 10 . 40 ( 1h , brs ). [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ] monophosphate ( 800 mg , 1 . 83 mmol ) was suspended in isopropyl alcohol ( 30 ml ). a 1n - potassium hydroxide aqueous solution ( 3 . 66 ml , 3 . 66 mmol ) was added thereto at 0 ° c . the resulting mixture was stirred at 0 ° c . for 1 . 5 hours . the generated insoluble matter was collected by filtration , recrystallized from acetone - water and then dried , giving a white powder of [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ] monophosphate dipotassium salt ( 445 mg , yield : 47 %). 1 h - nmr ( d 2 o ) δ ppm : 0 . 97 ( 3h , t , j = 7 . 4 hz ), 1 . 79 - 1 . 88 ( 2h , m ), 3 . 76 ( 3h , s ), 4 . 01 ( 2h , t , j = 6 . 7 hz ), 6 . 05 ( 2h , d , j = 9 . 1 hz ), 6 . 93 - 7 . 01 ( 3h , m ), 7 . 19 ( 1h , dd , j = 4 . 6 , 9 . 1 hz ), 7 . 43 ( 2h , d , j = 8 . 8 hz ), 8 . 16 ( 1h , s ). [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ] monophosphate disodium salt ( 800 mg , 1 . 66 mmol ) was dissolved in water ( 4 ml ). a calcium chloride ( 202 mg , 1 . 82 mmol ) aqueous solution ( 1 ml ) was added thereto at room temperature . the deposited solid was collected by filtration , washed with water and acetone , and then dried , giving a white powder of [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ] monophosphate calcium salt ( 690 mg , yield : 87 %). 1 h - nmr ( dmso - d 6 , 80 ° c .) δ ppm : 0 . 79 - 0 . 89 ( 3h , m ), 1 . 68 - 1 . 76 ( 2h , m ), 3 . 62 ( 3h , s ), 3 . 91 - 4 . 01 ( 2h , m ), 6 . 09 - 6 . 16 ( 2h , m ), 6 . 74 - 6 . 90 ( 3h , m ), 7 . 09 - 7 . 15 ( 1h , m ), 7 . 40 - 7 . 70 ( 2h , m ), 8 . 32 ( 1h , s ). [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ] monophosphate disodium salt ( 1 . 0 g , 2 . 07 mmol ) was suspended in methanol ( 10 ml ). a methanol solution ( 4 . 3 ml ) of magnesium chloride ( 198 mg , 2 . 08 mmol ) was added thereto at room temperature . the resulting mixture was stirred at room temperature for 20 minutes . the solid deposited after condensation was collected by filtration , washed with water and acetone , and then dried , giving a white powder of [ 5 - fluoro - 3 -( 4 - methoxyphenyl )- 4 - oxo - 8 - propoxy - 4h - quinolin - 1 - ylmethyl ] monophosphate magnesium salt ( 845 mg , yield : 88 %). 1 h - nmr ( dmso - d 6 , 80 ° c .) δ ppm : 0 . 99 ( 3h , t , j = 7 . 4 hz ), 1 . 76 - 1 . 86 ( 2h , m ), 3 . 64 ( 3h , s ), 4 . 05 ( 2h , t , j = 6 . 5 hz ), 6 . 09 ( 2h , d , j = 10 . 4 hz ), 6 . 80 - 6 . 98 ( 3h , m ), 7 . 24 ( 1h , dd , j = 4 . 6 , 8 . 6 hz ), 7 . 58 ( 2h , d , j = 8 . 7 hz ), 8 . 00 ( 1h , s ). evaluation of the improvement of mitochondrial dysfunction using human neuroblastoma cell lines sh - sy5y treated with 1 - methyl - 4 - phenylpyridinium ( mpp + ) in human neuroblastoma cell lines sh - sy5y in which mitochondrial activity was injured by mpp + treatment ( bollimuntha s . et al ., j biol chem , 280 , 2132 - 2140 ( 2005 ) and shang t . et al ., j biol chem , 280 , 34644 - 34653 ( 2005 )), the improvement of mitochondrial dysfunction was evaluated on the basis of measurement values for mitochondrial oxidation reduction activity using alamar blue fluorescent dye after the compound addition ( nakai m . et al , exp neurol , 179 , 103 - 110 ( 2003 )). the human neuroblastoma cell lines sh - sy5y were cultured in dulbecco &# 39 ; s modified eagle &# 39 ; s medium containing 10 % fetal bovine serum ( dmem containing 50 units / ml penicillin and 50 μg / ml streptomycin as antibiotics ) at 37 ° c . in the presence of 5 % carbon dioxide . cells were scattered on a poly - d - lysine - coated 96 - well black plate at a concentration of 3 - 6 × 10 4 cells / cm 2 ( medium amount : 100 μl / well ), and cultured in the above medium for two days . further , the medium was changed to dmem containing a 1 % n2 supplement ( n2 - dmem ) or to a medium ( 100 μl / well ) in which 1 . 5 mm mpp + was dissolved . the cells were cultured therein for 39 to 48 hours , and then subjected to a mitochondrial oxidation reduction activity measurement system . a sample compound that had been previously dissolved in dimethyl sulfoxide ( dmso ) was diluted with n2 - dmem , and added in a volume of 10 μl / well 24 hours before the activity measurement ( final compound concentration : 0 . 01 to 1 μg / ml ). after removal of the medium by suction , a balanced salt solution containing 10 % alamar blue ( 154 mm sodium chloride , 5 . 6 mm potassium chloride , 2 . 3 mm calcium chloride , 1 . 0 mm magnesium chloride , 3 . 6 mm sodium bicarbonate , 5 mm glucose , 5 mm hepes , ph 7 . 2 ) was added in a volume of 100 μl / well , and reacted in an incubator at 37 ° c . for 1 hour . the fluorescent intensity was detected using a fluorescence detector ( a product of hamamatsu photonics k . k ., excitation wavelength 530 nm , measurement wavelength 580 nm ) to thereby measure the mitochondrial oxidation reduction activity . the fluorescent intensity of the well of the cells cultured in a medium containing mpp + and in each of the sample compounds was relatively evaluated based on the 100 % fluorescent intensity of the well of the cells cultured in a medium containing dmso alone ( final concentration : 0 . 1 %). when the mpp + - induced cell groups exhibited higher florescent intensity than the cell groups cultured in dmso alone , the test compound was judged to have improved the activity of the mitochondrial dysfunction . using a mouse having mptp - induced dopaminergic neurons ( chan p . et al ., j neurochem , 57 , 348 - 351 ( 1991 )), the dopamine neuroprotective activity was evaluated based on dopamine contents and protein levels of tyrosine hydroxylase ( th ) and dopamine transporter ( dat ) ( i . e ., dopaminergic neuronal marker proteins ) in the brain corpus striatum region after the compound administration ( mori a . et al ., neurosci res , 51 , 265 - 274 ( 2005 )). a male c57bl / 6 mouse ( provided by japan charles river inc ., 10 to 12 weeks ) was used as a test animal . mptp was dissolved in a physiological salt solution so that the concentration became 4 mg / ml , and then administered to the mouse subcutaneously in a volume of 10 ml / kg . the test compound was suspended in a 5 % gum arabic / physiological salt solution ( w / v ) so that a compound having a concentration of 1 mg / ml could be obtained . each of the test compounds or solvents thereof was orally administered to the mouse after 30 minutes , 24 hours , and 48 hours of the mptp administration . the mouse was decapitated after 72 hours of the mptp administration , the brain was removed , and each side of the striatum was dissected . the left striatum was used as a sample to detect the protein levels by western blot analysis . each tissue was homogenized in a hepes buffer sucrose solution ( 0 . 32 m sucrose , 4 μg / ml pepstatin , 5 μg / ml aprotinin , 20 μg / ml trypsin inhibitor , 4 μg / ml leupeptin , 0 . 2 mm phenylmethanesulfonyl fluoride , 2 mm ethylenediaminetetraacetic acid ( edta ), 2 mm ethylene glycol bis ( β aminoethyl ether ) tetraacetic acid , 20 mm hepes , ph 7 . 2 ), and assayed for protein using a bicinchoninic acid kit for protein assay ( provided by pierce corporation ). each homogenized sample , having an equal amount of protein that had been dissolved in a laemmli sample buffer solution , was subjected to electrophoresis through sodium dodecyl sulfurate polyacrylamide gels . the protein separated by electrophoresis was electrically transferred to polyvinylidene fluoride membranes . the membranes were reacted with specific primary antibodies for th , dat , and housekeeping proteins , i . e ., the al subunit of na + / k + - atpase and actin ( na + / k + - atpase , a product of upstate biotechnology inc . ; others are products of chemi - con corporation ). subsequently , a horseradish peroxidase - labeled secondary antibody ( a product of amersham k . k .) for each primary antibody was fixed , and the chemiluminescence associated with enzyme activity of peroxidase was detected using x - ray film . the density of the protein band on the film was analyzed using a densitometer ( a product of bio - rad laboratories inc .) to obtain the th value relative to na + / k + - atpase and the dat value relative to actin . the right striatum , the tissue weight of which was measured immediately after dissection , was used as an analysis sample for determining the dopamine content . each tissue was homogenized in a 0 . 1 n perchloric acid solution containing isoproterenol as an internal standard substance of the measurement , using an ultrasonic homogenizer while being cooled with ice . the supernatant obtained from 20 , 000 g of homogenate that had been centrifuged at 4 ° c . for 15 minutes was subjected to a high performance liquid chromatography with a reversed phase column ( a product of eicom corporation ). a mobile phase 15 % methanol 0 . 1 m citric acid / 0 . 1 m sodium acetate buffer solution ( containing 190 mg / l 1 - sodium octane sulfonate , 5 mg / l edta , ph 3 . 5 ) was flowed at a rate of 0 . 5 ml / min , and the dopamine peak of each sample was detected using an electrochemical detector ( applied voltage + 750 mv vs . ag / agcl , a product of eicom corporation ). with reference to the identified dopamine peak , the dopamine content per tissue weight was calculated in each sample using analysis software ( a product of gilson inc .). in both analyses , the value of the sample derived from the mptp - induced mice in which only the test compound or the solvent was administered was expressed relative to the value of the sample derived from the mice without mptp treatment ( 100 %). values were analyzed statistically using a nonclinical statistical analysis system . values of significance probability & lt ; 0 . 05 were defined as statistically significant . in the mptp - induced mice , when the test drug group showed an increase in protein level compared to the solvent group , and a significant difference was observed between these groups in the t - assay , the test drug was judged to have dopamine neuroprotective activity . evaluation of the neuroprotective action in rat middle cerebral artery occlusion - reperfusion model the neuroprotective action of an experimental compound was evaluated in a middle cerebral artery ( mca ) occlusion - reperfusion rat model of stroke [ koizumi j . et al ., jpn j stroke , 8 , 1 - 8 ( 1986 )] using the cerebral infarct volume as an index [ kitagawa h . et al ., neurol res , 24 , 317 - 323 ( 2002 )]. male wistar rats ( 12 - 16 weeks old , japan slc , inc .) were used as the experimental animals . each rat was kept at 37 ° c . under isoflurane anesthetization , and immobilized in the supine position while breathing voluntarily . each rat was subjected to a median incision in the cervical region , and the right common carotid artery ( cca ), the right external carotid artery ( eca ) and the right internal carotid artery ( ica ) were exposed without damaging the vagus nerve . subsequently , the right cca and the right eca were ligated , the right ica was controlled with a suture at its origin and a small incision was made in the right cca . the occlusion of the right mca at its origin was produced by insertion of a silicon coated no . 4 - 0 nylon filament having 0 . 30 - 0 . 35 mm in diameter and about 17 mm in length into the ica . the right ica was ligated together with the filament , the skin was temporarily sutured , and the rats were returned to their cages . after 1 . 5 hours of occlusion , the cervical wound was reopened under isoflurane anesthesia , and the filament was slightly withdrawn to allow reperfusion . the cervical wound was closed , and the rats were returned to their cages . the experimental compounds were dissolved in a tris buffer solution or a physiological saline solution to produce a concentration of 1 . 5 to 15 mg / ml , and the prepared solutions or vehicle were intravenously administered in the quantity of 2 ml / kg immediately after the vascular occlusion and reperfusion . twenty - four hours after reperfusion , the rat whole brains were removed and the forebrain coronal sections were prepared in 2 - mm thick from the boundary of the cerebrum and cerebellum . the slices were incubated in a 1 % 2 , 3 , 5 - triphenyltetrazolium chloride ( ttc ) solution at 37 ° c . for 30 minutes and fixed by immersion in 10 % neutralized formalin . the images of the slices were scanned , and the area of the ttc achromatic region on the surface was measured using image - analysis software ( win roof ver . 5 . 6 , mitani corporation ). the measured area value was multiplied by the thickness of 2 mm to determine the volume of each slice , and the sum of the thus - obtained volumes was defined as the total cerebral infarct volume . the statistical difference in cerebral infarct volume between the vehicle administered group ( control group ) and the compound administered group was analyzed by a t - test ( two - tailed ) using a non - clinical statistical analysis system . a probability less than 0 . 05 was defined as a statistically significant difference . when a statistically significant decrease in the cerebral infarct volume was observed in the compound administered group compared to the control group , it was determined that the experimental compound had a neuroprotective effect . | 2 |
the advanced platform rocker described here can tilt the platform as a function of time , including non - periodical movement . the angle of the platform can be accurately controlled , thereby enabling the platform rocker to perform advanced routines as well as use the angular position of the platform to drive other functions . the electronic circuit accurately controls the angular position of the shaft of the motor . a stepper motor is used , whereby the electronic circuit controls its position , to within a fraction of a step or of a degree of rotation . a home sensor is used to determine when the cam is in a known reference position . the following provides a means to controllably couple the platform to the motor . the motor rotates the cam . the cam is either on the shaft of the motor or on a separate shaft , coupled by some means , such as with a belt or chain . the platform is connected by a linkage to the cam , so as the cam revolves , the platform tilts back and forth . by controlling the angular position of the cam , the tilt of the platform is controlled . because there is a defined relationship between the angular position of the shaft of the motor and the angular position of the cam , the tilt of the platform can be controlled accurately . the platform can be electronically controlled to tilt or rock back and forth at a smaller tilt angle , e . g . reversing the rotation of the cam , in order to rotate back and forth for only a portion of a revolution . in standard platform rockers , the motor does not reverse direction , and require mechanical changes to change the range of tilt , e . g . changing the radial distance from the center of the cam to where the linkage pivots . the ability to rock back and forth within a smaller range of tilt angles , and then tilt further as needed , enables this platform rocker to perform additional functions . for example , by tilting further , liquid can be poured out of trays on the platform . to prevent the trays from sliding off the platform , they can be clamped in place . by tilting further in the opposite direction , the liquid can be poured into a different container . likewise , with a means for piercing on the trays , with the action of tilting a platform , the tray can pierce a reservoir holding reagent , and the reagent can flow , under gravity , into the tray on the platform . while contemporary platform rockers run at a constant speed , the electronic circuit in the advanced platform rocker described here can drive the motor for a period of time , then pause , then continue to repeat this pattern . this platform rocker can also rock at very slow speeds , run quickly in one direction , then slowly in the other , or even run with a high frequency oscillation superimposed on another motion , leading to a vigorous agitation , e . g . for more rapid washing of blots and gels . the routines can be preprogrammed and / or programmed by the user . this advanced platform rocker incorporates automated fluid handling , eliminating the need for pumps and valves . a reagent is loaded in reservoir tubes with sealed bottoms , such as with foil seals . seals are pierced to release reagents which are gravity fed into the trays . lances are located on the trays and the same motor and controller that drive the rocking of the trays can cause the trays to tilt further from horizontal , enabling the lances to pierce the foil seals . similarly , this advanced platform rocker incorporates a separate slider which contains the reagent reservoir tubes . by maintaining the platform in a level position , driving the slider into position above the platform , and then tilting the platform , the lances are moved into contact with and puncture the seals of the reagent reservoir tubes . after which , the platform returns to the horizontal position and the slider returns to its home position , allowing the tray holding platform to rock without interference . this method uses only a single motor or just two motors to control the dispensing of the reagents without the use of a pump or valve and similarly reduces the required sets of tubing . reagent volumes are determined by the amount pre - loaded into the reagent reservoir tubes . tilting the tray holding platforms to a steep angle , the liquid pours out of the trays , into catch tanks or containers . the liquids is transferred to these waste containers or recovery containers without the use of a pump , valves , or tubing . a cover for each tray is mounted with slotted holes or other gravity based mechanism so that the entire tray or most of the tray is covered to prevent evaporation . the cover can slide . when the tray is tilted at a relatively large angle in one direction , the drain spout is exposed . when the tray is tilted in the other direction beyond the typical rocking angle , the inlet region by the lances is exposed . this advanced platform rocker can wash blots more aggressively by superimposing a higher frequency vibration onto the rocking motion . advanced rocking such as moving forward 3 steps of rotation , back 2 , forward 3 , back 2 , can be performed rather than a continuous progression in one direction . in addition , external devices or sensors can communicate with the electronic circuit , thereby affecting the rocking parameters and / or signaling the advancement to the subsequent step in the rocking routine . for instance , a camera could monitor the blots and image processing software could be used to determine when the washing was completed , so as not to overwash or underwash , ensuring the best contrast . another feature would be a bluetooth or internet connection to signal the user when the program was done or the status of the program at any time . programs could be introduced via bluetooth , sd cards , ethernet , wi - fi or usb memory sticks , or other method , in addition to programming at the instrument itself . while the preferred embodiment uses a microcontroller in the electronic circuit , a field programmable gate array , logic chips , or other electronic means could control the rocking and other actions of the platform rocker . in other embodiments , one or more sensors monitor the angular position of the motor shaft , such as with an encoder , the tilt of the platform , or the angle or position of the linkage . in one embodiment , the electronic circuit also controls a means for transferring heat to or from the trays , such as a thermoelectric device or refrigeration unit mounted adjacent to the trays . in another embodiment , external sensors communicate with the electronic circuit . for example , an optical sensor , such as a ccd , signals that a predetermined amount of contrast in fluorescence is detected in a blot in the tray , thereby signaling that the washing is complete and the rocking proceeds to the next step in the routine . likewise , sensors monitor the ambient temperature , and the electronic circuit changes the rocking rate or times in response . signals from another device , at times such as when liquid pours into a tray on the platform , indicate to the electronic circuit that it needs to alter the rocking or to proceed to the next rocking step or to pause for an image to be taken of samples in the trays . | 1 |
the collection of pyrimidine intermediates disclosed in this invention which are suitable for eventual conversion to rnfx must allow formation of a tetrahydropyrimidin - 5 ( 4h )- one having the following structure : wherein z 1 is selected from the group consisting of halosulfonyl , polyhaloalkanesulfonyl , polyhaloarenesulfonyl , a regioisomer of fluoroarenesulfonyl , polyhaloarenesulfonyl , a regioisomer of cyanoarenesulfonyl , polycyanoarenesulfonyl , a regioisomer of nitroarenesulfonyl , and polynitroarenesulfonyl . further , the regioisomer of fluoroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - fluoro - substituted arenesulfonyl , the regioisomer of cyanoarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - cyano - substituted arenesulfonyl and the regioisomer of nitroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - nitro - substituted arenesulfonyl . in the invention , a tetrahydropyrimidin - 5 ( 4h )- one is a necessary precursor to a 5 , 5 - bis ( difluoramino ) hexahydropyrimidine , based on the known conversion of ketone carbonyl groups by reaction with difluoramine or difluorosulfamic acid in the presence of a strong acid . the nitrogen - protecting groups chosen for the new pyrimidine intermediates and precursors are certain sulfonyl substituents . the particular sulfonyl substituents are chosen from a group that favorably affects the basicity of the pyrimidine nitrogens to make them less basic than the oxygen sites in the pyrimidine intermediates , in order to allow difluoramination of the carbonyl oxygens to proceed to geminal - bis ( difluoramino ) alkylene derivatives . suitable intermediates leading to tetrahydropyrimidin - 5 ( 4h )- ones include hexahydro - 5 - pyrimidinols ( including their oxygen - protected derivatives ) and hexahydro - 5 -( methylene ) pyrimidines . these novel n - sulfonylpyrimidine derivatives include hexahydro - 5 - pyrimidinols having the structure : wherein z 1 is selected from the group consisting of halosulfonyl , polyhaloalkanesulfonyl , polyhaloarenesulfonyl , a regioisomer of fluoroarenesulfonyl , polyhaloarenesulfonyl , a regioisomer of cyanoarenesulfonyl , polycyanoarenesulfonyl , a regioisomer of nitroarenesulfonyl , and polynitroarenesulfonyl . further , the regioisomer of fluoroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - fluoro - substituted arenesulfonyl , the regioisomer of cyanoarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - cyano - substituted arenesulfonyl and the regioisomer of nitroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - nitro - substituted arenesulfonyl . ; and wherein r 1 is selected from the group consisting of hydrogen and an alcohol - protecting group . the novel n - sulfonylpyrimidine derivatives also include hexahydro - 5 -( methylene ) pyrimidines having the following structure : wherein z 1 is selected from the group consisting of halosulfonyl , polyhaloalkanesulfonyl , polyhaloarenesulfonyl , a regioisomer of fluoroarenesulfonyl , polyhaloarenesulfonyl , a regioisomer of cyanoarenesulfonyl , polycyanoarenesulfonyl , a regioisomer of nitroarenesulfonyl , and polynitroarenesulfonyl . further , the regioisomer of fluoroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - fluoro - substituted arenesulfonyl , the regioisomer of cyanoarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - cyano - substituted arenesulfonyl and the regioisomer of nitroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - nitro - substituted arenesulfonyl . in the preferred embodiment , a hexahydro - 5 -( methylene ) pyrimidine is utilized as the intermediate leading to a tetrahydropyrimidin - 5 ( 4h )- one . in the present invention , the production of hexahydro - 5 -( methylene ) pyrimidines is accomplished as follows : wherein z 1 is selected from the group consisting of halosulfonyl , polyhaloalkanesulfonyl , polyhaloarenesulfonyl , a regioisomer of cyanoarenesulfonyl , polycyanoarenesulfonyl , a regioisomer of nitroarenesulfonyl , and polynitroarenesulfonyl . further , the regioisomer of fluoroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - fluoro - substituted arenesulfonyl , the regioisomer of cyanoarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - cyano - substituted arenesulfonyl and the regioisomer of nitroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - nitro - substituted arenesulfonyl . hexahydro - 5 - pyrimidinols and hexahydro - 5 -( methylene ) pyrimidines are suitable intermediates that can be converted to tetrahydropyrimidin - 5 ( 4h )- one precursors . for example , hexahydro - 5 -( methylene ) pyrimidines are converted to tetrahydropyrimidin - 5 ( 4h )- ones by ozonlysis of the exo - methylene substituent . next , these precursors are converted to novel 5 , 5 - bis ( difluoramino ) hexahydropyrimidines and other geminal - bis ( difluoramino ) alkylene derivatives by difluoramination . in the preferred embodiment of the invention , the general path of the reaction , after the formation of a tetrahydropyrimidin - 5 ( 4h )- one , is illustrated as follows : wherein z 1 is selected from the group consisting of halosulfonyl , polyhaloalkanesulfonyl , polyhaloarenesulfonyl , a regioisomer of fluoroarenesulfonyl , polyhaloarenesulfonyl , a regioisomer of cyanoarenesulfonyl , polycyanoarenesulfonyl , a regioisomer of nitroarenesulfonyl , and polynitroarenesulfonyl . further , the regioisomer of fluoroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - fluoro - substituted arenesulfonyl , the regioisomer of cyanoarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - cyano - substituted arenesulfonyl and the regioisomer of nitroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - nitro - substituted arenesulfonyl . ; and wherein r 2 is selected from the group consisting of hydrogen , c 1 - c 2 alkyl , protected hydroxymethyl and 1 , 2 ethanediyl . in another embodiment of the invention , the reaction may also be accomplished using a carbonyl , rather than the r 2 groups illustrated above . that general path is illustrated as follows : wherein z 1 is selected from the group consisting of halosulfonyl , polyhaloalkanesulfonyl , polyhaloarenesulfonyl , a regioisomer of fluoroarenesulfonyl , polyhaloarenesulfonyl , a regioisomer of cyanoarenesulfonyl , polycyanoarenesulfonyl , a regioisomer of nitroarenesulfonyl , and polynitroarenesulfonyl . further , the regioisomer of fluoroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - fluoro - substituted arenesulfonyl , the regioisomer of cyanoarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - cyano - substituted arenesulfonyl and the regioisomer of nitroarenesulfonyl is selected from the group consisting of 2 -, 3 - and 4 - nitro - substituted arenesulfonyl . tetrahydropyrimidin - 5 ( 4h )- ones suitable for conversion to 5 , 5 - bis ( difluoramino ) hexahydropyrimidines are substituted on the nitrogens ( positions 1 and 3 ) by electron - withdrawing sulfonyl substituents . the particular sulfonyl substituents are chosen from a specific group that imparts lower basicity to the nitrogens than to the oxygen in the tetrahydropyrimidin - 5 ( 4h )- ones . therefore , the substitituent causes the nitrogens to have acid dissociation constants ( pk a ) of the ( protonated ) conjugate acid forms of the nitrogen sites to be less than that of the ketones , typically about − 7 . the sulfonyl substituents may include alkanesulfonyl , halosulfonyl , or arenesulfonyl substituents , but the arenesulfonyl must have electron - withdrawing subsitituents on the phenyl rings . for example , the nitro group ( no 2 ) is a suitable electron - withdrawing subsitituent . any single or multiple electron - withdrawing subsitituent ( s ) that collectively lower ( s ) the basicity of the arenesulfonyl - protected nitrogens below that of the oxygen in corresponding tetrahydropyrimidin - 5 ( 4h )- ones is ( are ) suitable . similarly , alkanesulfonyl protecting groups may be electronegatively substituted to impart the same property on the protected nitrogens . in general , the sulfonyl substituent must have an inductive substituent constant ( σ i or f ) of a value greater than that of unsubstituted benzenesulfonyl , approximately 0 . 58 . such electronegatively substituted pyrimidines are unprecedented . the geminal - bis ( difluoramino ) alkylene derivatives must be susceptible to nitrolysis to form n - protected nitramines ( i . e . nitramides ) and the intermediate nitramides must be susceptible to deprotection to form desired nitramine intermediates . those intermediates then undergo cyclization by reaction with aldehydes or other alkylating reagents to form difluoramino - substituted heterocyclic nitramines . in the final step of the process , 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine intermediate is reacted with an electrophile or alkylating reagent , such as aldehyde , alkylene dihalide , aldehyde equivalent or alkylene di ( pseudohalide ), to undergo cyclization to a desired difluoramino - substituted heterocyclic nitramine . a cyclic 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine is the same as a generic 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - dinitropyrimidine when the cyclization is effected by a group containing only a single - carbon linkage between the two nitrogens ( positions 1 and 3 ). this linkage may have additional substituents , but the pyrimidine linkage contains n — c — n atoms directly bonded . the process of making rnfx consists of nitrolyzing the cyclic 2 , 2 - bis ( difluoramino )- n , n ′- disulfonyl - 1 , 3 - propanediamine with nitric acid or other nitronium source to prepare a 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - n , n ′- disulfonyl - 1 , 3 - propanediamine . this nitrolysis may proceed via a 2 , 2 - bis ( difluoramino )- n - nitro - 1 , 3 - propanediamine intermediate , if a chemical linkage bridging the precursor &# 39 ; s sulfonamide nitrogens is retained by one of the nitrogens upon nitrolysis . the resulting 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - n , n ′- disulfonyl - 1 , 3 - propanediamine is then subjected to nucleophilic displacement of the sulfonyl protecting group . in 2 , 2 - bis ( difluoramino ) propanamine derivatives , this deprotection is relatively facile , and appropriate nucleophiles include a wide variety of oxygen , nitrogen and other heteroatom derivatives , examples of which include water , alcohols and amines . the resulting deprotected nitramine , 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine , is then reacted with a difunctional electrophile suitable for cyclizing the bisnitramine . a variety of electrophiles are suitable for this purpose , including aldehydes , dihaloalkanes , alkyl pseudohalides , other typical alkylating reagents , acylating reagents , and sulfonating reagents . the use of formaldehyde as the cyclizing reagent produces the simple hexahydropyrimidine product ( rnfx ). in the successful examples cited below , 4 - nitrobenzenesulfonyl was used as a role model nitrogen - protecting sulfonyl group to prepare electronegatively substituted pyrimidines as intermediates and precursors leading to geminal - bis ( difluoramino ) alkylene derivatives . a wide variety of other heretofore unknown pyrimidine derivatives suitable for conversion , successively , to tetrapyrimidin - 5 -( 4h )- ones and then to geminal - bis ( difluoramino ) alkylene derivatives becomes apparent from a review of known electron - withdrawing properties of sulfonyl substituents , such as reviewed by hansch et al ., chemical reviews 1991 , 91 , 165 ; these require that inductive substituent constants , σ i or f , are greater than approximately 0 . 58 , the value known for unsubstituted benzenesulfonyl . thus , other suitable electronegatively substituted pyrimidines include those protected on nitrogen by chlorosulfonyl ; fluorosulfonyl ; cyanosulfonyl ; polyhaloalkanesulfonyls , such as difluoromethanesulfonyl , trifluoromethanesulfonyl , and all perfluoroalkanesulfonyls ; arenesulfonyls appropriately substituted such that collective effects of substituents on the arene impart the desired electronegativity on the arenesulfonyl , including , but not limited to , nitrobenzenesulfonyl ( all isomers ) and all polynitrobenzenesulfonyls . arenesulfonyl substituents may be based on arenes other than benzene , including various aromatic heterocycles , such as azines . individual substituents on the arenesulfonyl of electronegativity comparable to or greater than that of nitro impart suitable electronegativity to the sulfonyl subsitituents to make suitable pyrimidine intermediates . the collective effect of multiple electronegative substituents of electronegativity less than that of nitro would also impart , collectively , the same necessary property of lowered basicity ; examples include polyhaloarenesulfonyl and polycyanoarenesulfonyl protecting groups ; other examples are apparent from compilations of quantitative inductive effects , such as hansch et al . ( op . cit .). in the successful examples cited below , 4 - nitrobenzenesulfonyl was used as a model nitrogen - protecting sulfonyl group to prepare 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - n , n ′- bis ( 4 - nitrobenzenesulfonyl )- 1 , 3 - propanediamine intermediates susceptible to nucleophilic n - desulfonation and subsequent cyclization by appropriate electrophiles . based on the known general susceptibility of n - alkyl - n - nitrosulfonamides to nucleophilic n - desulfonation , it would be apparent that a variety of other n - sulfonyl subsituents are suitable for the present process of preparing 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine and subsequent cyclized derivatives , including alkanesulfonyl , arenesulfonyl ( including heteroarenesulfonyl ), and halosulfonyl protecting groups . in the successful examples cited below , a cyclic 2 , 2 - bis ( difluoramino )- n , n ′- disulfonyl - 1 , 3 - propanediamine precursor [ specifically , 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidine ] contained methylene ( ch 2 ) as a bridging link between sulfonamide nitrogens of the reactant ; the methylene bridge was susceptible to nitrolysis to an n - nitratomethyl substituent which was also nitrolyzed , forming an n - nitrosulfonamide . based on the known susceptibility to nitrolysis of “ substituted methylene ” linkages bridging heterocyclic nitrogens , other 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - disulfonylpyrimidines substituted in the 2 - position are also suitable reactants for the nitrolysis step generating 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine derivatives . the 2 - position substituents that remain feasible within the present process include a wide variety of alkyl , aryl ( including heteroaryl ) and cyclic alkyl ( including heterocyclic alkyl ) substituents . the class of feasible examples thus includes perhydro - 2 , 2 ′- bipyrimidines and a variety of other bicyclic systems linked to the 2 - position of the reactant 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - disulfonylpyrimidine . in the successful examples cited below , a formaldehyde equivalent generated in situ during nitrolysis of an n - nitratomethyl substituent was used to recyclize 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine to form rnfx . based on the known general reactivity of primary nitramines with aldehydes ( under acid catalyzed conditions ) and other electrophiles , the present process is extensible to the formation of other cyclic 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine derivatives via cyclization with alternative electrophiles . for example , 1 , 3 - propanediamines are known to condense with glyoxal to form perhydro - 2 , 2 ′- bipyrimidines ; 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine thus forms 5 , 5 , 5 ′, 5 ′- tetrakis ( difluoramino ) perhydro - 1 , 1 ′, 3 , 3 ′- tetranitro - 2 , 2 ′- bipyrimidine with glyoxal . although the description above contains many specificities , these should not be construed as limiting the scope of the invention but as merely providing an illustration of the presently preferred embodiment of the invention . thus the scope of this invention should be determined by the appended claims and their legal equivalents . a 37 % aqueous solution of formaldehyde ( 1 . 34 ml ) was added dropwise to a stirred solution of 1 , 3 - diamino - 2 - hydroxypropane ( aldrich chemical co ., 95 % purity , 1 . 5 g , 17 mmol ) in 8 ml of water over 30 minutes at room temperature . after stirring at room temperature for 3 days , the solvent was removed via distillation to give a light yellow solid , hexahydro - 5 - pyrimidinol . a solution of hexahydro - 5 - pyrimidinol ( 1 . 0 g , 9 . 8 mmol ) and sodium carbonate ( 1 . 04 g , 9 . 8 mmol ) in 10 ml of water in a 250 ml round bottom flask was stirred with a magnetic stir bar for 10 minutes . a solution of 4 - nitrobenzenesulfonyl chloride ( 4 . 4 g , 19 . 8 mmol ) in 10 ml of toluene was added dropwise over a period of 30 minutes . the reaction mixture formed a white suspended solid . a mixture of 100 ml of water and 20 ml of toluene was added to the reaction mixture and stirred overnight . the reaction mixture was filtered and the solid was washed with 100 ml of toluene , then with 100 ml of water . the solid was dried at room temperature under reduced pressure to give 4 . 4 g ( 95 %) of crude product , hexahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl )- 5 - pyrimidinol . [ 1 h nmr ( dmso - d 6 ): δ 2 . 29 ( s , 1h ), 2 . 84 , 3 . 47 { ab q of d , j = 12 . 4 ( 3 . 8 ) hz , 12 . 4 ( 7 . 9 ) hz , 4h }, 3 . 30 ( m , 1h ), 4 . 46 , 5 . 07 ( ab q , j = 12 . 5 hz , 2h ), 5 . 31 ( s , 1h ), 8 . 11 , 8 . 41 ( ab q , j = 8 . 7 hz , 8h ); 13 c nmr ( dmso - d 6 ): δ 50 . 0 , 59 . 8 , 60 . 6 , 124 . 6 , 128 . 9 , 143 . 3 , 150 . 1 ]. a suspended mixture of 4 - nitrobenzenesulfonamide ( 2 . 0 g , 9 . 9 mmol ) and potassium carbonate ( 0 . 68 g , 4 . 9 mmol ) in 100 ml water was stirred and heated at 70 ° c . until the reaction mixture turned clear . aqueous 37 % formaldehyde ( 0 . 2 ml , 4 . 9 mmol ) was added and the mixture heated at 70 ° c . for 3 days . the reaction mixture was concentrated by removal of water via rotary evaporation at reduced pressure . the reaction mixture was neutralized to ph 7 with hydrochloric acid . the resulting solid was filtered and washed with water to give 0 . 7 g ( 18 %) of methylenebis ( 4 - nitrobenzenesulfonamide ) [ 1 h nmr ( acetone - d 6 ): δ 2 . 82 ( s , 2h ), 4 . 86 ( m , 2h ), 8 . 07 , 8 . 35 ( ab q , j = 8 . 9 hz , 8h ); 13c nmr ( acetone - d 6 ) δ 53 . 0 , 125 . 2 , 129 . 1 , 148 . 4 , 151 . 0 ]. the yield of this reaction ranged from 10 - 30 %. a mixture of methylenebis ( 4 - nitrobenzenesulfonamide ) ( 1 . 0 g , 2 . 4 mmol ), potassium carbonate ( 0 . 66 g , 4 . 8 mmol ), and 3 - chloro - 2 -( chloromethyl )- 1 - propene ( 0 . 3 g , 2 . 4 mmol ) in 150 ml of acetonitrile was stirred and heated at reflux under a nitrogen atmosphere for 20 h . the solvent was removed under reduced pressure , and the remaining solid was chromatographed ( silica gel - ethyl acetate ) to give 0 . 84 g ( 75 %) of solid , hexahydro - 5 -( methylene )- 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidine [ 1 h nmr ( acetone - d 6 ): δ 3 . 90 ( s , 4h ), 4 . 95 ( m , 2h ), 5 . 00 ( s , 2h ), 8 . 18 , 8 . 44 ( ab q oft , j = 9 . 0 ( 2 . 2 ) hz , 8h ); 13 c nmr ( acetone - d 6 ): δ 51 . 0 , 61 . 7 , 116 . 2 , 125 . 3 , 130 . 6 , 133 . 6 , 144 . 6 , 151 . 6 ]. a stream of ozone in oxygen was bubbled into a solution of hexahydro - 5 -( methylene )- 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidine ( 0 . 6 g , 1 . 3 mmol ) in 150 ml acetone at − 78 ° c . ( dry ice - acetone bath ) until a blue color persisted for 5 minutes . the reaction was stirred for 15 minutes under a nitrogen atmosphere . next , 2 . 0 ml of dimethyl sulfide was added . after stirring for 10 minutes , the solvent was removed and the solid dried under reduced pressure to give 0 . 5 g ( 83 %) of tetrahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidin - 5 ( 4h )- one . [ 1 h nmr ( acetone - d 6 ): δ 3 . 95 ( s , 4h ), 5 . 25 ( s , 2h ), 8 . 20 , 8 . 48 ( ab q , j = 9 . 0 hz , 8h ); 13 c nmr ( dmso - d 6 ): δ 53 . 8 , 58 . 8 , 124 . 8 , 129 . 3 , 141 . 9 , 150 . 4 , 196 . 2 ]. difluoramine ( 2 . 2 g , 41 . 5 mmol ) was absorbed into a mixture of 3 . 0 ml fuming sulfuric acid ( 30 % so 3 ) plus 100 ml of trichlorofluoromethane in a temperature range of — 15 to + 5 ° c . tetrahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidin - 5 ( 4h )- one ( 0 . 255 g , 0 . 54 mmol ) was added via a solid addition funnel with another 15 ml of trichlorofluoromethane to wash out the funnel . after 3 h stirring at − 15 ° c ., the reaction mixture was poured onto ice . the mixture was basified with aqueous sodium carbonate to ph 6 and then extracted with dichloromethane . the solvent was removed from this extract by rotary evaporation and the residue was redissolved in chloroform and chromatographed on silica gel , eluting successively with chloroform ( two fractions ) and dichloromethane ( three fractions ). fraction # 2 , eluted by chloroform , contained a mixture of 2 , 2 - bis ( difluoramino )- n , n ′- bis ( difluoraminomethyl )- n , n ′-( 4 - nitrobenzenesulfonyl )- 1 , 3 - propanediamine [ 1 h nmr ( chloroform - d ): δ 4 . 39 ( s ), 5 . 09 ( t ), 8 . 12 , 8 . 44 ( ab q , j = 8 . 9 hz ); 19 f nmr ( chloroform - d ): δ 30 . 59 ( s ), 44 . 86 ( t , j = 22 . 9 hz )] and n , n - bis ( difluoraminomethyl )- 4 - nitrobenzenesulfonamide [ 1 h nmr ( chloroform - d ): δ 5 . 03 ( t , j = 22 . 6 hz , 4h ), 8 . 09 , 8 . 42 ( ab q , j = 8 . 9 hz , 8h ); 19 f nmr ( chloroform - d ): δ 43 . 53 ( t , j = 22 . 4 hz )]. the same reaction as described in example 4 is performed . elution of chromatography fraction # 3 with dichloromethane produced a mixture containing predominantly 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidine [ 1 h nmr ( dichloromethane - d 2 - chloroform - d ): δ 3 . 98 ( s , 4h ), 4 . 98 ( s , 2h ), 8 . 07 , 8 . 42 ( ab q , j = 9 . 0 hz , 8h ); 13 c nmr ( dichloromethane - d 2 - chloroform - d ): δ 44 . 3 ( m , j = 9 . 0 hz ), 60 . 4 , 89 . 7 ( m ), 125 . 3 , 129 . 5 , 144 . 0 , 151 . 4 ; 19 f nmr ( dichloromethane - d 2 - chloroform - d ): δ 27 . 27 ] plus minor amounts of 5 , 5 - bis ( difluoramino )- 1 -( difluoraminomethyl ) hexahydro - 3 -( 4 - nitrobenzenesulfonyl ) pyrimidine [ 19 f nmr ( dichloromethane - d 2 - chloroform - d ): δ 21 . 65 , 28 . 15 ( ab q , j = 610 hz , 4 f ), 45 . 38 ( t , j = 20 . 8 hz , 2 f )], n -( difluoraminomethyl )- 4 - nitrobenzenesulfonamide [ 19 f nmr ( dichloromethane - d 2 - chloroform - d ): δ 39 . 86 ( td , j = 22 . 6 , 7 . 6 hz )] and n , n - bis ( difluoraminomethyl )- 4 - nitrobenzenesulfonamide . the same reaction as in example 4 is performed . elution of chromatography fraction # 4 with dichloromethane produced effectively pure 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidine . 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - bis ( 4 - nitrobenzenesulfonyl ) pyrimidine is dissolved in a large excess of ca . 98 % nitric acid . nitrolysis of the methylene bridge in this reactant is conveniently followed by 19 f nmr spectrometry . nitrolysis initially produces 2 , 2 - bis ( difluoramino )- n -( nitratomethyl )- n ′- nitro - n , n ′- bis ( 4 - nitrobenzenesulfonyl )- 1 , 3 - propanediamine [ 1 h nmr ( hno 3 ): δ 4 . 53 ( s ), 5 . 09 ( s ), 5 . 88 ( s ), 8 . 42 , 8 . 78 ( ab q , j = 9 . 0 hz , 4h , n - aryl ), 8 . 43 , 8 . 70 ( ab q , j = 9 . 0 hz , 4h , n ′- aryl ); 13 c nmr ( hno 3 ): δ 44 . 2 , 45 . 8 , 60 . 6 , 90 . 8 , 125 . 6 , 128 . 6 , 131 . 3 , 143 . 1 , 146 . 6 , 150 . 5 , 151 . 6 ; 19f nmr ( hno 3 ): δ 29 . 39 ]. nitrolysis of the intermediate formed in example 7 replaces the n - nitratomethyl substitituent with n - nitro . the reaction rates of the successive nitrolysis steps are expectedly influenced by the concentration of reactants — the sulfonamides and nitric acid . with a proper proportion of reactants , the next step of the sequence occurs spontaneously : 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - n , n ′- bis ( 4 - nitrobenzenesulfonyl )- 1 , 3 - propanediamine is adventitiously n - desulfonated by the water contained in the concentrated nitric acid , forming 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine , which does not accumulate but combines spontaneously with the formaldehyde equivalent generated in this nitrolysis , as described in example 9 . under the conditions of nitrolysis of 2 , 2 - bis ( difluoramino )- n -( nitratomethyl )- n - nitro - n , n ′- bis ( 4 - nitrobenzenesulfonyl )- 1 , 3 - propanediamine in ca . 98 % nitric acid , the liberated formaldehyde equivalent becomes available for cyclization of the n - desulfonated bis ( primary nitramine ), 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine . the cyclization occurred spontaneously at room temperature , consuming the 2 , 2 - bis ( difluoramino )- n , n ′- dinitro - 1 , 3 - propanediamine intermediate and forming 5 , 5 - bis ( difluoramino ) hexahydro - 1 , 3 - dinitropyrimidine ( rnfx ) [ 1 h nmr ( cd 3 cn ): δ 4 . 85 ( s , 4h ), 6 . 06 ( s , 2h ); 1 h nmr ( acetone - d 6 ): δ 5 . 07 ( s , 4h ), 6 . 31 ( s , 2h ); 13 c nmr ( cd 3 cn ): δ 45 . 3 ( m , j = 6 hz ), 60 . 6 ( s ) ( not all carbons detected due to low s / n ); 19 f nmr ( cd 3 cn ): δ 29 . 67 ; 19 f nmr ( acetone - d 6 ): δ 29 . 31 )]. | 2 |
the present invention provides an improved process for the purification of tiacumicin b , resulting in a product with a purity of at least 95 %. the method according to the invention uses hydrophobic interaction chromatography ( hic ). in addition to said step , normal isolation procedures can be performed , such as insolubilisation or crystallisation of the end product . the process described is simpler than those described in the prior art , and makes the use of rp - hplc superfluous . we have now found that when hic columns with different ph values are used , different types of impurities can be eluted differentially , and therefore separated , which considerably improves the quality of the product . said characteristic is unprecedented in this field , and could not be foreseen on the basis of the chemical properties and structure of the product . the method , which is described in greater detail below , provides a very simple purification process and a substantially pure product . the present invention relates to a process for the recovery and purification of tiacumicin b which involves subjecting a liquid containing tiacumicin b to at least one hydrophobic interaction chromatography step . hydrophobic interaction chromatography uses a resin selected from the group of styrene - divinylbenzene absorbent resins . in particular , resins hp20 , hp21 , hp20ss , sp20 , sp2oss , sp825 , sp850 , sp207 , xad16 , xad1600 , xad18 , etc ., obtainable from mitsubishi , rohm & amp ; haas , can be used . in a preferred form of embodiment , the resin is hp20ss with a very fine particle size . the starting material of the process according to the present invention can be prepared by the method described in u . s . pat . no . 4 , 918 , 174 . the fermentation broth used as starting material of the present invention is filtered and then purified by hic . the filtered broth can be pre - purified before the chromatography step to eliminate compounds chemically different from tiacumicins and correlated substances with a significantly different polarity . non - limiting steps of pre - treatment of the filtered broth include , for example , extraction with a water - immiscibile solvent or precipitation of the crude product . a ) loading the liquid containing tiacumicin b at a ph from 2 . 0 to 8 . 0 , preferably from 2 . 5 to 6 . 5 , onto the hydrophobic interaction resin ; b ) eluting the impurities from the hydrophobic interaction resin with a mixture consisting of water and an organic solvent selected from methanol , ethanol , acetonitrile , acetone , thf or a mixture thereof with a ph from 2 . 0 to 8 . 0 , preferably from 2 . 5 to 6 . 5 ; c ) eluting tiacumicin b from the hydrophobic interaction resin with a mixture consisting of water and an organic solvent selected from methanol , ethanol , acetonitrile , acetone , thf or a mixture thereof at a ph from 2 . 0 to 8 . 0 , preferably from 2 . 5 to 6 . 5 . according to a preferred embodiment of the present invention , tiacumicin b is purified using two successive hydrophobic interaction chromatography steps . during elution of the product , the fractions are isolated ; the fractions containing the product of the desired purity are combined to give the eluate from the first hic . this first step of hic increases the purity of tiacumicin b from approx . 40 % to 80 % or more . next , after removal of the solvent , the solution of partly purified tiacumicin b is reloaded onto a column containing the same resin as the first hydrophobic interaction chromatography step , and undergoes a second hydrophobic interaction chromatography step . the solution is loaded onto the column at a ph in the 2 . 0 to 8 range ; the ph of the solution is preferably in the 2 . 5 to 6 . 5 range . at the second step of hic the resin , after loading , is washed with a suitable mixture consisting of water and an organic polar solvent under conditions wherein the impurities are dissociated from the resin , whereas the tiacumicin b remains bound to it . finally , tiacumicin b is eluted under conditions wherein it is dissociated from the resin . the organic solvent is chosen from methanol , ethanol , acetonitrile , acetone , thf or mixtures thereof . during elution of the product , the fractions are isolated ; the fractions containing the product of the desired purity are combined to give the eluate from the second hic step . this second step of hic increases the purity of tiacumicin b from approx . 80 % to 95 % or more . tiacumicin b is then isolated from the purified solution under standard conditions ( i . e . by insolubilisation with an anti - solvent ). the purified end product has a purity of at least 95 %. in a preferred form of embodiment of this invention , the two hic columns are used at different ph values . this allows different types of compound to be separated on the basis of their differences of polarity , and the purity of the product to be improved . the order in which the two steps of hic are conducted ( at different ph values ) is not crucial . according to one form of embodiment of the invention , the first step is conducted at ph 2 . 0 - 5 . 0 , preferably 2 . 5 - 3 . 5 , and the second step is conducted at ph 3 . 5 - 7 . 0 , preferably 5 - 6 . 5 . the fermentation broth ( 10 1 ) containing tiacumicin b was extracted with 10 1 of ethyl acetate . the ethyl acetate extract was concentrated to obtain 320 g of oily residue . the residue was dissolved in methanol at a concentration of 200 g / l . the resulting solution was loaded onto a column packed with hp20ss resin ( 1 1 − 50 × 5 cm ) previously equilibrated with 5 bed volumes ( bv ) of phosphate buffer at ph 3 . 5 . the column was washed with 10 bv of acetonitrile in phosphate buffer ph 3 . 5 ( the % of acetonitrile ranges between 10 % and 50 %). the tiacumicin b was eluted with 5 bv of acetonitrile in acetate buffer ph 3 . 5 ( the % of acetonitrile ranges between 52 % and 60 %). the eluate from the column was divided into fractions , and each fraction was analysed by hplc to evaluate its purity . the fractions with a purity greater than 75 % were combined and concentrated , and the concentrate was extracted with ethyl acetate . the ethyl acetate layer was concentrated to dryness , and the residue was redissolved in methanol at a concentration of 200 g / l . the resulting solution was loaded onto a column packed with hp20ss resin ( 0 . 2 1 − 40 × 2 . 5 cm ) previously equilibrated with 5 bv of acetate buffer at ph 6 . 5 . the column was washed with 10 bv of acetonitrile in acetate buffer ph 6 . 5 ( the % of acetonitrile ranges between 10 % and 45 %). the tiacumicin b was eluted with 5 bv of acetonitrile in acetate buffer ph 6 . 5 ( the % of acetonitrile ranges between 48 % and 52 %). the eluate from the column was divided into fractions , and each fraction was analysed by hplc to evaluate its purity . the fractions with a purity greater than 95 % were combined and concentrated , and the concentrate was extracted with ethyl acetate . the ethyl acetate layer was washed with 3 volumes of water and concentrated to a small volume , and 5 volumes of cyclohexane were added ; the suspension was kept at 4 ° c . to complete the crystallisation . the product was filtered and dried . 0 . 45 g of white powder with a purity of 97 . 4 % was obtained . crude tiacumicin b ( 16 g ) was dissolved in methanol at a concentration of 200 g / l . the resulting solution was loaded onto a column packed with hp20ss resin ( 1 1 − 50 × 5 cm ) previously equilibrated with 5 bv of acetate buffer at ph 5 . 0 . the column was washed with 10 bv of acetonitrile in acetate buffer ph 5 . 0 ( the % of acetonitrile ranges between 10 % and 48 %). the tiacumicin b was eluted with 5 bv of acetonitrile in acetate buffer ph 5 . 0 ( the % of acetonitrile ranges between 50 % and 55 %). the eluate from the column was divided into fractions , and each fraction was analysed by hplc to evaluate its purity . the fractions with a purity greater than 75 % were combined and concentrated , and the concentrate was extracted with ethyl acetate . the ethyl acetate layer was concentrated to dryness , and the residue was redissolved in methanol at a concentration of 200 g / l . the resulting solution was loaded onto a column packed with hp20ss resin ( 1 1 − 50 × 5 cm ) previously equilibrated with 5 bed volumes ( bv ) of phosphate buffer at ph 3 . 0 . the column was washed with 10 bv of acetonitrile in phosphate buffer at ph 3 . 0 ( the % of acetonitrile ranges between 10 % and 52 %). the tiacumicin b was eluted with 5 bv of acetonitrile in phosphate buffer at ph 3 . 0 ( the % of acetonitrile ranges between 55 % and 60 %). the eluate from the column was divided into fractions , and each fraction was analysed by hplc to evaluate its purity . the fractions with a purity greater than 95 % were combined and concentrated , and the concentrate was extracted with ethyl acetate . the ethyl acetate layer was washed with 3 volumes of water and concentrated to a small volume , and 5 volumes of cyclohexane were added ; the suspension was kept at 4 ° c . to complete the crystallisation . the product was filtered and dried . 2 . 8 g of white powder with a purity of 96 . 8 % was obtained . | 2 |
the term “ assay ” as used herein refers to the analytic procedure for qualitatively assessing or quantitatively measuring the presence or amount or the functional activity of a target entity ( the analyte ). the term “ chandler loop assay ” as used herein refers to a system of rotating tubes that simulates the circulation of blood . this assay is suitable for testing the hemocompatibility of medical devices placed into the blood stream . the term “ coagulation ” or “ blood clotting ” as used herein refers to the process by which blood changes from a liquid to a gel . it potentially results in hemostasis , the cessation of blood loss from a damaged vessel , followed by repair . the term “ coating ” or “ coated ” as used herein refers to the functional layer of material that is applied to the surface of an object , usually referred to as the substrate . the term “ covalent bonding ” as used herein refers to the chemical bond that is formed as a result of the stable balance of attractive and repulsive forces between atoms when they share electrons . the term “ endothelial cells ” as used herein refers to the cells that line the blood vessels . the term “ enzyme ” as used herein refers to a biological catalyst that facilitates a metabolic process . the term “ fibrin ” as used herein refers to a fibrous , non - globular protein involved in the clotting of blood . it is formed by the action of the protease thrombin on fibrinogen , which causes the latter to polymerize . the polymerized fibrin together with platelets forms a hemostatic plug or clot over the wound site . the term “ fibrinolysis ” as used herein refers to the degradation of fibrin . the term “ fibrinolytic ” as used herein refers to the ability of a substance to degrade fibrin and hence prevent blood clots from growing and becoming problematic . the term “ freeze - dried ” or “ lyophilized ” as used herein refers to materials that are dehydrated for the purpose of preservation . the term “ hemocompatible ” refers to a set of properties that allow contact with flowing blood without causing adverse reactions such as thrombosis , hemolysis , complement activation , or inflammation . the term “ immobilization ” as used herein refers to the attachment of a substance to an inert , insoluble material , allowing for increased resistance to changes in conditions such as pi or temperature . in particular , it allows enzymes to be held in place throughout a reaction , thus facilitating their reuse . the term “ mediator ” as used herein refers to an agent that mediates a physical , chemical , or biological process , such as a coating that facilitates the immobilization of enzymes to a substrate . the term “ non - thrombogenic ” as used herein refers to the tendency of a material in contact with the blood to prevent the formation of a thrombus , or clot . the term “ plasma - activated coating ” or “ pac ” as used herein refers to a process of immobilizing plasmin on stainless steel substrates using a plasma - activated coating mediator to create a surface that substantially attenuates thrombus formation . the term “ plasmin ” as used herein refers to the enzyme present in blood that degrades many blood plasma proteins , including fibrin clots . the term “ plasminogen ” as used herein refers to the blood circulating glycoprotein which is the precursor of plasmin . the term “ platelets ” or “ thrombocytes ” as used herein refers to blood cells whose function is to stop bleeding . platelets have no nucleus , they are fragments of cytoplasm which are derived from the megakaryocytes of the bone marrow , and then enter the circulation . the term “ reduced ” as used herein refers to having been made smaller or less in amount , degree , or size . the term “ stent ” as used herein refers to a mesh tube that is inserted into a natural passage or conduit in the body to prevent or counteract a disease - induced , localized flow constriction . the term “ streptokinase ” as used herein refers to the enzyme secreted by several species of streptococci that can bind and activate human plasminogen . the term “ substrate ” as used herein refers to the material that underlies the mediator and non - thrombogenic protein . the term “ thrombin ” as used herein refers to the serine protease that converts soluble fibrinogen into insoluble strands of fibrin , and that catalyzes many other coagulation - related reactions . the term “ thrombogenicity ” as used herein refers to the tendency of a material in contact with the blood to produce a thrombus , or clot . the term “ thrombosis ” as used herein refers to the formation of a blood clot inside a blood vessel that obstructs the flow of blood through the circulatory system . the term “ thrombus ” or “ blood clot ” as used herein refers to a solid or semi - solid mass formed from the constituents of blood within the vascular system that is the product of blood coagulation . there are two components to a thrombus , aggregated platelets that form a platelet plug , and a mesh of cross - linked fibrin protein . the term “ tissue plasminogen activator ” or “ tpa ” as used herein refers to a protein involved in the breakdown of blood clots . it is a serine protease found on endothelial cells . as an enzyme , it catalyzes the conversion of plasminogen to plasmin , the major enzyme responsible for clot breakdown . the term “ urokinase ” as used herein refers to the serine protease that is present in the bloodstream and acts on plasminogen . the term “ valve ” as used herein refers to a device that controls the passage of fluid through a pipe or duct , allowing movement in one direction only . the term “ vain ” as used herein refers to the plasmin substrate d - val - leu - lys - p - nitroanilide . the term “ valy activity assay ” as used herein refers to an assay that measures the cleavage of valy by plasmin into p - nitroanilide and d - val - leu - lys . the term “ zymogen ” as used herein refers to an inactive enzyme precursor that requires biochemical change to become an active enzyme . it has been discovered that plasma polymerization of a substrate can greatly enhance biocompatibility , which is further enhanced by coupling of enzymes and other anti - thrombotics such as heparin that inhibit clotting and platelet activation . these are collectively referred to herein as “ anti - thrombotics ”. the anti - thrombotic coating is robust enough to withstand deployment and blood flow and presents the anti - thrombotic in a biologically active conformation , thereby decreasing thrombogenicity . the enzyme is covalently bound to metal substrates via a polymer intermediary such as acetlyene ( ethylene ). the acetylene layer is blended with the metal surface using plasma polymerisation , converting the inert metal surface into a reactive polymer surface . the composition of the polymer layer can be widely varied and conditions for optimal anti - thrombotic binding varied . similar results can be achieved using other carbon chains ( such as hexane ) or different plasma conditions . fig1 is a schematic showing the steps or stages of plasmin immobilization . in the absence of modification ( step 1 ), stainless steel recruits platelets and red blood cells , and activates fibrin ( step 2 ), leading to clot formation ( step 3 ). following surface activation with the pac process ( step 4 ), plasmin can be covalently retained ( step 5 ) and it can prevent the formation of fibrin networks , resisting clot formation ( step 6 ). given the current problems with regards to late stent thrombosis in drug eluting stents , many groups are exploring the use of biodegradable coatings for drug release . in such instances , a biodegradable drug release coating may be applied over a biocompatible coating such as enzyme covalently bound by plasma polymerization . this would allow local elution of a drug , leaving behind a stent with a biocompatible coating . stents can also be manufactured from degradable materials as alternatives to permanent metallic scaffolds . these bioresorbable stents have commonly been manufacted from polymers such as poly - lactic acid and poly - glycolic acid , which remain in the body for 6 - 24 months ( zilberman and eberhard , ann . rev . biomed . eng ., 8 : 153 - 180 ( 2006 )). bioresorbable stents can also be made from metal alloys such as magnesium . these are completely resorbed within 2 months and have shown promising clinical outcomes ( erbel , di mario , et al ., lancet , 369 : 1869 - 75 ( 2007 )). plasma polymerisation and / or coating with enzyme is also relevant to the improvement of the short term biocompatibility of these temporary scaffolds and could easily be adapted for their modification . materials which can be plasma polymerized include metals , polymers , carbon , and ceramic . the anti - thrombotic , can be applied to , crosslinked with , tethered to , blended with , or laminated as part of , one or more materials to form a surface , component , or device . in the preferred embodiment , a graded polymer such as acetylene layer is deposited on the surface of a metal , such that the initial deposition is metal , with increasing polymer , finishing with 100 % polymer . the effect of this graded layer is that there is no defined metal / polymer interface and no resultant peeling off of the coating . the polymer layer is chemically activated using treatment with gas plasma , pre - disposing it to form covalent bonds with anti - thrombotics . immersion of the plasma polymerised surface in a anti - thrombotic solution is sufficient for covalent attachment , with no separate cross - linking agent required . importantly , bioactivity is retained . typical metals include stainless steel and titanium . in one embodiment , the material is or includes one or more biodegradable or non - biodegradable synthetic polymers such as polylactides , polyglycolic acids , polycaprolactones , polycaprolactams , polyhexamethylene adipamide , polycarbonates , polyamides , polyanhydrides , polyamino acids , polyesters , polyacetals , polycyanoacrylates , polyvinyl alcohols , polyvinyl chlorides , polyethylenes , polyurethanes , polypropylenes , polyacrylates , polystyrenes , polyvinyl oxides , polyvinyl fluorides , poly ( vinyl imidazoles ), polyethylene oxides , polytetrafluoroethylenes , silicone polymers and copolymers and combinations thereof . in another embodiment , the material is or includes one or more natural materials such as a protein , sugar or polysaccharide , or combination thereof . representative examples include collagen , preferably type 1 and / or type 3 , fibrin , gelatin , vitronectin , fibronectin , hyaluronic acid , glycosaminoglycans , their derivatives and mixtures thereof . preferred glycosaminoglycans include chondroitin sulfate , dermatan sulfate , keratan sulfate , heparan sulfate , heparin and hyaluronan . the application will determine the selection and design of the mechanical properties . the material can be applied as a part of a variety of clinical vascular applications including a vascular conduit , a stent , a stent - graft , a surgically or percutaneously implantable heart valve , a vascutarlseptal occlusion device , avascular closure device , endovascular implant , stent graft , graft , pacemaker lead vascular occluder , left atrial appendage occlusion device , endovascular valve , vascular closure devices including atrial septal and patent foramen ovale closure , or vena caval filters , or as a surface coating for a vascular device / application . the protein can also be used to form coatings on materials such as microchips , which may be formed of a material such as a silicon chip , which may be used as sensors , electrodes , or for drug delivery , or a device such as an implantable pump . other useful materials are matrices for tissue engineering and / or drug delivery , bone implants and prosthetics including pins , rivets , screws and rods , as well as artificial knees and other joints , especially at the surfaces where the metal , ceramic or bone interfaces with the host tissue . in the majority of these cases , the critical role of the enzyme is to increase the biocompatihility of the implant or matrix , promoting cell attachment or diminishing the formation of scar tissue , abnormal proliferation of cells ( i . e ., restenosis or scarring ), and integration of the implant into the host . preferred enzymes include streptokinase , urokinase , tissue plasminogen activator ( tpa ) including alteplase , reteplase , tenecteplase and desmoteplase , and plasmin . other anti - thronogenic proteins such as direct thrombin inhibitors ( e . g . bivalirudin etc .) and anti - platelet agents can also or alternatively be immobilized on the substrates . other materials such as heparin and heparin fragment can also be immobilized on metal or polymeric substrates . a plasma - activated coating ( pac ) process covalently binds biomolecules in their bioactive state , has low thrombogenicity and can be robustly applied to medical devices , resisting delamination when deployed in vivo ( yin et al ., biomaterials , 30 : 1675 ( 2009 ); waterhouse et al ., biomaterials , 31 : 8332 ( 2010 ); waterhouse et al ., biomaterials , 33 : 7984 ( 2012 )). the substrate material is modified to create reactive surface groups which facilitate covalent interaction . in the case of inert polymeric materials like eptfe , the surface requires activation . both ‘ classical ’ plasma processes ( bilek et al . ( 2004 ) in smart materials iii , vol . 5648 ( ed , wilson , a . r .) spie , pp . 62 - 67 ) and higher energy plasma immersion ion implantation ( bilek , et al . surface and coatings technology , 156 : 136 - 142 ( 2002 )) ( piii ) can be used . in a preferred embodiment , the enzyme is covalently tethered to the polymer when a solution of the protein is incubated with the activated surface . piii has recently been shown to increase the functional lifetime of attached proteins and may be preferred ( nosworthy , et al . acta biomater , 3 : 695 - 704 ( 2007 )). metallic substrates can be also be functionalized by applying a modified plasma process to the substrate while it is immersed in a carbon containing plasma or in a vapor of the monomer used to deposit the plasma polymer layer or by codeposition of a graded substrate / polymer layer which terminates in the polymer ( yin , et al ., surf . coat . technol ., 203 : 1310 - 1316 ( 2009 )). a range of short chain carbon - based polymers including hexane and acetylene can be used to form the basis of the plasma polymer layer . the plasma chamber also contains a background carrier gas , examples of which include oxygen , hydrogen , argon , nitrogen and combinations thereof this plasma mixture is essential to efficacy . in a preferred embodiment acetylene is injected into the plasma chamber and activated together with a combination of nitrogen and argon background gas , subsequently condensing to form polymerized surfaces . this technique can be used to bind enzyme to a range of metals including stainless steel , as demonstrated by yin , et al ., biomaterials , 30 : 1675 - 1681 ( 2009 ). the present invention will be further understood by reference to the following non - limiting examples . reagents : all reagents were purchased from sigma - aldrich , st louis and used without further purification unless otherwise noted . human umbilical vein endothelial cells ( huvecs ) were harvested enzymatically from umbilical cords . endothelial cells from passages 2 - 4 were used . sample preparation : the substrates were 316l , stainless steel foil ( ss ) 25 μm thick ( brown metals ), or 3 . 0 × 10mm 316lvm stainless steel stents ( laserage , calif ., usa ). plasma - activated coating on 316l stainless steel ( pac ) surfaces were generated from acetylene in , argon mixed with nitrogen . stainless steel stents were imaged with a zeiss evo 50 scanning electron microscope . samples were incubated with increasing concentrations of plasmin ( 0 . 1 , 1 . 0 and 10 μg ) in pbs at 37 ° c . overnight and washed in pbs prior to use . surface characterization : the contact angle between pac and de - ionized water was measured using a kruss contact angle analyzer ds10 employing the sessile drop method . x - ray photoelectron spectroscopy ( xps , specs - xps , mode xp - 50 high performance twin anode with focus 500 ellipsoidal crystal monochromator and promos 150 mcd - 9 analyser ) was utilized to provide data on the elemental composition of pac variants over time . casa xps was used to calculate areas of elemental peaks with the concentration of each element expressed as an atomic percentage . as shown in fig2 a , the relative percentage of nitrogen in the surface decreased from 32 . 3 ± 1 . 0 % on day 1 , to 24 . 2 ± 0 . 5 % on day 23 . this corresponded to a small increase in oxygen from 7 . 1 ± 0 . 5 % up to 8 . 2 ± 0 . 3 % and in the relative carbon content from 60 . 6 ± 1 . 7 % to 67 . 6 ± 1 . 1 % from day 1 to 23 , respectively . the starting water contact angle of the pac was 42 . 9 ± 2 . 4 ° 30 minutes after treatment , increasing to 52 . 9 ± 1 . 0 ° after 2 hours ( fig2 b ). surface chemistry appeared to have stabilized by day 7 , when the water contact angle was observed to be 61 . 6 ± 0 . 4 °. only minor changes were observed from this time , out to 24 days . spectra of pac and ss surfaces after incubation with plasmin contained characteristic peaks associated with the internal protein vibrations and confirmed the presence of a cross - linked polymeric layer containing predominantly carbon and nitrogen , with hydrogen and oxygen terminations ( fig2 c ). bond vibrations attributed to both saturated and unsaturated c — c and c — n bonds are observed . c — h , o — h , and n — h absorptions indicate that hydrogen terminations are present and that the surface has been oxidized by exposure to atmosphere . the relative intensities of characteristic amide a , i , and ii ftir peaks for plasmin were compared before and after washing with detergent ( fig2 )). after detergent washing , surfaces displayed only covalently attached plasmin , with retention of 54 . 2 ± 3 . 8 % of originally bound plasmin on pac , but complete removal from stainless steel . covalent attachment : samples were washed with water to remove salt and dried prior to accumulation of spectra using a digilab fts7000 ftir spectrometer fitted with an attenuated total reflection ( atr ) accessory with a trapezium germanium crystal at incidence angle of 45 °. to obtain sufficient signal / noise ratio and resolution of spectral bands , 500 scans with a resolution of 1 cm − 1 were taken . difference spectra were used to detect changes associated with the presence of plasmin , and analysis carried out . unbound protein was removed by aspiration and the surfaces were washed with pbs . non - covalently bound protein was removed by sds - washing . samples were treated with 5 % ( w / v ) sds for 1 hat 80 ° c . following the sds treatment , samples were washed with pbs and distilled water . bioactivity assay : the enzymatic activity of plasmin was monitored using a commercially available kit . one unit of activity is defined as the production of one micromole of p - nitroartilide from d - val - leu - lys - p - nitroanilide ( valy ) at ph 7 . 5 at 37 ° c . activity was monitored over time , up to 210 mins , and compared free plasmin in solution to plasmin immobilized on pac and pac alone as a negative control . measuring the color change that occurs as valy is converted to p - nitroanilide at 405 nm was used to monitor the enzymatic activity of plasmin . both fresh plasmin solution and plasmin immobilized on pac were able to convert the substrate , showing an increased absorbance over the time course , up to 290 minutes ( fig3 a ). pac alone did not produce p - nitroanilide . endothelial cell interactions : for proliferation assays , huvecs ( 20 , 000 cells / ml ) were plated in 24 - well plates for 3 and 5 days . attachment and proliferation of cells to and on plasmin - coated wells was analyzed in comparison to tissue culture plastic alone and to wells coated with fibronectin ( 10 μg / well ). cells were quantified at 3 and 5 days post - seeding using the mtt ( 3 [ 4 , 5 - dimethylthiazol - 2 - yl ]- 2 , 5 diphenyl tetrazolium bromide ) assay according to manufacturer &# 39 ; s instructions . dimethyl sulfoxide ( dmso ) was used to dissolve insoluble formazan crystals , and the absorbance at 540 nm was measured using a spectrophotometer ( biorad ). after 3 days of incubation , cell numbers on tcp , plasmin and fibronectin ( fn ) were not significantly different ( fig3 b ). at day 5 , cell proliferation on plasmin was 56 . 40 ± 3 . 2 % higher than tcp alone ( p & lt ; 0 . 001 ), but remained statically less than then fn positive control , which was a further 22 . 12 ± 1 . 8 % higher than plasmin ( p & lt ; 0 . 01 ). when immobilized on pac , there was again no significant difference between the conditions on day 3 ( fig3 c ). by day 5 , pac and pac + plasmin showed a 20 . 47 ± 1 . 6 % and 31 . 16 ± 2 . 4 % increase over stainless steel ( ss ) respectively , though this did not reach statistical significance . pac + fn increased huvec proliferation 53 . 49 ± 2 . 8 % ( p & lt ; 0 . 01 ) over stainless steel , but only 17 . 02 ± 1 . 2 % more than pac + plasmin ( p = ns ). example 4 , thrombogenicity in vitro . thrombogenicity assessment : whole blood was obtained from healthy , non - smoker , male volunteers with informed consent in accordance with the declaration of helsinki , who had not taken aspirin two weeks prior to donation . approval for this work was granted by the university of sydney , human research ethics committee ( protocol 05 - 2009 / 11668 ). experiments were conducted at least three times with different donors &# 39 ; blood . samples of ss , pac or pac + plasmin were incubated with heparinized whole blood ( 0 . 3 u / ml ) for 30 min at 37 ° c . whilst rocking . concentrations of plasmin increased from 0 . 1 - 10 u were used initially to determine an optimal coating density . thrombogenicity under flow conditions was investigated using a modified chandler loop . briefly , samples were balloon expanded into 28 cm lengths of tygon s - 50 - ht tubing ( sdr , australia ), connected into loops using 1 cm silicone connectors and filled with heparinized whole blood ( 0 . 5 u / ml , 2 . 5 ml ). the loops were rotated at 34 rpm at 37 ° c . for 60 min . the thrombus and steel from each loop was removed for imaging and weighing . the blood from each loop was combined with 10 % ( v / v acid citrate dextrose ( acd ) and centrifuged at 1000 rpm for 15 min to obtain serum . soluble p - selectin was detected via an elisa ( r & amp ; d systems , usa ). for stent evaluation , 0 . 3 u / ml heparin , 90 mins , was evaluated . the relative thrombogenicity of stainless steel , pac alone , and plasmin covalently bound to pac was studied using a whole blood adhesion assay ( fig4 ). increasing concentrations of plasmin , 0 . 1 u , 1 . 0 u , and 10 u , immobilized on pac demonstrated a dramatic reduction of thrombus weight in a dose - dependent manner , compared to stainless steel controls . pac alone reduced thrombus weight by 45 . 4 ± 9 . 1 %, but further reductions were observed for 0 . 1 u ( 62 . 3 ± 6 . 4 %), 1 u ( 78 . 3 ± 6 . 4 %) and 10 u ( 90 . 5 ± 1 . 3 %) plasmin , relative to stainless steel ( p & lt ; 0 . 001 ). the reductions in thrombus weight are also demonstrated in representative images of the samples . surface fibrinolysis was also demonstrated by incubation with whole blood containing fluorescently labeled fibrinogen . a complete interconnected fibrin network was observed on stainless steel after 30 minutes , while on pac only this network was also present but notably less dense . on plasmin coated pac only the rudiments of interconnected fibrin were observed . to more directly assess the contribution of surface - bound plasmin , the enzyme was denatured prior to incubation with pac . following repeated freeze - thaw cycles , plasmin was confirmed to be inactive using the valy conversion described above ( fig5 a ). denatured plasmin - bound surfaces continued to show superiority to stainless steel , but were statistically equivalent to pac only surfaces and had significantly higher clot weights than fresh plasmin on pac ( fig5 b ). considering the potential to store plasmin coated pac surfaces , samples were freeze - dried prior to rehydration and re - tested with whole blood . immediately following freeze - drying ( fig5 c ) and up to 14 weeks later ( fig5 d ), clot weights of freshly prepared and stored plasmin on pac were equivalent . under flow conditions in a modified chandler loop ( fig6 a ), stainless steel samples generated substantial thrombus formation ( 61 . 8 ± 8 . 3 mg ) ( fig6 b ). in contrast , the thrombogenicity of pac alone was reduced significantly to 15 . 8 ± 1 . 1 mg ( p & lt ; 0 . 001 ), while immobilization of 10 u plasmin on pac further reduced clot weight to 1 . 4 ± 0 . 4 mg ( p & lt ; 0 . 001 ), a 97 . 7 ± 1 . 3 % reduction relative to stainless steel controls . these differences are well demonstrated in the representative images , which show a clear contrast between the clotted stainless steel samples , and the 10 u plasmin samples , which are largely thrombus free . this striking thrombus reduction was driven by a significant decrease in the amount of sp - selectin detected in the samples ( fig6 d ). stainless steel controls , activating platelets generated 119 . 7 ± 4 . 8 ng / ml of sp - selectin , reduced to 88 . 1 ± 0 . 9 ng / ml in the presence of pac only . addition of plasmin to pac resulted in a further reduction to 57 . 16 ± 3 . 5 ng / ml , significantly lower than both stainless steel ( p & lt ; 0 . 001 ) and pac alone ( p & lt ; 0 . 01 ), and not significantly different from the no implant control which represents the baseline level of activation in this assay . stainless steel stents ( 3 mm × 10 mm , 316 lvm ) were laser cut and electropolished to remove any surface contaminants . pac treated stents were macroscopically darker than untreated stainless steel stents . under scanning electron microscopy ( 50 × magnification ), pac coated stents had a smooth , contiguous appearance , free from cracking or delamination . the blood compatibility of stainless steel , pac only and pac + plasmin steins was demonstrated by incubation with whole blood containing fluorescently labeled fibrinogen in a chandler loop . after 15 minutes , only faint fluorescence was observed for all conditions . in contrast , after 30 minutes , significant fibrin deposition was observed for stainless steel , while little was seen on pac + plasmin . fibrin fluorescence on pac only was intermediate between these two conditions . | 0 |
a first embodiment of the present invention will be described below with reference to fig5 to 7 . [ 0074 ] fig5 shows the structure of a digital image signal transmission apparatus . this image signal transmission apparatus comprises a transmission unit 10 set in a personal computer , a liquid crystal projector 20 and a cable 30 connecting them . the transmission unit 10 includes a vga controller ( graphic chip ) 11 , a switch circuit 12 , a cpu 13 , a one - phase to two - phase converter circuit 14 , a first panellink transmitter 15 and a second panellink transmitter 16 . the liquid crystal projector 20 includes a first panellink receiver 21 , a second panellink receiver 22 and a liquid crystal panel 23 of digital drive type . the first panellink receiver 21 incorporates a one - phase to two - phase converter circuit 21 a . the cable 30 comprises six pairs of signal lines for transmitting image data and one pair of signal lines for transmitting a clock signal . the cpu 13 detects which the image signals to be transmitted are of , a high resolution ( equal to or lower than the resolution of sxga ) or an ultrahigh resolution ( equal to or higher than the resolution of uxga ), on the basis of a control signal ( or both of the control signal and image data ) applied from the vga controller 11 . the cpu 13 controls the switch circuit 12 in accordance with the result of this detection . [ 0079 ] fig6 shows the data flow of a case when the cpu 13 detects that the image signals to be transmitted is of a high resolution ( equal to or lower than the resolution of sxga ). parallel image data ( r , g , b ) output by the vga controller 11 are input to the first panellink transmitter 15 via the switch circuit 12 . the panellink transmitter 15 converts the image data from the parallel signals to serial ones . the resultant serial r , g , and b signals each for a respective channel are transmitted through the cable 30 to the first panellink receiver 21 , which converts the received serial signals into the parallel ones . when the second panellink receiver 22 receives no image signals , the first panellink receiver 21 uses the one - phase to two - phase converter circuit 21 a to perform a one - phase to two - phase conversion of the obtained parallel signals , thereby obtaining the rgb even and odd data , which are then applied to the liquid crystal panel 23 of digital drive type . the information as to whether or not the second panellink receiver 22 receives any image signals is sent therefrom to the first panellink receiver 21 . in a case when the second panellink receiver 22 does receive the image signals , the first panellink receiver 21 applies the obtained parallel signals , as they are , to the liquid crystal panel 23 . [ 0084 ] fig7 shows the data flow of a case when the cpu 13 detects that the image signals to be transmitted is of an ultrahigh resolution ( equal to or higher than the resolution of uxga ). parallel image data ( r , g , b ) output by the vga controller 11 are applied through the switch circuit 12 to the one - phase to two - phase converter circuit 14 , being separated into even and odd data . the even data are applied to the first panellink transmitter 15 , while the odd data are applied to the second panellink transmitter 16 . the first panellink transmitter 15 converts the even data from the parallel signals to serial ones . the second panellink transmitter 16 converts the odd data from the parallel signals to serial ones . the serial r , g and b signals , each for two channels , obtained by panellink transmitters 15 and 16 are transmitted through the cable 30 to the first and second panellink receivers 21 and 22 . the first panellink receiver 21 converts the received even data from the serial signals to the parallel signals , while the second panellink receiver 22 converts the received odd data from the serial signals to the parallel signals . the parallel signals , rgb even and odd data , thus obtained by the first and second panellink receivers 21 and 22 are applied to the liquid crystal panel 23 . in the above - described embodiment , when it is detected that the image data to be transmitted are of a high resolution , the image data are transmitted by use of the “ single link ” method . when it is detected that the image data to be transmitted are of an ultrahigh resolution , the image data are transmitted by use of the “ dual link ” method . in the above - described first embodiment , the cpu 13 detected which the image signals to be transmitted were of , a high resolution ( equal to or lower than the resolution of sxga ) or an ultrahigh resolution ( equal to or higher than the resolution of uxga ), and the result of this detection was used to control the switch circuit 12 . instead , it may be arranged that the user selects , according to the resolution of the image signals to be transmitted , the high or ultrahigh resolution and that the switch circuit 12 is controlled based on his selected resolution . a second embodiment will be described below with reference to fig8 to 10 . [ 0094 ] fig8 shows the structure of a digital image signal transmission apparatus . this image signal transmission apparatus comprises a transmission unit 10 set in a personal computer ( pc ) 1 , a receiving - side unit 105 set in a liquid crystal projector 20 , and a cable 30 connecting the transmission unit 10 and the receiving - side unit 105 . the transmission unit 10 includes a graphics controller ( graphic board ) 101 , a switch circuit 102 , a one - phase to two - phase converter circuit 103 and a transmitting - side unit 104 . the graphics controller 101 is connected to a main cpu 2 in the pc 1 via a bus 3 also therein . the main cpu 2 is connected to a line receiver 146 . the transmitting - side unit 104 includes first and second panellink transmitters 111 and 112 , respectively . the receiving - side unit 105 in the liquid crystal projector 20 is connected to a liquid crystal panel 106 of digital drive type in the liquid crystal projector 20 . the receiving - side unit 105 includes a first panellink receiver 131 , a second panellink receiver 132 and a coupler 141 . the first panellink receiver 131 incorporates a one - phase to two - phase converter circuit 131 a . the liquid crystal projector 20 also includes a detector circuit 142 , an a / d converter 143 , a cpu 144 and a line driver 145 . the transmitting - side unit 104 in the transmission unit 10 is connected through the cable 30 to the receiving - side unit 105 in the liquid crystal projector 20 . the cable 30 comprises six pairs of signal lines for transmitting the image data and one pair of signal lines for transmitting the clock signal . this image signal transmission apparatus has , as its operation modes , a duallink mode for performing the signal transmission by use of the dual link method , and a singlelink mode for performing the signal transmission by use of the single link method . when the singlelink mode is selected as the operation mode , the parallel image data ( r , g , b ), the clock signal and the control signals ( h , v , de ( display enable )) from the graphics controller 101 are applied through the switch circuit 102 directly to the first panellink transmitter 111 without being applied to the one - phase to two - phase converter circuit 103 . in that case , the second panellink transmitter 112 is inactive in a power down mode . the first panellink transmitter 111 encodes the image data and clock signal , and performs a parallel - serial conversion that converts the image data from the parallel signals to serial ones . the thus obtained serial r , g and b signals each for a respective channel are transmitted through the cable 30 to the first panellink receiver 131 in the receiving - side unit 105 . in that case , the second panellink receiver 132 is inactive , entering the power down mode . the first panellink receiver 131 performs a data extraction , a serial - parallel conversion and a decoding with respect to the codes applied from the first panellink transmitter 111 in the transmitting - side unit 104 , thereby producing the parallel image data , h , v and de . when the second panellink receiver 132 receives no image signals , the first panellink receiver 131 uses the one - phase to two - phase converter circuit 131 a to perform a one - phase to two - phase conversion of the produced parallel image signals , and then applies the thus obtained rgb even and odd data to the liquid crystal panel 106 . the first panellink receiver 131 also uses the one - phase to two - phase converter circuit 131 a to perform one - half frequency divisions of the produced h , v and de and of the received clock signal , and then applies them to the liquid crystal panel 106 . the information as to whether or not the second panellink receiver 132 receives any image signals is sent therefrom to the first panellink receiver 131 . in a case when the second panellink receiver 132 does receive the image signals , the first panellink receiver 131 applies its obtained parallel signals , as they are , to the liquid crystal panel 106 . when the duallink mode is selected as the operation mode , the parallel image data ( r , g , b ) output by the graphics controller 101 are applied through the switch circuit 102 to the one - phase to two - phase converter circuit 103 , being separated thereby into even and odd data . the even data are applied to the first panellink transmitter 111 in the transmitting - side unit 104 , while the odd data are applied to the second panellink transmitter 112 also in the transmitting - side unit 104 . in the meantime , the clock signal and control signals ( h , v , de ( display enable )) output by the graphics controller 101 are applied to the one - phase to two - phase converter circuit 103 , being one - half frequency divided thereby , and then being applied to the first and second panellink transmitters 111 and 112 in the transmitting - side unit 104 . the first panellink transmitter 111 encodes the even data and clock signal , and performs a parallel - serial conversion that converts the even data from the parallel signals to serial ones . the second panellink transmitter 112 encodes the odd data and clock signal , and performs a parallel - serial conversion that converts the odd data from the parallel signals to serial ones . the r , g and b serial signals each for two channels , obtained by the first and second panellink transmitters 111 and 112 , are transmitted through the cable 30 to the first and second panellink receivers 131 and 132 in the receiving - side unit 105 . the first panellink receiver 131 performs a data extraction , a serial - parallel conversion and a decoding with respect to the codes applied from the first panellink transmitter 111 , thereby producing the parallel signals with respect to the even data and also producing h , v and de . the second panellink receiver 132 performs a data extraction , a serial - parallel conversion and a decoding with respect to the codes applied from the second panellink transmitter 112 , thereby producing the parallel signals with respect to the odd data . the parallel signals ( rgb even and odd data ) obtained by the first and second panellink receivers 131 and 132 are applied to the liquid crystal panel 106 . the control signals ( h , v and de ) produced by the first panellink receiver 131 and the clock signal received thereby are also applied to the liquid crystal panel 106 . incidentally , the three pairs of image data of the r , g and b signals and one pair of clock signals each are transmitted as a pair of differential signals from the transmitting - side unit 104 to the receiving - side unit 105 , and hence are almost at the same signal level . the transmission speed of the digital image data ( the serial image data ) along the cable 30 is , for example in the case of uxga , 1 . 65 gbps in the singlelink mode , and half the same , 825 mbps , in the duallink mode . in this embodiment , the coupler 141 is located on one of two signal lines for the pair of differential signals , clk + and clk −, received as the clock signal , specifically , on the signal line of signal clk −, as shown in fig9 and its coupling output is applied to the detector circuit 142 . the clk + and clk − signal lines each exhibit a characteristic impedance of 50 ohms at the single end , and a terminating resistor 141 a of the coupler 141 exhibits , for example , 50 ohms . the detector circuit 142 converts the clk − coupling output signal into an analog signal of a dc voltage proportional to the amplitude level of the clk − coupling output signal . the detector circuit 142 may comprise , for example , an ic of ad8313 available from analog devices inc . the detection signal output by the detection circuit 142 is converted into a digital signal by the a / d converter circuit 143 and then applied to an input port of the cpu 144 . the cpu 144 compares the level of the received clk − signal with a predetermined threshold value and provides a control signal for switching the operation mode ( from the singlelink mode to the duallink mode or vice versa ). this control signal is transmitted through the line driver 145 to the line receiver 146 in the pc 1 on the transmitting side as a feedback signal . as to the transmission of the control signal responsive to the level of the received signals to the line receiver 146 in the pc 1 , in a case of using , for example , a 24 - pin connector of digital visual interface ( dvi ) standard specified as a digital interface between pcs and liquid crystal projectors or the like in the united states , its unused pin terminal 8 ( nc ) can be utilized , without any additional wiring , to effect a serial transmission of the one - bit control signal . instead , however , an additional signal wiring may be used as the interface for transmitting the control signal . the control signal received by the line receiver 146 in the pc 1 is applied to the main cpu 2 . on the basis of the control signal applied to the main cpu 2 , the pc 1 sends an operation mode switch signal for switching between the singlelink mode and the duallink mode to the graphics controller 101 via the bus 3 . when receiving the operation mode switch signal , the graphics controller 101 sends a control signal responsive to this operation mode switch signal to the switch circuit 102 . in this embodiment , the initial operation mode of the transmission unit 10 has been set to the singlelink mode . when the transmission of image data to the liquid crystal projector 20 is started for the first time after turn - on of the transmission unit 10 , it is decided which mode should be used as the operation mode . in a case of using a short cable of three meters or less as the cable 30 , even when the image signals to be transmitted are of a high resolution of uxga that exhibits a transmission speed of 1 . 65 gbps in the single link method , the attenuation amount of the signals transmitted through the cable 30 is less than five or six db . thus , the singlelink mode can be used to provide a sufficient c / n ratio to reproduce the received signals without any errors . in such a case , the amplitude of a clk − coupling output signal developed by the coupler 141 is large , and the amplitude level of a signal output by the detector circuit 142 is high . thus , the cpu 144 develops a control signal for selecting the singlelink mode as the operation mode . this control signal is conveyed through the line driver 145 to the transmitting side . when receiving this control signal , the main cpu 2 in the pc 1 selects the singlelink mode as the operation mode and applies an operation mode switch signal responsive to this mode selection to the graphics controller 101 . the graphics controller 101 then applies a switch control signal for the singlelink mode to the switch circuit 102 . as a result , the initial operation mode ( singlelink mode ) remains unchanged . in a case of using a long cable of ten meters or more as the cable 30 , when the image signals to be transmitted are of a high resolution of uxga that exhibits a transmission speed of 1 . 65 gbps in the single link method , the attenuation amount of the signals transmitted through the cable 30 is 20 db or so . thus , the singlelink mode cannot be used to provide any sufficient c / n ratio to reproduce the received signals to a normal degree . in such a case , the amplitude of a clk − coupling output signal developed by the coupler 141 is small , and the amplitude level of a signal output by the detector circuit 142 is low . thus , the cpu 144 develops a control signal for selecting the duallink mode as the operation mode . this control signal is conveyed through the line driver 145 to the transmitting side . when receiving this control signal , the main cpu 2 in the pc 1 selects the duallink mode as the operation mode and applies an operation mode switch signal responsive to this mode selection to the graphics controller 101 . the graphics controller 101 then applies a switch control signal for the duallink mode to the switch circuit 102 . as a result , the initial operation mode ( singlelink mode ) is switched to the duallink mode . when the operation mode is thus switched to the duallink mode , the transmission speed of the signals through the cable 30 is reduced to 825 mbps , and the attenuation amount of the signals through the cable 30 is reduced to , for example , 10 db or so , resulting in a sufficient c / n ratio to reproduce the received signals . in a case of using a cable of five meters as the cable 30 , it is possible for the single link method to transmit uxga resolution signals . however , when qxga resolution signals , the transmission speed of which is higher , are transmitted , the amplitude of a clk − coupling output signal developed by the coupler 141 is small and hence the amplitude level of a signal output by the detector circuit 142 is low . consequently , the operation mode is automatically switched from the singlelink mode to the duallink mode in the same manner as stated above , resulting in a reproduction of the received signals without any errors . according to the second embodiment described above , an appropriate transmission method , either the single link method or the dual link method , can automatically be selected , as the method for transmitting the signals from the transmitting - side unit , in accordance with the resolution of the image data to be transmitted and the length of the cable actually used . in the second embodiment described above , the coupler 141 was located on the clk − signal line , but it may be located on the clk + signal line , or on any one of the other rxr +, rxr −, rxg +, rxg −, rxb +, and rxb − image signal lines . additionally , as shown in fig1 , the transmission of the control signal from the liquid crystal projector 20 on the receiving side to the pc 1 on the transmitting side may be effected by use of a wireless interface such that the control signal output by the cpu 144 is transmitted from a wireless transmitter 147 and received by a wireless receiver 148 . a third embodiment will be described blow with reference to fig1 to 14 . [ 0129 ] fig1 shows the structure of an image signal transmission apparatus . in fig1 , elements corresponding to the same elements in fig3 and 4 are identified by the same reference designations . this image signal transmission apparatus comprises a transmission unit 10 set in a personal computer pc 1 , a receiving - side unit 153 set in a liquid crystal projector 20 , and a cable 154 connecting the transmission unit 10 and the receiving - side unit 153 . the transmission unit 10 comprises a graphics controller ( graphics board ) 151 and a transmitting - side unit 152 connected thereto . the graphics controller 151 is connected to a main cpu 2 in the pc 1 via a bus 3 also therein . the transmitting - side unit 152 in the transmission unit 10 is connected to the receiving - side unit 153 via the cable 154 . the main cpu 2 is connected to a line receiver 196 . the receiving - side unit 153 in the liquid crystal projector 20 is connected to a liquid crystal panel 155 of digital drive type in the liquid crystal projector 20 . the liquid crystal projector 20 also includes a detector circuit 192 , an a / d converter 193 , a cpu 194 and a line driver 195 . the transmitting - side unit 152 includes an encoding / parallel - serial converting circuit 161 , a pll circuit 162 , and an amplitude control circuit 163 . the encoding / parallel - serial converting circuit 161 receives image data , de ( a display enable signal ) and a control signal from the graphics controller 151 . in the encoding / parallel - serial converting circuit 161 , a parallel - serial conversion of the 24 - bit parallel image data is performed . then , the signal amplitude is reduced so as to effect a reduction of emi noise . additionally , an encoding is performed at the time of the parallel - serial conversion . when this encoding is performed , the variation of the level of the signals to be transmitted is reduced so as to further reduce the emi noise . the pll circuit 162 generates a clock signal for the encoding / parallel - serial converting circuit 161 on the basis of a clock signal applied from the graphics controller 151 . the cable 154 comprises three pairs of signal lines for transmitting the codes including both the image data and the control signal , and one pair of signal lines for transmitting the clock signal generated by the pll circuit 162 . the amplitude control circuit 163 adjusts , in accordance with the resistance value of an external variable resistor circuit 164 , the amplitude of the signals ( i . e ., the codes including both the image data and the control signal , and the clock signal ) to be applied from the transmitting - side unit 152 to the cable 154 . as shown in fig1 , the variable resistor circuit 164 comprises a parallel combination of a series circuit of a first resistor 201 and a first switch 205 , a series circuit of a second resistor 202 and a second switch 206 , a series circuit of a third resistor 203 and a third switch 207 , and a series circuit of a fourth resistor 204 and a fourth switch 208 . for example , the resistance value of the first resistor 201 is 820 ohms , that of the second resistor 202 is 620 ohms , that of the third resistor 203 is 390 ohms , and that of the fourth resistor 204 is 180 ohms . the switches 205 to 208 are controlled by a 2 - bit amplitude control signal ( 00 , 01 , 10 , 11 ). when the amplitude control signal is , for example , “ 00 ”, the first switch 205 only is turned on , the other switches 206 , 207 and 208 being turned off . in that case , the variable resistor circuit 164 exhibits the resistance value of 820 ohms . when the amplitude control signal is , for example , “ 01 ”, the second switch 206 only is turned on , the other switches 205 , 207 and 208 being turned off . in that case , the variable resistor circuit 164 exhibits the resistance value of 620 ohms . when the amplitude control signal is , for example , “ 10 ”, the third switch 207 only is turned on , the other switches 205 , 206 and 208 being turned off . in that case , the variable resistor circuit 164 exhibits the resistance value of 390 ohms . when the amplitude control signal is , for example , “ 11 ”, the fourth switch 208 only is turned on , the other switches 205 , 206 and 207 being turned off . in that case , the variable resistor circuit 164 exhibits the resistance value of 180 ohms . in this way , the resistance value of the variable resistor circuit 164 can be switched among the four values . in other words , the on / off control of the switches 205 , 206 , 207 and 208 can switch , among four values , the amplitude of the signals to be applied from the transmitting - side unit 152 to the cable 154 . the receiving - side unit 153 includes a data extracting / serial - parallel converting / decoding circuit 181 , a pll circuit 182 and a coupler 191 . the data extracting / serial - parallel converting / decoding circuit 181 performs a data extraction , a serial - parallel conversion and a decoding with respect to the codes applied from the transmitting - side unit 152 to produce the image data , de and the control signal . the pll circuit 182 produces a clock signal for the data extracting / serial - parallel converting / decoding circuit 181 on the basis of the clock signal applied from the transmitting - side unit 152 . the image data , de and control signal produced by the data extracting / serial - parallel converting / decoding circuit 181 and the clock signal produced by the pll circuit 182 are applied to the liquid crystal panel 155 . the three pairs of image data of r , g and b signals each pair are transmitted as a pair of differential signals from the transmitting - side unit 152 to the receiving - side unit 153 , and hence are almost at the same signal level . the transmission speed of the digital image data ( the serial image data ) along the cable is , for example in a case of sxga signals , 1 . 08 gbps . in this embodiment , the coupler 191 is located on one of two signal lines for the pair of differential signals , rxr + and rxr −, received as the r signal , specifically , on the line for the signal rxr −, as shown in fig1 , and its coupling output is applied to the detector circuit 192 . the rxr + and rxr − signal lines each exhibit a characteristic impedance of 50 ohms at the single end , and a terminating resistor 501 of the coupler 191 exhibits , for example , 50 ohms . the detector circuit 192 converts the rxr − coupling output signal into an analog signal of a dc voltage proportional to the amplitude level of the rxr − coupling output signal . the detector circuit 192 may comprise , for example , an ic of ad8313 available from analog devices inc . a detection signal output by the detection circuit 192 is converted into a digital signal by the aid converter circuit 193 and then applied to an input port of the cpu 194 . the cpu 194 provides , in response to the level of the rxr − received signal , a control signal to be conveyed so as to change the level of the signals to be transmitted from the transmitting side . this control signal is conveyed through the line driver 195 to the line receiver 196 in the pc 1 on the transmitting side as a feedback signal . as to the transmission of the control signal responsive to the level of the received signals to the line receiver 196 in the pc 1 , in a case of using , for example , a 24 - pin connector of digital visual interface ( dvi ) standard specified as a digital interface between pcs and liquid crystal projectors or the like in the united states , its unused pin terminal 8 ( nc ) can be utilized , without any additional wiring , to effect a serial transmission of the one - bit control signal . instead , however , an additional signal wiring may be used as the interface for transmitting the control signal . the control signal received by the line receiver 196 in the pc 1 is applied to the main cpu 2 . on the basis of the control signal applied to the main cpu 2 , the pc 1 sends a command signal ( amplitude command signal ) to the graphics controller 151 via the bus 3 . when receiving the command signal , the graphics controller 151 applies an amplitude control signal responsive to this command signal to the variable resistor circuit 164 . in a case of using a short cable of one meter or less as the cable 154 , the amplitude of a rxr − coupling output signal developed by the coupler 191 is large , and the amplitude level of the signal output by the detector circuit 192 is high . thus , the aforementioned control signal , developed by the cpu 194 , to be conveyed so as to change the level of the signals to be transmitted from the transmitting side is conveyed through the line driver 195 to the transmitting side so as to reduce the amplitude level of the signals to be transmitted from the transmitting side . on the basis of the control signal conveyed from the receiving side , the pc 1 applies a command signal ( amplitude command signal ) through the bus 3 to the graphics controller 151 , which then provides a 2 - bit amplitude control signal of “ 00 ”. in that case , the switch 205 is in the on - state , while the other switches 206 to 208 being in the off - state . thus , the variable resistor circuit 164 exhibits the largest one of the four resistance values , 820 ohms , so that the amplitude of the signals to be applied from the transmitting - side unit 152 to the cable 154 becomes the smallest one of the four amplitude values . in a case of using a long cable of ten meters or more as the cable 154 , the amplitude of a rxr − coupling output signal developed by the coupler 191 is small , and the amplitude level of a signal output by the detector circuit 192 is low . thus , the aforementioned control signal , developed by the cpu 194 , to be conveyed so as to change the level of the signals to be transmitted from the transmitting side is conveyed through the line driver 195 to the transmitting side so as to raise the amplitude level of the signals to be transmitted from the transmitting side . on the basis of the control signal conveyed from the receiving side , the pc 1 applies a command signal ( amplitude command signal ) through the bus 3 to the graphics controller 151 , which then provides a 2 - bit amplitude control signal of “ 11 ”. in that case , the switch 208 is in the on - state , while the other switches 205 to 207 being in the off - state . thus , the variable resistor circuit 164 exhibits the smallest one of the four resistance values , 180 ohms , so that the amplitude of the signals to be applied from the transmitting - side unit 152 to the cable 154 is the largest one of the four amplitude values . according to the third embodiment described above , the pc 1 , in which the graphics controller 151 has been set , can automatically adjust the amplitude of the signals to be applied from the transmitting - side unit 152 to the cable 154 so that the amplitude level of the image data will be appropriate on the receiving side . the third embodiment was described above with respect to the case of adjusting , among the four values , the amplitude of the signals to be applied from the transmitting - side unit 152 to the cable 154 . the present invention , however , is not limited only to this number of signal amplitude values but may be applied to any other number of signal amplitude values . in the third embodiment described above , the coupler 191 was located on the rxr − signal line , but it may be located on the rxr + signal line , or on any one of the other rxg +, rxg −, rxb +, and rxb − image signal lines . additionally , as shown in fig1 , the transmission of the control signal from the liquid crystal projector 20 on the receiving side to the pc 1 on the transmitting side may be effected by use of a wireless interface such that the control signal output by the cpu 194 is transmitted from a wireless transmitter 197 and received by a wireless receiver 198 . | 8 |
in accordance with the invention , formulations are provided for use with the inventive method that incorporate civamide into sterile solutions or suspensions suitable for intrathecal administration such as cerebrospinal injection . in each of the foregoing formulations , civamide may be present in a single dosage of from about 0 . 001 mg to about 1 mg . the civamide can be present as the compound civamide or as a pharmaceutically acceptable salt thereof , such as a hydrochloride salt or an acetate salt . the civamide composition can be in the form of a suspension with a pharmaceutically acceptable suspension agent , such as dimethylsulfoxide or cyclodextrin . the composition will include a pharmaceutically acceptable vehicle suitable for introduction into the intrathecal space , such as normal saline . in a preferred form , the composition will be packaged in sterile ampules or vials . civamide is synthesized according to a proprietary process and supplied by winston laboratories , vernon hills , ill . the instant invention comprises the method of instilling or injecting sterile solutions or suspensions of civamide or one of its salts into the cerebrospinal fluid in a single dose or very infrequent doses ( monthly or bimonthly ) in order to treat a variety of painful disorders including post - surgical pain and chronic neuropathic disorders such as postherpetic neuralgia , diabetic neuropathy , reflex sympathetic dystrophy , and post - mastectomy pain . the civamide or its salt will be present in each dose in the amount of about 0 . 001 mg to about 1 mg . the method of the instant invention will be more readily comprehended from the following examples . civamide in amounts of 1 φg , 5 φg , 10 φg , 50 φg , and 100 φg was dispersed in both 10 φl and 20 φl of each of the following : 100 % dimethylsulfoxide ( dmso ), normal saline ( 0 . 9 % w / v sodium chloride ) with 10 % dmso as suspending agent , normal saline with 0 . 5 % dmso and 10 % cyclodextrin , 10 % cyclodextrin and 10 % dmso as suspending agent , and normal saline with 10 % cyclodextrin suspending agent , and normal saline with 25 % dmso . in each case , the saline was 0 . 9 % usp . these compositions were physically and chemically stable , and used for injection into the cerebrospinal fluid of male sprague - dawley rats . civamide and capsaicin were each separately administered intrathecally , in dosages of 1 φg , 5 φg , 10 φg , 50 φg , or 100 φg in either 10 φl or 20 φl of 0 . 9 % usp saline with 25 % dmso suspending agent , 0 . 9 % usp saline and 10 % cyclodextrin , and 0 . 9 % usp saline with 0 . 5 % dmso and 10 % cyclodextrin , to male sprague - dawley rats into whom intrathecal catheters had been inserted . seven days later , tail flick , hot plate ( 49 ° c ., 52 ° c .) and paw pressure pain models were evaluated . in these pain models , intrathecally administered civamide was significantly more effective than saline , as well as more effective than intrathecally administered capsaicin . civamide 10 φg / 10 φl saline , 25φg / 10 φl saline , and 50 φg / 10 φl saline and saline itself were administered intrathecally to male sprague - dawley rats . each of the civamide compositions also included either 20 % dmso or 25 % dmso as a suspending agent . the saline used was 0 . 9 % usp . eighteen hours , 7 days , 14 days and 28 days after administration of a single intrathecal dose of either civamide or saline , models for various types of pain were evaluated . these included models for acute nociceptive processing ( i . e . thermal escape ), post tissue injury hyperpathic states ( i . e . formalin and thermal injury evoked hyperalgesia ) and nerve injury induced hyperpathia ( i . e . tactile allodynia in the chung model of neuropathy ). the results of these studies demonstrated that within 18 hours after administration , intrathecal civamide produced effective pain amelioration , and the effects of a single dose lasted for at least 28 days after admistration . while the foregoing is a description of the preferred embodiments of the invention , it will be readily apparent to those skilled in the art that various modifications may be made therein without departing from the true scope and spirit of the invention as set forth in the appended claims . | 0 |
“ rebacuo superconductor ” means rare earth ( re ), barium ( ba ), copper ( cu ) and oxygen ( o ) containing compositions that constitute superconductors at cryogenic temperatures . “ substantially pure rebacuo superconductor ” means a rebacuo superconductor that contains less than 2 %, preferably less than 1 %, most preferably less than 0 . 5 % by weight of materials other than re , ba , cu and o . fig1 shows a cross - section of one embodiment of the coated conductor 10 . at least a substrate 12 and ( re ) bco layer 14 are provided . the substrate 12 supports , either directly or through the presence of one or more intermediate layers , the ( re ) bco ( re ) bco layer 14 . optionally , a solution deposition planarization layer 16 is formed at the surface of the substrate 12 . the solution deposition planarization layer 16 may then directly support the ( re ) bco layer 14 , or may interface with an intermediate layer 18 . in one implementation , the intermediate layer 18 may be an ibad epitaxial layer , such as an ibad epi mgo layer . the intermediate layer 18 may directly support the ( re ) bco layer 14 , or may interface with a optional buffer layer 20 , which in turn can support the ( re ) bco layer 14 . the substrate may be either non - flexible or flexible . if non - flexible , it may be a crystal substrate , such as an mgo substrate . if the substrate is flexible , it may be for example a flexible metal tape . in one implementation , substrate 10 is a flexible metal substrate that can for example be stainless steel or hastelloy . the thickness of the substrate is often in the range of 0 . 002 to 0 . 004 inch . the substrate material must meet certain selection criteria : it must be mechanically and chemically stable at the growth temperature of the superconductor (˜ 800 c ), it must have a thermal expansion coefficient similar to the superconductor (˜ 12 - 13 ), a high yield strength , and be non - magnetic . with reference to fig2 and 3 , an optional planarization step is performed . the planarization provides an amorphous metal oxide layer that is solution deposited preferably using a solution deposition planarization ( sdp ) process on the substrate . this one layer provides a diffusion barrier , planarizes the rough metal surface , is chemically stable and provides an amorphous surface suitable for the growth of subsequent layers . often to otherwise accomplish all of these features several separate steps including electropolishing , the addition of a diffusion barrier and a amorphous bed layer for ion beam assisted deposition ( ibad ), would be required . substrate tape stock 24 may be fed from a spool into a bath 26 containing the planarization solution . the coated conductor passes through dryer 28 onto a take up spool having the now planarization layer coated substrate 30 . fig3 shows an exploded view of the substrate 12 and the solution deposition planarization layer 16 . the solution deposition planarization ( sdp ) process uses metal organic precursor dissolved in solvent . this solution can be applied to the metal substrate utilizing techniques such as dip coating , spray coating , meniscus coating or slot die coating . the solution deposited on the metal substrate travels into a heater where the solvent is evaporated out , and the organic carrier is volatilized leaving behind only the dense , amorphous , metal oxide film . multiple coatings deposited by sequentially repeating this process creates a smooth ( roughness ˜ 1 nm ), planarized , chemically stable , and amorphous surface . with reference to fig4 , the optional next layer is deposited using an ion beam assisted deposition ( ibad ) technique . a metal oxide having a rock - salt - like crystal structure , usually mgo , is deposited with the assistance of an ion beam ( see , e . g ., do et al ., u . s . pat . no . 6 , 190 , 752 entitled “ thin films having rock - salk - like structure deposited on amorphous surfaces ”, see also wang , et al ., “ deposition of in - plane textured mgo on amorphous si 3 n 4 substrates by ion - beam - assisted deposition and comparisons with ion - beam - assisted deposited yttria - stabilized - zirconia ” appl . phys . lett . 71 ( 20 ), pp . 2955 - 2957 , 17 nov . 1997 and iijima et al , “ research and development of biaxially textured ibad - gzo templates for coated superconductors ”, mrs bulletin , august 2004 pp . 564 - 571 , all incorporated herein as if fully set forth herein ) to permit the formation of a 3 - dimensionally ordered , crystalline thin film . optionally a thicker layer of the metal oxide can be grown epitaxially to increase thickness and improve crystallinity . ion beam assisted deposition ( ibad ) is typically done by vacuum evaporating magnesium oxide ( mgo ) ( source 32 ) while directing an ion beam 34 at an angle to the substrate 12 . when the ion beam is set to the correct energy and density , it gives bi - axially textured orientation to the mgo . this ibad textured layer then provides a seed layer for the epitaxial growth of ( re ) bco material . next an optional buffer layer 20 ( fig1 ) is grown on the ibad layer to improve the lattice match to the ( re ) bco film . the epitaxial hts layer is next grown , preferably using a reactive co - evaporation cyclic deposition and reaction ( rce - cdr ), described in more detail , below . lastly an optional cap layer 22 of metal , preferably silver is deposited on the hts to provide electrical contact to the superconducting film and physical protection . with reference to fig5 , the rce - cdr uses high purity metal targets 36 of one or more of the following rare earths ( yttrium , samarium , gadolinium , neodymium , dysprosium , etc . ), barium and copper in an oxygen background environment of 10 − 5 torr . the film growth occurs when it passes through the oxygen pocket where the pressure is maintained at 10 - 30 mtorr . this deposition and film growth cycle is done at 5 - 10 hz by rotating the sample holder . heater 38 heats the substrate . after the film is fully grown it is cooled down in oxygen pressure of 600 torr . techniques for rce - cdr are now known to those skilled in the art , see , e . g ., ruby et al , “ high - throughput deposition system for oxide thin film growth by reactive coevaporation ”, now published as us published application 2007 / 0125303 , which is incorporated herein by reference for the teaching of rce - cdr , as if fully set forth herein . fig6 is a plot of the critical current ( i c ) ( left vertical axis ) and critical current density ( j c ) ( right vertical axis ) as a function of magnetic field strength applied parallel to the sample , for two different temperatures . the graph shows the critical current of ( re ) bco grown on flexible metal tape measured in magnetic field at different temperatures . as the magnetic field increases the critical current decreases . at a field of 3 t , with the magnetic field parallel to the film , the i c is approximately 290 a / cm - width , and j c is approximately 0 . 66 ma / cm 2 . the upper data set is at 65 k and the lower data set is at 75 k . fig7 is a plot of the critical current ( i c ) ( left vertical axis ) and critical current density ( j c ) ( right vertical axis ) as a function of the angle from the c - axis applied to the sample . fig7 shows the critical current of the same sample as in fig6 measured at 75 k as a function of the angle of the applied magnetic filed . it shows a very strong peak when the magnetic filed is perpendicular to the film normal . the upper data set is at 75 k in a 3 t field , and the lower data set is at 75 k in a 5 t field . fig8 is a plot of the critical current ( i c ) ( left vertical axis ) and critical current density ( j c ) ( right vertical axis ) as a function of magnetic field strength applied parallel to the sample . fig8 is the same type of measurement as fig7 but done at a lower temperature of 65 k . the critical current increases significantly when cooled from 75 k . at 65 k and 3 t the minimum critical current is 250 a . the upper data set is at 65 k in a 3 t field , and the lower data set is at 55 k in a 5 t field . fig9 is a plot of the critical current ( i c ) ( left vertical axis ) and critical current density ( j c ) ( right vertical axis ) as a function of magnetic field strength applied parallel to the sample , at two different temperatures . it shows the critical current of the same ( re ) bco deposited on single crystal mgo instead of the metal tape . this was measured in magnetic field at different temperatures under the same condition as fig6 . the minimum critical current improves roughly 50 % when ( re ) bco is grown on single crystal . the upper data set is at 65 k and the lower data set is at 75 k . fig1 is a plot of the critical current density ( j c ) ( left vertical axis ) and critical current ( i c ) ( right vertical axis ) as a function of magnetic field strength applied parallel to the sample . fig1 shows the critical current of the sample grown on single crystal mgo measured at 65 k as a function of the angle of the applied magnetic field . comparing fig8 to fig1 shows a minimum critical current improvement of 80 %. the uppermost data set is at 3 t , the middle data set is at 5 t and the bottom data set is at 7 t . fig1 is a plot of the critical current density ( j c ) as a function of the angle from the c - axis of the magnetic field applied to a three different ndbco samples . the field is 1 t , at 75 . 5 k . at angle 0 , the uppermost data set is for a field of 1 t , with ndbco of thickness 0 . 7 μm , the middle data set is for a field of 0 . 9 t , for nd 1 . 11 bco of thickness 0 . 7 and the bottom data set is for a field of 1 t for ndbco of thickness 1 . 4 μm . the off - stoichiometry for nd rich films significantly enhanced the minimum j c values , by approximately a factor of 4 . fig1 is a plot of the critical current density ( j c ) as a function of the angle from the c - axis of the magnetic field applied to a three different smbco samples and one ndbco sample . fig1 may be compared to fig1 for the difference between the two rare earths ( nd and sm ). at angle 0 , the uppermost data set is for a field of 0 . 9 t , with smbco of thickness 0 . 7 μm , the second data set is for a field of 0 . 9 t , for sm 1 . 1 bco of thickness 0 . 8 μm , the third data set is for a field of 0 . 9 t , for sm 1 . 2 bco of thickness 0 . 86 μm , and the bottom data set is for a field of 0 . 9 t for ndbco of thickness 0 . 7 μm . the off - stoichiometry for sm rich films significantly enhanced the minimum j c values , especially those having a sm enhancement of substantially 1 . 1 , or 10 %. fig1 is a plot of the critical current density ( j c ) as a function of the angle from the c - axis of the magnetic field applied to a series of smbco samples having various thicknesses . at angle 0 the upper most data are for the 0 . 7 μm film , the 1 . 6 μm film , then the 4 . 4 μm film , then the 3 . 3 μm film , with the 2 . 2 μm film showing at angle 0 as the lowest datapoint . for films less than 1 . 6 μm , and particularly for films at substantially 2 . 2 μm and thicker , the angular dependence of the j c is essentially flat . fig1 a and b show x - ray diffraction patterns showing 2θ - ω and ω scans for : fig1 a ybco on mgo single crystal and fig1 b ybco on ibad / epi mgo on sdp hastelloy . the δ2θ is preferably less than 0 . 2 , more preferably less than 0 . 1 , and most preferably less than 0 . 050 . the δω is preferably less than 0 . 5 , more preferably less than 0 . 36 , and most preferably less than 0 . 15 . these results establish that the films are of very high crystal quality . fig1 shows the x - ray diffraction pattern of ( re ) bco grown on metal tape substrate . ( 001 ) peaks are well defined and it is a clear indication that the hts is growing c - axis orientated . there are no signs of polycrystalline material nor evidence of a , b oriented growth . fig1 is a x - ray diffraction pole of ( re ) bco ( 103 ) peak which shows that in - plane texture is well defined having four strong peaks . fig1 is an atomic force microscopy ( afm ) image showing the surface image of a thin layer of silver deposited on ( re ) bco grown on metal substrate . the large particles are copper oxide covered by silver and the short needle - like microstructure comes from the silver grains grown on top of ( re ) bco . fig1 is a resistivity vs . temperature curve of ( re ) bco grown on mgo single crystal substrate . the single crystal was inserted next to the metal substrate as a process monitor . this particular sample had a critical temperature of 93 . 7 kelvin . fig1 a , b and c are graphs of critical current ( i c ) under magnetic field of 0 . 66 t as a function of position along a tape for a 70 cm long tape ( fig1 a ), a 120 cm long tape ( fig1 b ) and a 24 cm long tape ( fig1 c ), for self - field at 77 k . high temperature superconductor ( re ) bco is deposited on 2 different types of substrates : flexible metal substrate and single crystal magnesium oxide . the dimension of the metal tape is 4 cm long , 1 cm wide and 0 . 004 inch thick . solution deposition layer of metal oxide is deposited on the metal substrate followed by ion beam assisted deposition of magnesium oxide . single crystal magnesium oxide substrate is cut into 1 cm length , 1 cm width and 0 . 02 inch thick piece and crystal orientation is ( 100 ). the method of deposition is reactive co - evaporation . high purity metal targets of rare earths ( yttrium , samarium , gadolinium , neodymium , dysprosium , etc . ), barium and copper are used for evaporation . barium and copper can be evaporated with a thermal source , whereas most of the rare earths require electron beam source because of their high melting temperature . samarium is an exception due to its nature to sublimate . it is easily deposited with special thermal source with baffles . the evaporation rate is monitored and controlled by quartz crystal monitors ( qcm ). each elemental source has its own qcm directed line - of - sight through multiple collimators . the oxygen is directly supplied through the heater and its flow is controlled by a mass flow controller . the overall background oxygen pressure is monitored by a hot cathode ion gauge . typical background pressure during deposition is in the range of 10 − 5 torr . this deposition and film growth cycle is done at 5 / 10 hz by rotating the sample holder attached to the heater . the film growth occurs when the sample passes through the oxygen pocket where the pressure is maintained at 10 / 30 mtorr . heater temperature ranges between 750 - 800 ° c . after the film is fully grown it is cooled down in oxygen pressure of 600 torr . these inventions provide cutting edge high - magnetic - field test results for second generation ( 2g ) hts wire . this demonstrates exceptional in - field critical current values . this world - class current - carrying capability in high magnetic field demonstrates the effectiveness of the disclosed hts fabrication process at producing 2g hts wire for demanding applications such as superconducting fault current limiters and high - power wind turbine generators . the 2g hts coated conductor sample on a template that exhibits a minimum critical current of 228 amperes ( a ) at a temperature of 65 kelvin ( k ) in an applied magnetic field of 3 tesla ( t ), corresponding to 256 a / centimeter ( cm )- width . this critical current is the minimum value as a function of magnetic field angle . the maximum critical current of this sample at 65 k exceeded 404 a / cm - width for a 3 - t magnetic field oriented parallel to the coated conductor surface ; this latter current value was limited by the amount of current supplied by the measurement apparatus . in a st field at 65 k , the coated conductor exhibited a minimum critical current of 143 a / cm - width and a maximum critical current of 322 a / cm - width . this sample was fabricated using a straightforward hts structure and did not need to add additional elements or so - called artificial pinning centers to the coated conductor to obtain this result . these 2g hts wires utilize hts material deposition processes and volume manufacturing to produce energy - efficient , cost - effective , and high - performance 2g hts wire for next generation power applications . 2g hts wire is fabricated using its deposition technology known as reactive coevaporation with cyclic deposition and reaction ( rce - cdr ). this specific sample of 2g hts wire is 8 . 9 millimeters wide × 4 . 4 microns thick and was grown on a 1 - cm - wide × 4 - cm - long template . this simplified template contained a reduced number of layers compared to competing 2g hts wire technologies . the template consisted of a non - magnetic nickel - alloy substrate followed by layers of only two materials : a solution - deposition planarization ( sdp ) layer and an ion - beam assisted deposition ( ibad ) layer . an advantage of the rce - cdr technology is that it allows high - performance 2g hts wire to be grown on these simplified templates . this simplified template platform combined with the rce - cdr process results in a superior high - yield , low - cost 2g hts wire technology . coated conductors are useful in a wide variety of applications including but not limited to high power transmission cables ( ac ), superconducting fault current limiters , wind turbine ( generator ), industrial motors and generators , and magnetic resonance imaging machines . all publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference . although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity and understanding , it may be readily apparent to those of ordinary skill in the at in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the following claims . | 7 |
the synthetic examples of the compounds of formula ( 1 ) of the present invention , and the organic el device applied with the compounds are explained through the synthetic examples and practicing examples below . additional advantages , objects , and features of the present invention will be set forth in the description which follows and will also become apparent to those who practice the present invention . the objectives and other advantages of the present invention will be explained in the written description including the claims . 60 g of 2 , 5 - dibromo - p - xylene ( 0 . 227 mole ), 42 . 4 g of cucn ( 0 . 568 mole ) and 300 ml of dimethylformamide were added into a round - bottom flask , and then the reaction was performed at 130 ° c . for 12 hours . after completion of the reaction , the reaction mixture was added to the mixing solution of 300 ml of water and 300 ml of aqueous ammonia , and extracted crystal therefrom was filtered . then , the crystal was added again to the mixing solution of 100 ml of water and 300 ml of aqueous ammonia , mixed and filtered . the obtained crystal was added to 2 , 000 ml of toluene , heated to dissolve , and treated with active carbon . the filtrate was evaporated in vacuum , and then 300 ml of hexane was added thereto to obtain 20 g of white crystal ( 0 . 128 mole , yield : 56 %). 2 g of 2 , 5 - dimethyl - terephthalonitrile ( 0 . 0128 mole ), 1 . 9 ml of bromine ( 0 . 384 mole ) and 100 ml of dichoromethane were added to a middle pressure tube , and the reaction was performed at 60 ° c . for 24 hours . after completion of the reaction , 200 ml of water was added thereto , and then the ph of the reaction solution was ph 10 with 2 % sodium hydroxide . after the organic layer was separated , extracted by 200 ml of water two times , and evaporated in vacuum . the concentrated crystal was loaded to column with hexane to obtain 1 . 1 g of product ( 3 . 5 mole , yield : 27 . 5 %). 3 g of 2 , 5 - dibromomethyl - terephthalonitrile ( 9 . 55 mmole ), 6 . 6 ml of triethoxyphosphate ( 0 . 038 mole ) and 100 ml of toluene were added into a round - bottom flask , and refluxed for 24 hours . after completion of the reaction , the reaction mixture was treated with active carbon , and the filtrate was evaporated in vacuum to obtain 3 g of white crystal ( 7 . 0 mmole , yield : 75 %). 1 . 3 g of [ 2 , 5 - dicyano - 4 -( diethoxy - phosphorylmethyl )- benzyl ]- phosphonic acid diethyl ester ( 3 . 03 mmole ), 1 . 4 g of 9 - ethyl - carbazolaldehyde , and 100 ml of tetrahydrofuran were added into a round - bottom flask . 0 . 7 g of t - butyloxide potassium ( 6 . 37 mmole ) divided by several times was slowly added to the reaction mixture , and then the resulting mixture was stirred at ambient temperature for 1 hour , 200 ml of water was added thereto , and then the produced crystal was filtered and washed with 50 ml of methyl alcohol . the obtained crystal was added to 100 ml of dichloromethane , mixed , and filtered to obtain 0 . 8 g of orange crystal ( 1 . 41 mmole , yield : 46 %). the melting point of the final compound was measured to 333 ° c . 1 . 3 g of [ 2 , 5 - dicyano - 4 -( diethoxy - phosphorylmethyl )- benzyl ]- phophosphonic acid diethyl ester ( 3 . 03 mmole ), 1 . 54 g of 10 - ethyl - 3 - phenocyazine aldehyde ( 6 . 06 mmole ), and 100 ml of tetrahydrofuran were added into a round - bottom flask . 0 . 7 g of t - butyloxide potassium ( 6 . 37 mmole ) divided by several times was slowly added to the reaction mixture , and then the reaction mixture was stirred at ambient temperature for 1 hour . then , 200 ml of water wad added thereto , and the produced crystal was filtered , and washed with 50 ml of methyl alcohol . 100 ml of dichloromethane was added to the obtained crystal , stirred and filtered to obtain 0 . 94 g of orange crystal ( yield : 49 %). 1 . 3 g of [ 2 , 5 - dicyano - 4 -( diethoxy - phosphorylmethyl )- benzyl ]- phophosphonic acid diethyl ester ( 3 . 03 mmole ), 1 . 45 g of 10 - ethyl - 3 - phenocyazine aldehyde ( 6 . 06 mmole ), and 100 ml of tetrahydrofuran were added into a round - bottom flask . 0 . 7 g of t - butyloxide potassium ( 6 . 37 mmole ) divided by several times was slowly added to the reaction mixture , and then the reaction mixture was stirred at ambient temperature for 1 hour . then , the produced crystal was filtered , and washed with 50 ml of methyl alcohol . 100 ml of dichloromethane was added to the obtained crystal , stirred and filtered to obtain 0 . 72 g of orange crystal ( yield : 39 %). 1 . 3 g of [ 2 , 5 - dicyano - 4 -( diethoxy - phosphorylmethyl )- benzyl ]- phophosphonic acid diethyl ester ( 3 . 03 mmole ), 1 . 65 g of 4 - formyltriphenyl aldehyde ( 6 . 06 mmole ), and 100 ml of tetrahydrofuran were added into a round - bottom flask . 0 . 7 g of t - butyloxide potassium ( 6 . 37 mmole ) divided by several times was slowly added to the reaction mixture , and then the reaction mixture was refluxed and cooled to obtain a crystal . then , the produced crystal was filtered , and washed with 200 ml of methyl alcohol . 100 ml of dichloromethane was added to the obtained crystal , stirred and filtered to obtain 0 . 8 g of orange crystal ( 1 . 41 mmole , yield : 39 %). a brome crude liquid ( 14 ml , 0 . 27 mmol ), iron powder ( 4 g , 72 mmol ), and carbon tetrachloride ( 30 ml ) were added to a reaction vessel , and then 1 , 3 , 5 - trimethylbenzene ( 2 ml , 14 mmol ) was slowly added thereto over 1 hour . the reaction mixture was further stirred for 1 hour , and then na 2 s 2 o 3 solution was excessively added thereto and brome was excluded . then , this solution was extracted with water / chloroform to eliminate solvent thereof , and re - crystallized with the mixing solution ( toluene / acetone = 1 / 5 ) to obtain white product [ yield : 3 . 5 g ( 70 % over )]. cucn ( 220 g , 243 mmol ) and pyridine ( 146 . 7 g , 1 . 85 mol ) were added to a high pressure reaction vessel , and well mixed , and then 2 , 4 , 6 - tribromo - 1 , 3 , 5 - trimethylbenzene ( 25 g , 75 . 8 mmol ) was added thereto . the reaction mixture was reacted at 205 ° c . for 2 hours . cu therein was excluded with excessive methylene diamine , and then filtered by mc . water in the reaction mixture was eliminated over mgso 4 , and then solvent therein was evaporated in vacuum . the residue was absorbed to silica gel column and separated with a tube chromatography ( hx : mc = 3 : 1 ) to obtain white solid [ yield : 6 g ( 40 . 59 %)]. tcm ( 1 g , 5 . 128 mmol ), bromine ( 2 . 86 g , 17 . 248 mmol ), and carbon tetrachloride ( 10 ml ) were added to a light reactor , and then reacted by tungsten lamp for 8 hours . the reaction mixture was extracted by mc , and water therein was excluded over mgso 4 , and then the solvent was evaporated in vacuum . the residue was separated with a tube chromatography ( hx : ea = 8 : 1 ) to obtain white solid [ yield : 1 . 32 g ( 60 %)]. tcbm ( 1 g , 2 . 32 mmol ), triethylphosphite ( 1 . 616 g , 13 . 92 mmol ), and toluene ( excess amount ) were added to a reaction vessel , and refluxed for 8 hours . after the solvent was evaporated in vacuum and excluded , the residue was separated with a tube chromatography ( hx : mc = 3 : 1 ) to obtain yellow liquid [ yield : 0 . 84 g ( 60 %)]. a high pressure tube , dried by a dry oven , was filled with argon gas , and then m - toryl amine ( 1 g , 9 mmol ), 1 - bromo - 4 - methyl - benzene ( 6 . 2 g , 36 mmol ), pd ( dba ) 3 ( 0 . 39 g , 0 . 43 mmol ), dppf ( 0 . 48 , 0 . 86 mmol ), naotbu ( 4 . 1 g , 43 mmol ), and toluene ( 20 ml ) were added thereto , and stirred at 120 ° c . for 72 hours . the reaction mixture was extracted by mc , and the solvent was evaporated in vacuum . the residue was filtered with a tube chromatography ( hx : ea = 10 : 1 ), and re - crystallized with hexane to obtain white solid [ yield : 1 . 07 g ( 40 %)]. after mtpa ( 0 . 2 g , 0 . 69 mmol ) was dissolved into dmf ( 20 ml ), pocl 3 ( 0 . 15 g , 1 mmol ) was added thereto dropwise at 0 ° c . the reaction mixture was stirred over 30 minutes , and then the temperature thereof was elevated to 90 ° c . to react for 4 hours . the reaction mixture was added to 50 ml of iced water , and neutralized with 20 % naoh solution , and extracted by mc . after the solvent was evaporated in vacuum and eliminated , the residue was separated a tube chromatography ( hx : ea = 15 : 1 ). [ yield : 0 . 16 g ( 80 %)] lda ( 0 . 84 ml , 0 . 51 mmol ) was added to tcpm ( 0 . 1 g , 0 . 17 mmol ) in 10 ml of thf at − 72 ° c . condition , and after 30 minutes the bath was eliminated , and the reaction mixture was further stirred for 30 minutes . then , the temperature thereof was lowered , tpad ( 0 . 16 g , 0 . 51 mmol ) was added thereto dropwise , stirred , and after 30 minutes the bath was eliminated for 30 minutes and allowed to overnight . the residue was separated with a tube chromatography ( hx : ea = 1 : 4 ). [ m . p . : 280 ° c ., yield : 0 . 070 g ( 38 %)]. other compounds including formula ( 1 ) are synthesized by a similar method to synthetic examples 1 to 5 . the synthesized materials as above were further purified with a vacuum sublimation apparatus to use in the organic el device . for the present example , the organic el device using compound 10 as dopant and alq3 as host of a red color emitting layer was manufactured . first , a hole injection layer was formed with the thickness of 30 nm by depositing cupc ( copper ( ii ) phthalocyanine ) in vacuum on an ito - deposited glass washed by a microwave . then , after a hole transport layer was formed with the thickness of 50 nm by depositing npd ( n , n ′- dinaphthyl - n , n ′- phenyl -( 1 , 1 ′- biphenyl )- 4 , 4 ′- diamine ) in vacuum thereon , an emission layer is formed with the thickness of 30 nm on the hole transport layer by depositing alq3 ( host ), which was doped with compound 10 ( dopant ) by 1 . 0 %. an electron transport layer ( alq3 ; 40 nm ), an electron injection layer ( li 2 o ; 25 nm ), and a cathode ( mg / ag ; 100 nm ) were formed in order thereon by depositing in vacuum to complete the organic el device . the direct voltage of forward bias was applied to the organic el device manufactured by example 1 , and luminescent property thereof was evaluated . the luminescent color was red . as a result of spectroscopy , a spectrum having approximately 605 nm of luminescent peak was obtained . in addition , as a result of voltage - brightness test , 5 , 400 cd / m 2 of brightness at 8 v was obtained , at which point the efficiency was 1 . 88 lm / w ( see table 1 ). for the present example , the organic el device using compound 1 as host and dcm as dopant of a red color emitting layer was manufactured . first , a hole injection layer was formed with the thickness of 30 nm by depositing cupc in vacuum on an ito - deposited glass washed by a microwave . then , after a hole transport layer was formed with the thickness of 50 nm by depositing npd ( n , n ′- dinaphthyl - n , n ′- phenyl -( 1 , 1 ′- biphenyl )- 4 , 4 ′- diamine ) in vacuum thereon , an emission layer is formed with the thickness of 30 nm on the hole transport layer by depositing compound 1 ( host ), which was doped with dcm ( dopant ) by 1 . 0 %. an electron transport layer ( alq3 ; 40 nm ), an electron injection layer ( li 2 o ; 25 nm ), and a cathode ( mg / ag ; 100 nm ) were formed in order thereon by depositing in vacuum to complete the organic el device . the direct voltage of forward bias was applied to the organic el device manufactured by example 1 , and luminescent property thereof was evaluated . the luminescent color was red . as a result of spectroscopy , a spectrum having approximately 609 nm of luminescent peak was obtained . in addition , as a result of voltage - brightness test , 5 , 740 cd / m 2 of brightness at 8 . 7 v was obtained , at which point the efficiency was 1 . 92 m / w ( see table 1 ). for the present example , the organic el device using compound 22 as host and dcm as dopant of a red color emitting layer was manufactured . first , a hole injection layer was formed with the thickness of 30 nm by depositing cupc in vacuum on an ito - deposited glass washed by a microwave . then , after a hole transport layer was formed with the thickness of 50 nm by depositing npd ( n , n ′- dinaphthyl - n , n ′- phenyl -( 1 , 1 ′- biphenyl )- 4 , 4 ′- diamine ) in vacuum thereon , an emission layer is formed with the thickness of 30 nm on the hole transport layer by depositing compound 22 ( host ), which was doped with dcm ( dopant ) by 1 . 0 %. an electron transport layer ( alq3 ; 40 nm ), an electron injection layer ( li 2 o ; 25 nm ), and a cathode ( mg / ag ; 100 nm ) were formed in order thereon by depositing in vacuum to complete the organic el device . the direct voltage of forward bias was applied to the organic el device manufactured by example 1 , and luminescent property thereof was evaluated . the luminescent color was red . as a result of spectroscopy , a spectrum having approximately 621 nm of luminescent - peak was obtained . in addition , as a result of voltage - brightness test , 3 , 872 cd / m 2 of brightness at 8 . 5 v was obtained , at which point the efficiency was 1 . 48 m / w ( see table 1 ). for the present example , the organic el device using compound 1 as host and compound 22 as dopant of a red color emitting layer was manufactured . first , a hole injection layer was formed with the thickness of 30 nm by depositing cupc in vacuum on an ito - deposited glass washed by a microwave . then , after a hole transport layer was formed with the thickness of 50 nm by depositing npd ( n , n ′- dinaphthyl - n , n ′- phenyl -( 1 , 1 ′- biphenyl )- 4 , 4 ′- diamine ) in vacuum thereon , an emission layer is formed with the thickness of 30 nm on the hole transport layer by depositing compound 1 ( host ), which was doped with dcm ( dopant ) by 1 . 0 %. an electron transport layer ( alq3 ; 40 nm ), an electron injection layer ( li 2 o ; 25 nm ), and a cathode ( mg / ag ; 100 nm ) were formed in order thereon by depositing in vacuum to complete the organic el device . the direct voltage of forward bias was applied to the organic el device manufactured by example 1 , and luminescent property thereof was evaluated . the luminescent color was red . as a result of spectroscopy , a spectrum having approximately 617 nm of luminescent peak was obtained . in addition , as a result of voltage - brightness test , 4 , 200 cd / m 2 of brightness at 7 . 8 v was obtained , at which point the efficiency was 1 . 55 m / w ( see table 1 ). the results of the examples are summarized in table 1 below . as shown in the above table , the organic el devices applied with the red color emitting materials of the present invention shows high advanced luminescent efficiency and brightness than the organic el device applied with conventional red color emitting materials . in addition , the present materials contribute to enhance the safety and the life time of the device . | 8 |
in fig1 , a chromatic dispersion compensator 10 in accordance with a first embodiment of the invention is shown . compensator 10 includes a pbs 110 , a first ninety degree mirror 120 , a quarter - wave plate 130 , a gte 140 , a second ninety degree mirror 150 and a third ninety degree mirror 160 . pbs 110 is made from two right angle glass prisms joined at the hypotenuse . the hypotenuse face of one prism has a dielectric coating so as to make pbs 110 reactive to the polarization of light . that is , light is either transmitted or reflected at the hypotenuse of pbs 110 depending on its polarization . first ninety degree mirror 120 is a right angle glass prism whose hypotenuse is fully reflective . quarter - wave plate 130 is a birefringent crystal which converts linearly polarized light into circularly polarized light and vice versa . when quarter - wave plate 130 is double - passed , it acts as a half - wave plate and rotates the plane of polarization of light . gte 140 has a first mirror which is partially reflective , a second mirror which is fully reflective and a cavity in between . the spacing between the mirrors ( i . e . the thickness of the cavity ) is generally a function of the channel spacing of a dwdm system in which compensator 10 is operative . light arriving from pbs 110 or prismatic mirror 120 enters and exits gte 140 through the partially reflective mirror . gte 140 subjects different wavelength components of the light to variable delay in accordance with its resonant properties . that is , the partial reflectivity of the first mirror causes certain wavelength components to be restrained in the cavity between the first mirror and the second mirror longer than others . gte 140 thereby imposes a group delay on the wavelength components of the light which , when implemented over multiple instances , i . e . multiple bounces , can correct cd previously induced on the light &# 39 ; s pulses by a high speed , long haul , dwdm transmission system . second ninety degree mirror 150 is a right angle glass prism whose shortest two legs are fully reflective . third ninety degree mirror 160 is a right angle glass prism whose shortest two legs are fully reflective . in operation , an input optical beam 100 , which is unpolarized , is incident into pbs 110 . pbs 110 splits beam 100 into two polarized beams a 1 , b 1 . polarized beams a 1 , b 1 are directed ( with the help of mirror 120 in the case of beam b 1 ) toward gte 140 at normal incidence via quarter - wave plate 130 . gte 140 contributes a first unit of group delay on polarized beams a 1 , b 1 . upon reflecting from gte 140 and passing through quarter - wave plate 130 a second time on the return trip , the polarization plane of beams a 1 , b 1 is rotated . thus , when the beams a 1 , b 1 re - intersect at pbs 110 , they are recombined into an unpolarized beam and directed to mirror 150 . this completes the first cycle . prismatic mirror 150 redirects the unpolarized beam toward pbs 110 , beginning a second cycle in which gte 140 contributes a second unit of group delay on polarized beams a 2 , b 2 . upon reflecting from gte 140 and double passing through quarter - wave plate 130 , the polarization plane of beams a 2 , b 2 is once again rotated . thus , when the beams a 2 , b 2 re - intersect at pbs 110 , they are recombined into an unpolarized beam and directed to mirror 160 . this completes the second cycle . mirror 160 redirects the unpolarized beam toward pbs 110 , beginning a third cycle in which gte 140 contributes a third unit of group delay on polarized beams a 3 , b 3 . upon reflecting from gte 140 and double passing through quarter - wave plate 130 , the polarization plane of beams a 2 , b 2 is once again rotated . thus , when the beams a 3 , b 3 re - intersect at pbs 110 , they are recombined into an unpolarized beam and directed to mirror 150 . this completes the third cycle . mirror 150 redirects the unpolarized beam toward pbs 110 , beginning a fourth and final cycle in which gte 140 contributes a fourth unit of group delay on polarized beams a 4 , b 4 . upon reflecting from gte 140 and double passing through quarter - wave plate 130 , the polarization plane of beams a 4 , b 4 is once again rotated . thus , when the beams a 4 , b 4 re - intersect at pbs 110 , they are recombined into an unpolarized output optical beam 190 , which exits compensator 10 . all told , compensator 10 contributes four units of group delay over four cycles . that is , four interactions with gte 140 are made by the constituent components of input optical beam 100 , all at normal incidence . in general , any number of such interactions can be designed into this geometry . in fig2 , a chromatic dispersion compensator 20 in accordance with a second embodiment of the invention is shown . compensator 20 includes a pbs 210 , a first ninety degree mirror 220 , a quarter - wave plate 230 , a first gte 240 , a second gte 245 , a second ninety degree mirror 250 and a third ninety degree mirror 260 . elements 210 , 220 , 230 , 250 and 260 are similar in composition and operation to their counterparts 110 , 120 , 130 , 250 and 260 in fig1 . however , use of two gtes 240 , 245 having different resonant properties allows for polarization mode dispersion ( pmd ) in which the group delays induced on the beams may be made polarization - dependent . use of two gtes 240 , 245 also permits adjustments to ensure normal incidence of beams into gtes 240 , 245 , even if one or more of prismatic mirrors 220 , 250 , 260 are imperfect . finally , use of two gtes 240 , 245 enables cd correction of pulses transmitted on broader channels . in operation , an input optical beam 200 , which is unpolarized , is incident into pbs 210 . pbs 210 splits beam 200 into two polarized beams c 1 , d 1 . polarized beams c 1 , d 1 are directed ( with the help of mirror 220 in the case of d 1 ) toward gtes 240 , 245 , respectively , at normal incidence via quarter - wave plate 230 . gtes 240 , 245 contribute a first unit of group delay to polarized beams c 1 , d 1 , respectively . recall that the group delay induced by gte 240 may have different wavelength - dependence than the group delay induced by gte 245 owing to configurably different resonant properties of gtes 240 , 245 . upon reflecting from gtes 240 , 245 , respectively , and again passing through quarter - wave plate 230 , the polarization plane of beams c 1 , d 1 is rotated . thus , when beams c 1 , d 1 re - intersect at pbs 210 , they are recombined into an unpolarized beam and directed to mirror 250 . this completes the first cycle . mirror 250 redirects the unpolarized beam toward pbs 210 , beginning the second cycle in which gtes 240 , 245 contribute a second unit of group delay on polarized beams c 2 , d 2 , respectively . all told , compensator 20 contributes four units of group delay over four cycles . that is , four interactions with gtes 240 , 245 are made by the constituent components of input optical beam 200 before an unpolarized output optical beam 290 exits compensator 20 . moreover , the constituent portion of input optical beam 200 which had a first polarization is subjected to four interactions with gte 240 , while the constituent portion of inbound beam 200 which had a second polarization is subjected to four bounces off gte 245 , enabling pmd if desired by configuring gte 240 and gte 245 with different resonant properties . in general , any number of such interactions can be designed into this geometry . in fig3 , a chromatic dispersion compensator 30 in accordance with a third embodiment of the invention is shown . compensator 30 has a pbs 310 , two quarter - wave plates 320 , 350 , two gtes 330 , 360 and multiple elevator prisms 340 . the principle of operation is generally the same as in fig1 and 2 except in compensator 30 the beam migrates from ground level to higher levels with the assistance of elevator prisms 340 . elevator prisms 340 are right angle glass prisms whose shortest two legs are fully reflective and which are disposed to cause an input optical beam to project onto a higher plane upon reflection . in operation , an input optical beam 300 , which is unpolarized , is incident into pbs 310 ( identified as beam stage 1 in fig3 ). pbs 310 splits beam 300 into two polarized beams . the two polarized beams are directed toward gtes 330 , 360 , respectively , at normal incidence via quarter - wave plates 320 , 350 , respectively . gtes 330 , 360 contribute a first unit of group delay on the polarized beams , respectively . upon reflecting from gtes 330 , 360 and passing through quarter - wave plates 320 , 350 a second time on the return trip , the polarization plane of the beams is rotated . thus , when the beams re - intersect at pbs 310 , they are recombined into an unpolarized beam and directed to an elevator prism ( beam stage 2 in fig3 ). this elevator prism has been omitted from fig3 for clarity . this completes the first cycle . the elevator prism elevates and redirects , the unpolarized beam toward pbs 310 ( beam stage 3 in fig3 ), beginning a second cycle in which gtes 330 , 360 contribute a second unit of group delay on the respective polarized beams , upon reflecting from gtes 330 , 360 and completing another double - pass through quarter - wave plates 320 , 350 , the beams re - intersect at pbs 310 and are recombined into an unpolarized beam and directed to elevator prism 340 ( beam stage 4 in fig3 ). this completes the second cycle . all told , the beam completes beam stages 5 , 6 , 7 , . . . 11 in which compensator 30 contributes six units of group delay on the polarized beams , respectively , over six cycles . that is , six interactions with gtes 330 , 360 are made by the constituent components of input optical beam 300 , all at normal incidence , before output optical beam 370 , which is unpolarized , exits compensator 30 ( beam stage 12 in fig3 ). in fig4 , a crystal polarizer 40 is shown . crystal polarizer 40 includes a birefringent crystal 410 which is reactive to the polarization of light to create spatial separation , without altering direction . that is , light is either transmitted on the plane of entry or “ walks over ” and is transmitted on a different plane depending on its polarization . in the case of fig4 , ordinary beam “ o ” having a first polarization is transmitted as output optical beam 430 on the plane of entry while extraordinary beam “ e ” having a second polarization walks over and is transmitted as output optical beam 420 on a lower plane than the plane of entry . both output optical beams 420 , 430 continue in the direction of entry . in fig5 , a chromatic dispersion compensator 50 in accordance with a fourth embodiment of the invention is shown . compensator 50 has a crystal polarizer 520 , two quarter - wave plates 510 , 530 , three gtes 540 , 550 , 560 , a ninety degree mirror 570 and a pbs 580 . in operation , an input optical beam 500 , which is unpolarized , is incident into crystal polarizer 520 . crystal polarizer 520 splits beam 500 into two polarized beams e 1 ( ordinary beam “ o ”) and f 1 ( extraordinary beam “ e ”) in the general manner discussed above in connection with fig4 . that is , e 1 is transmitted on the plane of entry while f 1 walks down and is transmitted on a lower plane than the plane of entry . polarized beams e 1 , f 1 are directed toward gte 540 at normal incidence via quarter - wave plate 530 . gte 540 contributes a first unit of group delay on polarized beams e 1 , f 1 . upon reflecting from gte 540 and passing through quarter - wave plate 530 a second time on the return trip , the polarization plane of beams e 1 , f 1 is rotated . this completes the first cycle . when beams e 1 , f 1 reenter crystal polarizer 520 ( transitioning to beams e 2 , f 2 , respectively ), e 2 walks up for transmission on a higher plane than the plane of entry while f 2 is transmitted on the plane of entry . polarized beams e 2 , f 2 are directed toward gtes 560 , 550 , respectively , at normal incidence via quarter wave plate 510 . gtes 560 , 550 contribute a second unit of group delay to polarized beams e 2 , f 2 , respectively . upon reflecting from gtes 560 , 550 and passing through quarter - wave plate 510 a second time on the return trip , the polarization plane of beams e 2 , f 2 is rotated . this completes the second cycle . in similar fashion , compensator 50 contributes eight additional units of group delay on polarized beams e 3 . . . e 10 , f 3 . . . f 10 , respectively , over eight additional cycles . in all , a total of ten bounces off gtes 540 , 550 , 560 are made on the constituent portions of input optical beam 500 , all at normal incidence . then , polarized beams e 11 and f 11 are directed to pbs 580 ( with the help of mirror 570 in the case of beam e 11 ). at pbs 580 , beams e 11 , f 11 re - intersect and are recombined into output optical beam 590 which is unpolarized and which exits compensator 50 . in fig6 , a chromatic dispersion compensator 60 in accordance with a fifth embodiment of the invention is shown . compensator 60 has a pbs 610 , two quarter - wave plates 620 , 640 , two gtes 630 , 650 and two ninety degree mirrors 660 , 670 . in operation , an input optical beam 600 , which is unpolarized , is incident into pbs 610 . pbs 610 splits beam 600 into two polarized beams g 1 , h 1 . polarized beams g 1 , h 1 are directed toward gtes 630 , 650 , respectively , at normal incidence via quarter - wave plates 620 , 640 , respectively . gtes 630 , 650 contribute a first unit of group delay on polarized beams g 1 , h 1 . upon reflecting from gtes 630 , 650 and passing through quarter - wave plates 620 , 640 a second time on the return trip , the polarization plane of beams g 1 , h 1 is rotated . thus , when the beams g 1 , h 1 re - intersect at pbs 610 , they are recombined into an unpolarized beam and directed to mirror 660 . this completes the first cycle . mirror 660 redirects the unpolarized beam toward pbs 610 , beginning a second cycle in which gtes 630 , 650 contribute a second unit of group delay on polarized beams g 2 , h 2 , respectively . all told , compensator 60 contributes four units of group delay over four cycles . that is , four bounces off gtes 630 , 650 are made by the constituent components of input optical beam 600 , all at normal incidence , before output optical beam 680 , which is unpolarized , exits compensator 60 . it will be appreciated by those of ordinary skill in the art that the invention can be embodied in other specific forms without departing from the spirit or essential character hereof . the present invention is therefore considered in all respects to be illustrative and not restrictive . the scope of the invention is indicated by the appended claims , and all changes that come within the meaning and range of equivalents thereof are intended to be embraced therein . | 8 |
fig1 shows one embodiment of a system for handling messages in a software system . a report handler module 10 is contacted and activated by a subroutine 12 that has a message of a certain level ( ml ). as part of the contact between the subroutine 12 and the report handler 10 , the subroutine would pass its identification ( srid ) to the report handler . it is also possible that the subroutine could pass the message level ( ml ). the report handler 10 then makes contact with the operation system 14 to identify the process from which that subroutine is making contact . the report handler 10 also queries two tables to determine the message level for the process and the subroutine . the two tables could be implemented in several ways . for example , a list of possible messages and their priorities are shown below . the above table is for either processes or subroutines . the process level table ( pl ) lists the various processes and their message level . the subroutine level table ( srl ) lists the various subroutines and their respective message priority levels . once the report handler 10 has acquired the process identification ( pid ) and the subroutine identification ( srid ) it queries these two tables for the process message level ( pl ) and the subroutine message level ( srl ). the system developer could set these tables up manually during set up of the system . however , an executable file could be used to set up the tables with indices providing the correlation between the messages and the data . this would save the developer time and save execution time by not searching the table sequentially . the options for table set up are left up to the system designer and the above examples are merely considerations . returning to fig1 the procedure then moves to step 18 in which these levels are compared to the incoming message level received by the report handler from the subroutine . note that the message only contains the message information , the report handler must extract the context in which the message was sent . the report handler then compares the level of the incoming message ( ml ) to the process message level ( pl ) and the subroutine message level ( srl ). if the incoming message level is of a lower level than either the process message level or the subroutine message level , the message is reported at step 20 . if the message level is not a lower than either of the two message levels , no report is sent and the report handler process ends . note that the comparison of less than is dependent upon the manner in which the message priorities are laid out . if the ordering of severity were reversed , the message would be reported if it were of a higher level , rather than a lower level . the above example is merely for demonstrative purposes only and is in no way intended to limit the specifics of the how the comparison is performed . in this manner , then , only messages that are above a certain predetermined priority level are reported . this allows the system designer or troubleshooter to differentiate problem sources , between processes , subroutines or subroutines under different processes . this allows the user performing the analysis to more closely track and isolate problems in the system . one example of a situation in which it is difficult to isolate problems is in an instance of mutual exclusion , where two processes are prohibited by the system design from operating at the same time . if these two processes are using the same subroutine , it is impossible to tell which of these processes is actually running in current systems . the only message received is that the subroutine is running or has errors , with no idea of whether that subroutine had problems in one process and not in another , in current systems . an example of such a situation is shown in fig2 . in this example , there are two processes , process a and process b . both use a subroutine ( sr ). between the two processes , b has the higher operational priority , so it is programmed to take over the processor when it is running . however , there is a critical region of the subroutine in which all operational priorities are suspended until the critical region is completed . with these parameters established , the sequence of events is shown in fig2 . at step 22 , process a starts the common subroutine sr . process a enters the critical regions of the subroutine at step 24 . during performance of the critical region , a semaphore is set that prevents any other processes , including those with higher operation priority , from taking the processor . at step 26 , process b has tried to take the processor , but since a has set the semaphore , b is sent back to the semaphore queue . however , at step 28 , a exits the critical region of the subroutine , but is still in the subroutine itself . since b has higher operational priority , a is suspended from the subroutine and sent to the semaphore queue as soon as it releases the semaphore and b starts to operate . note that this happens regardless of b &# 39 ; s relationship to the critical region of the subroutine , with respect to process a . b can now only be preempted from the processor is a third process with a higher operational priority enters the subroutine and b is not in the critical region . once b completes the subroutine at step 30 , after it releases the semaphore . at step 32 , then , a finally completes the subroutine . the above example is merely a context in which a message control system that differentiates the priorities of messages between processes and subroutines would be helpful . for example , assume process b was set to a higher level than process a . in this example , the messaging system would report information from process b and only exceptions or errors from process a . the subroutine will probably be set to have a higher level as well . during the sequence of events described in fig2 then , the system designer or trouble shooter would be able to track the preemption of the processor by b , and would only be told if there were problems with the subroutine running under process a . in this method , the message level is not statically bound to the message . the same message can be used in different contexts without requiring creation of new messages . for example , if two drivers were being analyzed , one could have a timeout set as a warning or information , using the messaging scheme described in the table above . in the other driver , a timeout would be reported as an error . the same message , timeout , would be reported in one instance and not in the other . this saves message space and allows interoperability between message and severity . thus , although there has been described to this point a particular embodiment for a method and structure for a message control system , it is not intended that such specific references be considered as limitations upon the scope of this invention except in - so - far as set forth in the following claims . | 6 |
the vanadium complex can be prepared , for example , by the reaction of vcl 3 ( thf ) 3 in a thf ( tetrahydrofuran ) solution with an excess of a trialkylaluminum compound , adding the mixture to silica , and drying the mixture to a free flowing powder . a typical procedure for preparing the complex / excess trialkylaluminum / support component is set forth in example 1 , below . the complex is comprised of at least one cation and at least one anion . one of the cations can be represented by the formula v 2 x 3 ( ed ) m and one of the anions by the formula alcl 2 r 2 . the vanadium precursor can be a vanadium trihalide , a vanadium oxy trihalide , or a vanadium tetrahalide . the halide is either chlorine , bromine , or iodine , or mixtures thereof . the electron donor is a liquid , organic lewis base in which the vanadium compound and trialkylaluminum are soluble . it can be selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids , aliphatic ketones , aliphatic amines , alkyl and cycloalkyl ethers , and mixtures thereof , each electron donor having 2 to 20 carbon atoms . among these electron donors , the preferred are alkyl and cycloalkyl ethers having 2 to 20 carbon atoms ; dialkyl , diaryl , and alkylaryl ketones having 3 to 20 carbon atoms ; and alkyl , alkoxy , and alkylalkoxy esters of alkyl and aryl carboxylic acids having 2 to 20 carbon atoms . the most preferred electron donor is tetrahydrofuran . other examples of suitable electron donors are methyl formate , ethyl acetate , butyl acetate , ethyl ether , dioxane , di - n - propyl ether , dibutyl ether , ethyl formate , methyl acetate , ethyl anisate , ethylene carbonate , tetrahydropyran , and ethyl propionate . while an excess of electron donor is used initially to provide the reaction product of the vanadium compound , electron donor , and trialkylaluminum , the reaction product finally contains about 1 to about 20 moles of electron donor per mole of vanadium compound and preferably about 1 to about 10 moles of electron donor per mole of vanadium compound . about 3 moles of electron donor per mole of vanadium compound has been found to be most preferable . as noted , an excess of trialkylaluminum compound is also used . while the atomic ratio of aluminum to vanadium in the complex is about 0 . 5 : 1 , the molar ratio of trialkylaluminum compound adsorbed on the support to vanadium is in the range of about 2 . 5 : 1 to about 10 : 1 and is preferably in the range of about 3 : 1 to about 7 : 1 . silica is the preferred support . other suitable inorganic oxides are aluminum phosphate , alumina , silica / alumina mixtures , silica modified with an organoaluminum compound such as triethylaluminum , silica modified with diethylzinc , and a mixture of silica and calcium carbonate . a typical support is a solid , particulate porous material essentially inert to the polymerization . it is used as a dry powder having an average particle size of about 10 to about 250 microns and preferably about 30 to about 100 microns ; a surface area of at least about 3 square meters per gram and preferably about 50 square meters per gram ; and a pore size of at least about 80 angstroms and preferably at least about 100 angstroms . generally , the amount of support used is that which will provide about 0 . 05 to about 0 . 5 millimole of vanadium compound per gram of support and preferably about 0 . 2 to about 0 . 3 millimole of vanadium compound per gram of support . r = hydrogen or an unsubstituted or halogen substituted alkyl having 1 to 6 carbon atoms ; preferred promoters include fluoro -, chloro -, and bromo substituted methane or ethane having at least 2 halogen atoms attached to a carbon atom , e . g ., methylene dichloride , 1 , 1 , 1 - trichloroethane , chloroform , cbr 4 , cfcl 3 , hexachloroethane , ch 3 ccl 3 , and cf 2 clccl 3 . the first three mentioned promoters are especially preferred . about 0 . 1 to about 10 moles , and preferably about 0 . 2 to about 2 moles , of promoter can be used per mole of cocatalyst . the trialkylaluminum compound can be represented by the formula r 3 al wherein each r is an alkyl ; each r can be alike or different ; and each r has up to 14 carbon atoms , and preferably 2 to 8 carbon atoms . further , each alkyl can be straight or branched chain . examples of suitable alkyls are : methyl , ethyl , propyl , isopropyl , butyl , isobutyl , tert butyl , pentyl , neopentyl , n - hexyl , 2 - methylpentyl , heptyl , octyl , isooctyl , 2 - ethylhexyl , 5 , 5 - dimethylhexyl , nonyl , decyl , isodedcyl , undecyl , and dodecyl . the cocatalyst can be the same as the foregoing r 3 al except that r can also be aryl . examples of suitable hydrocarbyl aluminum compounds are as follows : triisobutylaluminum , tri n - hexylaluminum , di - isobutylhexylaluminum , isobutyl dihexylaluminum , trimethylaluminum , triethylaluminum , tripropylaluminum , triisopropylaluminum , tri - n - butylaluminum , trioctylaluminum , tridecylaluminum , tridodecylaluminum , tribenzylaluminum , triphenylaluminum , trinaphthylaluminum , and tritolylaluminum . the preferred trialkylaluminum compounds and hydrocarbyl aluminum compounds are triethylaluminum , triisobutylaluminum , and tri n - hexylaluminum . the cocatalyst and promoter can be added to the vanadium complex either before or during the polymerization reaction . they can be added together or separately , simultaneously or sequentially . the cocatalyst and promoter are preferably added separately as solutions in an inert solvent , such as isopentane , to the polymerization reaction at the same time as the flow of the comonomers is initiated . the cocatalyst is necessary to obtain any significant polymerization . the promoter , on the other hand , can be considered a preferred option . about 5 to about 500 moles , and preferably about 10 to about 40 moles , of cocatalyst can be used per mole of vanadium catalyst precursor , i . e ., the reaction product of the vanadium compound , the electron donor , and the trialkylaluminum . the polymerization can be conducted in the gas phase or liquid phase using conventional techniques such as fluidized bed , slurry , or solution processes . a continuous , fluidized bed process is preferred . using this fluidized bed process , the vanadium complex / excess trialkylaluminum / support component , the cocatalyst , the promoter , and comonomers are continuously fed into the reactor and product is continuously removed . the fluidized bed polymerization is conducted at a temperature below the sintering temperature of the product . the operatinq temperature is generally in the range of abut 10 ° c . to about 115 ° c . the fluidized bed reactor is typically operated at pressures of up to about 1 , 000 , and preferably about 50 to about 350 , psig . a chain transfer agent , such as hydrogen , can be used to terminate the polymer chain . usually the ratio of hydrogen to ethylene will vary between about 0 . 001 to about 0 . 1 mole of hydrogen per mole of ethylene . subject catalyst can be used in the polymerization of at least one alpha olefin havinq 2 to 20 carbon atoms . it is particularly useful in the production of copolymers in which a major proportion , i . e ., more than 50 percent by weight , is based on ethylene , propylene , and / or butene comonomers . it is understood that the term &# 34 ; copolymer &# 34 ; includes polymers having two or more different comonomers incorporated into the same polymer chain . the balance of the copolymer is attributed to various alpha olefins or diolefins having 2 to 20 carbon atoms , which are present in minor proportion . examples of the alpha olefins and diolefins are 4 - methyl - 1 - pentene , 1 - hexene , 1 - octene , 1 , 4 - hexadiene , and dicyclopentadiene . of particular interest are ethylene / propylene rubbers and ethylene / propylene / ethylidene norbornene rubbers . 3 . 0 millimoles of vcl 3 , dissolved in freshly distilled tetrahydrofuran ( thf ) is placed in a 200 milliliter flask and blanketed with nitrogen . the solution is stirred at room temperature and 18 millimoles of trimethylaluminum in hexane are added via syringe . the resulting deep violet solution is stirred at 45 ° c . for 30 minutes . during this time , the solution turns green , indicative of the vanadium + 2 species . 10 . 0 qrams of silica ( dried at 600 ° c .) is added and the slurry is dried down at 45 ° to 50 ° c . under vacuum for 2 hours . analysis shows 0 . 26 millimole vanadium per gram of catalyst and a thf / v mole ratio of 5 . 5 : 1 . a one liter autoclave reactor is heated to 110 ° c . and purged with nitrogen for 30 minutes . after cooling to 45 ° c ., 500 milliliters of dry , deaerated hexane are added . 0 . 8 millimole of triethylaluminum , 0 . 8 millimole of chcl 3 promoter , and the catalyst precursor ( 0 . 02 millimole of vanadium ) prepared in example 1 are added next . then , 10 milliliters of ethylidene norbornene , 1 . 5 psi of hydrogen , and 7 grams of propylene are charged to the reactor . the reactor is pressurized with 130 psi of ethylene and heated to 65 ° c . with stirring . ethylene is fed continuously and the polymerization is continued for one hour . the reactor is vented and the contents poured into isopropanol , stirred in a high speed blender , and filtered . the resulting resin is in a granular form and is dried overnight under vacuum in a 65 ° c . oven . comonomer content is determined by nuclear magnetic resonance analysis . the variables and results for examples 2 through 6 are given in the table . example 2 is repeated except that triethylaluminum is substituted for trimethylaluminum in example 1 . example 2 is repeated except that 4 millimoles of trimethylaluminum are used in example 1 . example 2 is repeated except that trisobutylaluminum is substituted for trimethylaluminum in example 1 . example 2 is repeated except that tri - nhexylaluminum is substituted for trimethylaluminum in example 1 . example 2 is repeated except that the catalyst is prepared in the same manner as the catalyst used in example 1 of u . s . pat . no . 4 , 508 , 842 , issued on apr . 2 , 1985 , incorporated by reference herein . table______________________________________ component % % example a1 / v ( iv ) activity propylene enb______________________________________2 6 tma 2536 4 . 1 1 . 13 6 teal 2513 5 . 1 2 . 04 4 tma 1300 -- -- 5 6 tiba 2200 -- -- 6 6 tnhal 2337 -- -- 7 4 . 5 deac 870 4 . 3 0 . 5______________________________________ notes with respect to the table : 1 . a1 / v is the molar ratio of excess trialkylaluminum compound adsorbed o the support to vanadium . 2 . the activity of the catalyst is measured in grams of ethylene / propylene / ethylidene norbornene terpolymer per millimole of vanadium per hour . 3 . % propylene is the percent by weight of the terpolymer attributed to the propylene monomer ( analyzed by nmr ). 4 . % enb is the percent by weight of the terpolymer attributed to the ethylidene norbornene monomer ( analyzed by nmr ). 5 . nmr = nuclear magnetic resonance . 6 . tma = trimethylaluminum . 7 . teal = triethylaluminum . 8 . tiba = triisobutylaluminum . 9 . tnhal = trin - hexylaluminum . 10 . deac = diethylaluminum chloride . the product of reduction of vcl 3 with trimethylaluminum is isolated as a green solid , dissolved in thf , and deposited on silica . no excess aluminum alkyl is present . extraction with thf shows only 9 mole percent of the vandium is adsorbed on the surface of the silica . a polymerization test of the catalyst according to example 2 gives an activity of 868 . a catalyst is prepared as in example 8 except that the silica is pretreated with triethylaluminum to react surface hydroxy moieties . extraction shows 39 mole percent of the vanadium to be adsorbed on the surface of the silica . a polymerization test of this catalyst according to example 2 gives an activity of 1045 . a catalyst prepared as in example 1 is extracted with thf . 49 mole percent of the vanadium is not extracted . a polymerization test of the catalyst according to example 2 gives an activity of 2263 . a fluidized bed reactor is operated as described in u . s . pat . no . 4 , 508 , 842 employing the catalysts used in examples 2 and 7 . the objective is the preparation of ethylene / propylene / diene terpolymer ( epdm ). ______________________________________example 11 12catalyst example 1 example 7______________________________________temperature (° c .) 40 40propylene / ethylene 0 . 41 0 . 37mole ratioethylene ( psi ) 126 123cocatalyst tiba tibapromoter chcl . sub . 3 chcl . sub . 3ethylidene norbornene ( enb ) 7 . 4 6 . 3 ( bed wt . %) propylene ( wt . %) 26 . 8 29 . 5enb ( wt . %) 3 . 5 4 . 9ash ( wt . %) 0 . 177 0 . 334g / g cat . 707 286______________________________________ notes : 1 . psi = pounds per square inch . 2 . tiba = triisobutylaluminum . 3 . ethylidene norbornene ( bed wt . %) = the percent by weight of ethyliden norbornene based on the weight of the fluidized bed . 4 . propylene ( wt . %) = the percent by weight of propylene based on the weight of the epdm . 5 . enb ( wt . %) = the percent by weight of ethylidene norbornene based on the weight of the epdm . 6 . ash ( wt . %) = the percent by weight of ash based on the weight of the epdm . 7 . vanadium ( ppm ) = parts per million by weight of vanadium based on the weight of epdm . 8 . g / g cat . = grams of epdm produced per gram of supported vanadium catalyst . examples 11 and 12 are repeated except that the objective is the preparation of linear low density polyethylene ( lldpe ). the reaction conditions , which differ from examples 11 and 12 , and the results are as follows : ______________________________________example 13 14______________________________________temperature (° c .) 90 901 - hexene / ethylene 0 . 043 0 . 049mole ratiohydrogen / ethylene 0 . 0191 0 . 0155mole ratioethylene ( psi ) 138 141cocatalyst teal tealmelt index 0 . 39 0 . 30melt flow ratio 99 92density ( g / cc ) 0 . 9293 0 . 9250vanadium ( ppm ) 6 . 79 7 . 43ash ( wt %) 0 . 049 0 . 053productivity 1915 1750 ( lb / lb / catalyst ) ______________________________________ notes ( also see notes for examples 11 and 12 ): 1 . teal = triethylaluminum . 2 . melt index , melt flow ratio , and density = see u . s . pat . no . 4 , 508 , 842 for definitions . 3 . productivity ( lb / lb catalyst ) = pounds of lldpe produced per pound of catalyst added to the reactor . | 2 |
the description and drawings merely illustrate the principles of the invention . it will thus be appreciated that those skilled in the art will be able to devise various arrangements that , although not explicitly described or shown herein , embody the principles of the invention and are included within its spirit and scope . furthermore , all examples recited herein are principally intended expressly to be only for pedagogical purposes to aid the reader in understanding the principles of the invention and the concepts contributed by the inventors to furthering the art , and are to be construed as being without limitation to such specifically recited examples and conditions . moreover , all statements herein reciting principles , aspects , and embodiments of the invention , as well as specific examples thereof , are intended to encompass equivalents thereof . fig1 shows a machine type communication scenario according to a preferred embodiment , comprising a first device , e . g . a base station 10 in a 4g wireless system or a 5g wireless system , and associated user equipment devices 12 , 14 , e . g . sensor devices or the like . the term user equipment device 12 , 14 is to be understood to cover sensor devices in a sensor network , other known user equipment devices like mobile phones , which might transmit and receive data with or without the interaction of a human being and other fixed installed or mobile communication devices able to transmit and receive data . the user equipment devices 12 , 14 and the base station 10 are located within the communication range of these devices and communication is performed via a transmission channel 16 , which is e . g . a wireless transmission channel . a multi - carrier system is used for communication between the base station 10 and the user equipment devices 12 , 14 , e . g . an ofdm , sc - fdma or fbmc system with resource allocation in transmission time intervals and frequency resources . in scenarios where devices are distributed over certain cell areas ( e . g . macro or micro cells ), larger dynamic ranges of receive signal powers are occurring due to the near - far - effect . some user equipment devices within the cell coverage of a base station 10 are considered as disadvantageous user equipment devices 14 . because of obstacles 18 blocking the direct wireless connection between a disadvantageous user equipment device 14 and a base station 10 or because the disadvantageous user equipment device 14 is relatively far away from the base station at the edge of a wireless cell , these user equipment devices 14 have difficulties in transmitting data without the need of many retransmission . fig2 discloses a simulation of an exemplary scenario , showing that a certain percentage of disadvantageous user equipment devices 14 , e . g . 20 %, have a large number of retransmissions . this results in a large delay for successful reception , which is disclosed in fig3 . those disadvantageous user equipment devices 14 have difficulties to get a fair access into the system . the reason is e . g . the residual interference from non - ideal interference cancellation of a real multi packet reception with real channel estimation . if the receiver uses successive interference cancellation ( sic ), errors in the residual signal occur when cancelling out the devices with strong receive signals from the superimposed receive signal . this is due to inaccuracies in channel knowledge . in sic , weakest devices are detected last . the accumulated errors from the previously cancelled devices increase the probability that the packets are not correctly decoded . fig4 discloses a frame structure , a superframe 40 for communication between a base station 10 and a user equipment device 12 , 14 via a wireless communication link 16 . the frame structure 40 includes an uplink control frame 42 , regular frames 44 and a reserved frame 46 dedicated to disadvantageous user equipment devices 14 , which have according to their geographical location in the cell or for any other reasons difficulties to communicate with the base station 10 . these difficulties may appear in a high bit error rate for these user equipment devices 14 and / or a large number of retransmissions before a transmission will have been successfully finished . only the disadvantageous user equipment devices 14 are allowed to access or at least are preferred in accessing the reserved frame 46 . in one embodiment , also multiple reserved frames 46 may be provided in a superframe 40 . the superframe 40 disclosed in fig4 is used e . g . in a slotted aloha cdma system . the time slots are defined for random access based transmission of data and are used as uplink control frame 42 , regular frames 44 or reserved frames 46 . in one embodiment , the reserved frame 46 has a longer duration than the other frames , e . g . twice as long as a regular frame as depicted in fig4 . fig5 illustrates a method for transmitting data in a system using reserved frames 46 for disadvantageous user equipment devices 14 . in step 50 , a user equipment device 12 , 14 transmits its data and id to the base station 10 within a timeslot of a regular frame 44 when a communication should be performed . in step 51 , the user equipment device checks if an acknowledgement ( ack ) is received from the base station 10 . if an ack is received , the transmission is completed and the method terminates in step 52 . if no ack is received , the user equipment device 12 , 14 checks how many attempts have been made so far to transmit the data , and if the number of attempts is lower than a predefined number , the user equipment device 12 , 14 increases the number of unsuccessful attempts by one and goes back to step 50 in order to transmit the data and id again . the retransmission may take place a predefined time or a randomly defined time after the previous attempt . if the number of transmission attempts exceeds the predefined number , the user equipment device 14 decides to be a disadvantageous user equipment device 14 . then , in step 53 a request for transmission in a reserved frame 46 is sent to the base station via the uplink control frame 42 . in one embodiment , the uplink control channel on which the uplink control frames 42 are transmitted has extended duration in order to allow efficient communication from the disadvantageous user equipment devices 14 . the base station 10 then decides about the request and the user equipment device 14 receives in step 54 an acknowledgement from the base station 10 for sending data in the reserved frames 46 . in one embodiment , the acknowledgment is transmitted with optional extra configurations for disadvantageous user equipment devices 14 . a downlink control channel may be used here . in step 55 , the user disadvantageous user equipment device 14 transmits its data in the reserved frame 46 . in one embodiment , the step 53 of requesting transmission in a reserved frame 46 and the step 54 for receiving an acknowledgment for transmission in a reserved frame 46 are omitted . instead , the disadvantageous user equipment device 14 whose transmission attempts exceeds a predefined number accesses the reserved frame 46 without a special uplink request to the base station . instead , it received repeatedly information regarding the reserved frame 46 communication or has this information stored . the control information may contain but is not limited to the predefined number of failed attempts until the machine can access the reserved frames 46 , and further configurations for accessing the reserved frames 46 , such as contention probability and maximum retransmissions . the information is evaluated in step 56 , and then the disadvantageous user equipment device 14 just sends the data in the reserved frame 46 in step 55 . thus , control information transmitted over the network is reduced . in one embodiment , multi - carrier cdma is used and a set of subcarriers ( physical resource blocks ) is reserved for the disadvantageous user equipment devices 14 . the rest of the band may be used by the other user equipment devices 12 , which are not necessarily machine to machine communication devices . different codes and subcarriers may be used for the reserved frames 46 . while multi - carrier cdma may be understood in the art as ofdm with additional spreading on top of the ofdm resource elements , within the scope of this disclosure with the expression multi - carrier cdma is to be interpreted more general , e . g . as a combination of cdma / spreading with any kind of multi - carrier modulation signal format , like fbmc ( filter bank based multi - carrier ) or iota - ofdm . the functions of the various elements shown in the figures , including any functional blocks , may be provided through the use of dedicated hardware as well as hardware capable of executing software in association with appropriate software . when provided by a processor , the functions may be provided by a single dedicated processor , by a single shared processor , or by a plurality of individual processors , some of which may be shared . moreover , the functions may be provided , without limitation , by digital signal processor ( dsp ) hardware , network processor , application specific integrated circuit ( asic ), field programmable gate array ( fpga ), read only memory ( rom ) for storing software , random access memory ( ram ), and non volatile storage . other hardware , conventional and / or custom , may also be included . | 8 |
referring to fig1 and 2 , an apparatus 10 is shown for controlling movement of a valve 12 in a camless engine between a fully closed position ( shown in fig1 ), and a fully open position ( shown in fig2 ). the apparatus 10 includes an electromagnetic valve actuator ( eva ) 14 with upper and lower coils 16 , 18 which electromagnetically drive an armature 20 against the force of upper and lower springs 22 , 24 for controlling movement of the valve 12 . switch - type position sensors 28 , 30 , 32 are provided and installed so that they switch when the armature 20 crosses the sensor location . it is anticipated that switch - type position sensors can be easily manufactured based on optical technology ( e . g ., leds and photo elements ) and when combined with appropriate asynchronous circuitry they would yield a signal with the rising edge when the armature crosses the sensor location . it is furthermore anticipated that these sensors would result in cost reduction as compared to continuous position sensors , and would be highly reliable . a controller 34 is operatively connected to the position sensors 28 , 30 , 32 , and to the upper and lower coils 16 , 18 in order to control actuation and landing of the valve 12 . the first position sensor 28 is located around the middle position between the coils 16 , 18 , the second sensor 30 is located close to the lower coil 18 , and the third sensor 32 is located close to the upper coil 16 . in the following description , only the valve opening control is described , which uses the first and second sensors 28 , 30 , while the situation for the valve closing is entirely symmetric with the third sensor used in place of the second . the key disadvantage of the switch - type position sensor as compared to the continuous position sensor is the fact that the velocity information cannot be obtained by simply differentiating the position signal . rather , the present invention proposes to calculate the velocity based upon the electromagnetic subsystem of the actuator . specifically , the velocity is estimated based upon the current and rate of change of current in the electromagnetic actuator 14 . because the disturbance due to gas force on the valve does not directly affect the electromagnetic subsystem of the actuator , this velocity estimation can be done reliably . the velocity estimation ( assuming no magnetic field saturation ) has the form : velocity = ( z + k b k a ) - ( l · i - ɛ ) + r · i - v i k a ( z + k b ) 2 where , z and vel are the armature position ( distance from an energized coil ) and velocity , respectively , r is the electrical resistance , v and i are voltage and current , respectively , and e is the dynamic state of the estimator and is derived from the dε / dt formula below . l is an estimator gain and k a and k b are constants that are determined by magnetic field properties and are calibrated from the relation between the force on the armature and the gap distance between the armature and the lower coil : f mag = k a i 2 ( z + k b ) 2 the rate of change of current in the eva is estimated as ( l · i − ε ) in the velocity formula above , where ɛ t = - l · ( l · i - ɛ ) and l & gt ; 0 is an estimator gain and the actual measurement of the current i is an input to the formula . accordingly , the calculated velocity is based on current and estimated rate of change of current in the eva . the estimate is implemented in discretized form on a microprocessor system dedicated to actuator control . the duty cycle of the eva is the excitation signal on - time divided by total time . the duty excitation signal applied to the lower coil 18 ( essentially a fraction of maximum voltage applied to the coil , i . e ., v = v max · d ) during a single cycle is shaped by changing the values of several parameters . one such scheme uses the following parameters : t 2 is the time instant when the duty cycle is applied to effect armature catching ; t 3 is the time instant when catching action is changed to holding action ; and an algorithm is proposed for adjusting these parameters that uses the information from the first and second sensors 28 , 30 , and accomplishes the tasks of both in - cycle control and cycle - to - cycle adaptation . when the armature passes the location of a switch - type position sensor , a rising signal edge from a sensor is detected , and the position at this time instant is known . using the above characterization of the electromagnetic subsystem , the armature velocity is backtracked and used for control . consequently , the velocity of the first sensor crossing can serve as an early warning about the magnitude of the disturbance affecting the valve motion , and this information can be used for in - cycle control . the cycle - to - cycle adaptation aims at regulating the velocity at the second sensor crossing to the desired value . experiments show that disturbances on the exhaust valves are largest at the beginning of the valve motion and , hence , regulating the velocity to the desired value near the end of the valve travel can be used as an enforcement mechanism for soft landing . finally , in situations when a valve is about to malfunction , as may be indicated by a serious velocity deficit at the second sensor crossing or a second crossing of the second sensor occurs , it may be necessary to apply the full duty cycle to ensure landing . in other words , voltage is continuously applied to the lower coil 18 . the below - described algorithm assumes ( for simplicity ) that the initial catching part of the duty cycle becomes active only after the first sensor crossing . at higher engine speeds , an earlier activation of the duty cycle may be needed to provide faster responses . in this situation , it is possible to use the crossing information from the third sensor 32 instead of the crossing information from the first sensor 28 . it is also possible to modify the algorithm so that it only applies to the part of the active duty cycle profile after the first sensor 28 crossing . finally , it should be clear that the crossing information from all three sensors 28 , 30 , 32 can be used to shape the duty cycle within a single valve opening or valve closing event . the main features of the algorithm described in fig5 are as follows . if the estimated velocity at the first sensor crossing , vel 1 , is below the desired value , vel 1d , the value of d c ( i . e ., the duty cycle ) is increased from its nominal value d c , 0 by a value , f p ( vel 1 , d − vel 1 ), whose magnitude is a faster than linear increasing function of the magnitude of the difference . this calculation is shown at block 40 in fig5 where f p is a calibratable gain . the increase in d c assures armature landing since lower than desired velocity indicates larger than expected disturbances counteracting the motion of the valve 12 . disproportionately more aggressive action is provided for a larger velocity deficit . if the estimated velocity at the first sensor crossing is above the desired value , the value of d c may be decreased from its nominal value by a conservative amount that may depend on the magnitude of the difference . still referring to block 40 , the adaptive term is added to the resulting d c value to provide cycle - to - cycle adaptation . this adaptive term is formed by multiplying a gain k times the integrator output θ that sums up the past differences between the estimated vel 2 and desired velocity , vel 2 , d at the second sensor crossing . referring to block 42 of fig5 if the resulting d c value exceeds one ( i . e ., not physically realizable ), d c is set to 1 and t 2 is advanced from its nominal value t 2 , 0 by a value whose magnitude is a monotonic function of the amount by which the originally calculated value of d c exceeds 1 . t 2 is the time instant when the duty cycle is applied to effect armature catching . in other words , when greater than 100 % duty cycle is demanded , catching current t 2 is initiated sooner to compensate for such demand . referring to blocks 44 and 46 of fig5 if the value of vel 2 is significantly lower than the desired value vel 2 , d , or if a second crossing of the second sensor has been detected ( indicating the valve 12 starting to move in the opposite direction ), an emergency pulse is formed to force the valve landing , wherein the duty cycle d c is set to the maximum value of 1 until a prespecified time t f elapses . after the time t f elapses , the duty cycle d c is set to the holding duty cycle d h . the results of simulating the actuator model in the closed loop with the proposed algorithm of fig5 are shown in table 1 below , and in fig3 a - 3 c and 4 a - 4 c . the unmeasured disturbance acting on the valve is assumed to be of initially persistent ultimately exponentially decaying type , to reflect the fact that the disturbance has initially larger size . in the case when the disturbance acts against the valve motion (“− w ”) applying the nominal duty cycle profile ( i . e . with algorithm off ) yields no landing at all ( in fact , the armature does not make it to the second sensor location ). when the disturbance acts in the direction of the valve motion (“+ w ”), large landing velocity results with the algorithm off . with the algorithm on , landing is ensured in “− w ” case and , in addition , the variability in the landing speed in both cases is greatly reduced . some residual variability is still present despite the fact that the velocity at the second sensor crossing is regulated to the desired value . this is because some - disturbance does remain and does affect the armature motion even after the second sensor crossing . table 1 illustrates steady state ( i . e ., after ten cycles ) landing velocity w ( in meters per second ) with and without compensation for the nominal case ( w = 0 ) and for the cases when the unmeasured disturbance of initially persistent , ultimately exponentially decaying type is acting on the valve . in the “− w ” case , the disturbance opposes the valve opening , while in the “+ w ” case , the disturbance acts in the direction of valve opening . referring to fig3 a - 3 c , the catching voltage v c = v max · d c ( v max equals 200 ), landing velocity and velocity of the second sensor crossing from one cycle to the next are shown . the desired value of vel 2 , d is shown by the dashed line in fig3 c . the nominal value of v c is 100 . here , an unknown disturbance force ( of initially persistent , ultimately exponentially decaying type ) acts on the valve , opposing the armature motion toward the lower coil . the emergency pulse compensation is used on the first and the third cycle to ensure that the armature actually lands . the armature crosses the second sensor location three times on the first and on the third cycle . aggressive compensation for the difference vel 1 , d − vel 1 , with f p ( vel 1 , d − vel 1 ) term , is clearly visible on fig3 a in the first cycle , as well as slower cycle - to cycle adaptation from the difference vel 2 , d − vel 2 . referring to fig4 a - 4 c , the catching voltage v c = v max d c ( v max = 200 ), landing velocity and velocity at the second sensor crossing from one cycle to the next in the “+ w ” case are shown . the desired value of vel 2 , d is shown by the dashed line on fig4 c . the nominal value of v c is 100 . here , an unknown disturbance force ( of initially persistent , ultimately exponentially decaying type ) acts on the valve , accelerating the armature toward the lower coil . here ( for illustration purposes ), the action f p ( vel 1 , d − vel 1 ) on the velocity difference at the first crossing was set to zero , to illustrate the effect of cycle - to - cycle adaptation . while the best mode for carrying out the invention has been described in detail , those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention within the scope of the appended claims . | 5 |
the orders of magnitude addressed with the touch fastener should suffice in the geometrical implementation and are designed such that interaction with a corresponding part , whether in the form of another touch fastener , or in the form of the surface of a body in the vicinity on which the touch fastener according to the invention is to be fixed , can preferably take place by van - der - waals forces . these van - der - waals forces constitute a subgroup of adhesion and are formed because the negatively charged electrons swirling around the positive nucleus in an atom are briefly concentrated on one side . for this reason , the atom on this side is temporarily negatively charged , while on the other side conversely it is positively charged . this charging also influences adjacent atoms . in this case , the atoms along the top of the support surface of the head cause the support surface of the head , depending on which charge it receives , to be attracted either by the positive atoms or the negative atoms of the respective opposite surface of the body in the vicinity . the larger the resulting contact surfaces are in total , the stronger the forces which arise . the resulting large - dimensioned head support surfaces arising as a result of the conically tapering stem ends are then favorable for achieving strong van - der - waals forces . although the van - der - waals forces are among the weakest forces in nature , the effect is sufficient to achieve relatively high fastening forces , especially considering that several thousand bonding elements can be on the extremely small space of the backing . if the surface of the respective head should be chemically modified in a corresponding manner , a true chemical bond as the adhesion connection is conceivable . the touch fastener shown in fig1 , for the purposes of this invention , can be obtained , for example , according to a micro - replication process described in de 196 46 318 a1 . the prior art process is used to produce a touch fastener with a plurality of interlocking means or elements made in one piece with the backing 10 in the form of stems 14 having heads 12 . preferably , a thermoplastic in the plastic or liquid state is delivered to the gap between a compression roll and a shaping roll . the shaping roll is provided with a screen with cavities open to the interior and the exterior . the two rolls for the production process are driven in opposite directions so that the backing material is formed in the gap between the rolls with the formation of the backing 10 . since the touch fastener according to the invention has stems 14 made conical , the screen cross section is matched to the exterior contour of the respective support stem 14 . in particular , the screen cross section uniformly tapers conically in the direction of the interior of the roll . another possibility for obtaining the fastener system shown in the figures is described in de 100 65 819 c1 . in this known method for producing touch fasteners , a backing material in at least one partial region of its surface is provided with touch fastener elements or bonding elements projecting from its plane . a plastic material forming the fastener elements is applied to the backing element providing the backing 10 . the elements are made without a shaping tool at least in one partial region in which the plastic material is deposited by at least one application device in successively delivered droplets . although the application device yields plastic material with a droplet volume of only a few picoliters via its nozzle , a high - speed process can be implemented such that a touch fastener as shown in fig1 is obtained in an extremely short period of time . this method also makes it possible , in particular , to produce individual bonding elements as shown in fig3 where each has a head 12 and a conical stem 14 with an articulation site on part 16 . in turn , these bonding elements can then be applied in a plurality of backings 10 of any form , for example , by cementing or melting on . this backing 10 then need not have a configuration extending flat , but may definitely follow curved paths with convex or concave radii ( not shown ). another option for producing the touch fastener according to the invention may involve a thin plastic film being applied , for example , doctored on , onto the free tapering stem end 14 and then to clip it , for example , by a laser , to obtain the desired geometry of the respective head 12 . films can also be applied in this way for the backing 10 . the backing 10 as well as the heads 12 and the tapering stems 14 with integrated articulation coupling are formed preferably of a plastic material chosen in particular from the group of acrylates such as polymethacrylates , polyethylenes , polypropylenes , polyoxymethylenes , polyvinylidene fluoride , polymethylpentene , poly ( ethylene )- chlorotrifluoroethylene , polyvinyl chloride , polyethylene oxide , polyethylene terephthalate , polybutylene terephthalate , nylon 6 , nylon 6 . 6 , and polybutene . essentially , plastics with long chains of molecules and good orientation behavior , as well as plastic materials with thixotropic behavior can be used especially effectively . thixotropic behavior for the purposes of the invention in this connection is to denote the reduction of structural thickness during the shear loading phase and its more or less a prompt but complete restoration during the following rest phase . this breakdown / restoration cycle is a completely reversible process , and thixotropic behavior can be defined as a time - dependent behavior . furthermore , plastic materials have proven favorable in which the viscosity measured with a rotational viscosimeter ranges from 7 , 000 to 15 , 000 mpas . preferably , it has a value of approx . 10 , 000 mpas at a shear rate of 10 l / sec . for the purposes of a self - cleaning surface , it has proven favorable to use plastic materials whose contact angle has at least a value of greater than 60 degrees as a result of its surface energy for wetting with water . under certain circumstances , this surface energy can be further changed by subsequent treatment processes . with respect to the aforementioned requirements , an especially interesting representative of suitable plastic materials is polyvinyl siloxane . the use of this plastic can be provided in particular for forming the heads 12 and their free surface side . for the sake of clarity , the individual bonding elements in fig1 are shown arranged spaced relatively far apart from one another . in reality , these bonding elements including of the stem 14 , articulation site or part 16 , and head 12 lie tightly against one another . thus 10 , 000 to 20 , 000 of these elements per square centimeter can be located on the homogenous backing 10 . a uniform arrangement is preferred in which all bonding elements have the same distance to one another . irregular arrangements or those in pattern form ( circular , stem - shaped , ellipsoidal , etc .) are also possible . the heads 12 which are disc - shaped in exterior contour can also have other shapes . for example , the heads can be made elliptical or in polygonal form . a hexagonal form has been found to be especially favorable , also relative to the screen shaping process . the same applies to the stems 14 . the conicity for the respective stem 14 is at least one degree of oblique tilt relative to horizontal . preferably , the conicity is approx . 2 . 5 to 5 degrees to be able to obtain slender stem elements . the articulation site 16 , shown in fig2 , has a diameter from approx . 1 to 5 μm , preferably 2 μm , this diameter range being shown in fig2 as z 2 . in the embodiment shown in fig2 , the conical stem 14 as a molded part is connected in one piece to the backing 10 . the connection of the stem 14 to the backing 10 can also be produced via a cement connection ( not shown ) in the same size range . the thickness of the backing 10 is shown in fig2 with the opposing arrows w and in terms of magnitude corresponds to the indicated size z 2 . in particular , when the bonding element as shown in fig3 is produced without backing 10 and is connected to it only later , for example , by a cement or melt connection method , the backing 10 can also be made larger in terms of the thickness w . on its end facing away from the articulation site 16 , the conical stem has a thickness z 1 from 5 to 25 μm , preferably from approx . 10 to 20 μm . the diameter y of the head 12 is in turn , depending on the stem geometry , 30 to 100 μm , preferably approx . 40 μm . the head 12 in terms of its thickness x is chosen to be exceptionally narrow - lipped , and the values can be & lt ; 1 μm . for an embodiment ( not shown ) originating from the transition region of the head 12 to the stem 14 , the head tapers to the exterior in terms of width and ends in an annular end edge . especially high holding forces for the head 12 can be expected for the narrow - lipped feature tapering in this way . the purpose of fig3 is to illustrate in particular a detachment of the head 12 as a peeling motion from the body 18 in the vicinity . when the stem 14 is tilted around the articulation part by an angle a of approx . 20 ° relative to the vertical 20 , the peeling motion takes place , i . e ., the edge of the head 12 which is the left edge as viewed in fig3 begins to detach over the contact surface 22 of the head 12 as a rolling motion . depending on the concept of the touch fastening element , this angle a can also be more than 20 °, in particular at least 40 °. if in the initial state the stem 14 is not located parallel to the vertical 20 , but rather , extends obliquely , the stem already assumes a starting angle a , that is , the tapered end of the stem 14 ends in an oblique arrangement on the otherwise flat head plate of the head 12 . for a detachment motion in turn a corresponding angle offset can be expected which is then lower this time than for a vertical arrangement of the stems 14 relative to the head plate of the head 12 . as shown , the head plate can be made flat and accordingly can have essentially a uniform thickness . other cross sectional shapes on head plates can be implemented within the framework of the solution according to the invention . in another embodiment , as shown in fig4 , the head plate viewed in cross section is made as a double wedge shape , i . e ., proceeding from the middle in the region of the stem 14 the head plate narrows to both sides , along bevels tapering away from one another . in the embodiment as shown in fig5 , a single wedge is formed with one side having the greatest thickness and the opposite side having the smallest thickness . in the illustrated embodiment only the top is tilted . the top and underside can also taper toward one another to form a wedge . in the embodiment as shown in fig6 , in contrast to the above described solutions , the stem 14 is arranged off - center on the underside of the head plate of the head 12 . the head forms a plate made flat . instead of the head plate made flat , in the embodiment as shown in fig6 , it can also have other shapes , in particular the wedge cross sectional shapes as shown in fig4 and 5 . if a tilted wedge shape is used for the head plate , the oblique surfaces are tilted between 5 ° to 15 °, preferably by 10 °. depending on the peeling direction , the associated angle a can then be set , in particular , can be enlarged . the sharp - edged transitions shown in the figures between the backing band , the stem 14 and the head 12 are preferably round , in particular at the transition between the underside of head 12 and stem 14 . the radial outside edges of the head 12 , at least partially , can likewise be provided with the corresponding rounding to simplify production . 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 . | 8 |
referring to fig1 , the protective ballistic armor carrier ( 10 ), comprises a securing region ( 12 ). in one example , both sides of the carrier may be held together with additional securing straps ( 14 ). in the preferred embodiment the securing region ( 12 ) has fastening material ( 11 ) disposed thereon . referring to fig2 , the shirt ( 20 ) comprises a securing region ( 22 ). in a preferred embodiment the securing region ( 22 ) is comprised of a fastening material ( 23 ). in another embodiment , a tactile region ( 21 ) of the shirt ( 20 ) has a grippingly adhesive tactile material disposed thereon , which maybe tucked into the pants of a user to provide additional stabilization along region ( 24 ). the regional line is not actually drawn on the shirt ( 20 ), it is simply illustrated in this way for convenience . referring to fig3 , the protective ballistic armor of the present invention has a corresponding securing region ( 32 ) on its interior surface . in another embodiment , both sides of the ballistic armor may be held together with additional securing straps ( 33 ). in the preferred embodiment the securing region ( 32 ) has fastening material ( 31 ) disposed thereon . fig4 shows the embodiment where the protective ballistic armor carrier has an interior region cut out ( 42 ) thereby exposing portion of the protective ballistic armor &# 39 ; s securing region ( 43 ) so that fastening material ( 41 ) is exposed there through . this allows the fastening material ( 41 ) to secure directly to the fastening material of the shirt shown in fig2 . it should be noted that the invention is not limited to only one securing region . in an alternative embodiment a plurality of securing regions may be used . additionally , the securing regions are not limited to specific location and can appear on any portion of the invention . in yet another embodiment a plurality of tactile regions can be used to further frictionally secure various portions of the invention . it is therefore the object of the present invention to provide a new body armor stabilization system , where comfort and stability are increased . with respect to the above description then , it is to be realized that the optimum dimensional relationships for the parts of the invention , to include variations in size , materials , shape , form , function and manner of operation , assembly and use , are deemed readily apparent to those skilled in the art , and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention . therefore , the foregoing is considered as illustrative only of the principles of the invention . further , since numerous modifications and changes will readily occur to those skilled in the art , it is not desired to limit the invention to the exact construction and operation shown and described , and accordingly , all suitable modifications and equivalents may be resorted to , falling within the scope of the invention . | 5 |
fig1 shows a hemispherical recess 1 in the surface 2 of a wind power unit in a sectional side view . as shown in fig1 , the surface 2 is subject to an incident flow essentially parallel to the surface . the hemispherical recess 1 shown in this exemplary embodiment should only be seen as an example . instead of a hemispherical form , the form of a half - teardrop or another form can be selected , which improves the flow . as the air sweeps past the recess 1 , an eddy 3 forms in the recess 1 , which assists the passage of the air and accelerates the air volume . the extent of this effect is a function of the incident flow speed , the angle of incidence , the air pressure , the air temperature , the form and configuration of the recess 1 . the eddies 3 forming in each recess act like a “ ball bearing ” for the passing air . the laminar flow at the surface 2 is not disturbed or is only slightly disturbed as a result . fig2 - 7 show the recess 1 shown in fig1 and the aerodynamic effects as air sweeps past in individual steps . fig2 is a top view and represents the surface 2 of a component of the wind power unit , which has a recess 1 . the circular edge of the hemispherical recess 1 can be seen in fig2 . the recess 1 is subject to an essentially laminar incident flow by the passing air , as a result of which two symmetrical eddies 3 , 4 are initially generated . fig3 shows the recess in fig2 a short time later . due to asymmetries in the incident flow , the dominant eddy has formed in the recess 1 , while the other eddy 4 has become weaker . it can also be seen in fig3 that the flow lines 5 of the passing air are deflected laterally between the eddies 3 , 4 . as shown in fig4 the dominant eddy 3 on the one side has become a “ tornado ”. in other words a small , local eddy has occurred , in which the air rises , so that it is moved away from the surface 2 . an eddy 3 has therefore formed out of the recess 1 , which drives the passing air further in the flow direction . fig4 also shows that the passing air is deflected laterally . fig5 shows the flow conditions a short time later . the eddy 3 collapses again after a short time due to flow asymmetries , so the strength of the dominant eddy is reduced . at the same time the other eddy 4 starts to extend . unlike the situation in fig4 , in this situation the passing air is not deflected laterally , in other words it is not affected . fig6 shows the flow conditions a little later . the eddy 4 starts to dominate , as it is significantly larger and stronger than the other eddy 3 . it can also be seen that the flow lines 6 of the passing air are deflected laterally . the eddies 3 , 4 have opposing rotation directions , so the flow lines 6 of the passing air are deflected in the opposite lateral direction compared with the situation in fig4 , in which the eddy 3 was dominant . fig7 shows the flow conditions a short time later . the eddy 4 , which is counter to the eddy 3 , has developed to become a larger eddy , which drives the passing air further out of the recess 1 in the flow direction . the eddy 4 also goes on to collapse again due to flow asymmetries and the sequence shown is repeated continuously . fig8 shows the development of flow eddies at the recesses . the wind power unit generally has a plurality of recesses , which are configured on the surface of the rotor blades , the mast , the gondola or another component around which there is a flow . small flow eddies form from each individual recess 1 and drive the passing air further in the flow direction . after some time the eddy collapses and an eddy with the opposite rotation direction develops . adjacent recesses 1 , 7 can thereby have the same or opposite rotation directions . the friction resistance in the boundary layer between the passing air and the surface is thereby reduced and the air flow at the surface is also assisted and accelerated . as the overall energy in a closed system cannot increase , energy is consumed at the same time at other points , for example due to friction effects , i . e . the friction energy of conventional systems is partly used to generate the eddies , which in turn reduce overall friction losses . fig9 shows a field with regularly arranged recesses and the resulting flow field . as shown in fig9 , the recesses are arranged in horizontal rows , adjacent rows being offset laterally such that each recess 1 is essentially the same distance from all adjacent recesses . the counter - clockwise and clockwise eddies alternate over time and a pattern of these alternating eddies develops on the surface 2 around which there is a flow , said eddies extending essentially from one recess 1 to the next recess 1 as a function of incident flow speed and further aerodynamic parameters . these eddies 3 , 4 assist and accelerate the air flow over the entire surface 2 . fig1 shows a schematic diagram of a rotor mast of a conventional wind power unit subject to an incident flow and the turbulence field generated in a horizontal sectional view . the rotor mast 8 has a circular cross - section . the incident air mass 9 is essentially laminar , i . e . the individual flow elements run parallel to each other and the air is turbulence - free . the transition points 9 are located on the left and right sides of the rotor mast viewed in the flow direction in the region of the maximum diameter . the transition point 10 characterizes the point at which the laminar flow 9 changes to a turbulent flow 11 . as shown in fig1 , the wake region with the turbulent flow is slightly tapered in form so the turbulent region increases behind the wind power unit . wind power plants behind are subject to the action of turbulent air , which reduces their efficiency . fig1 is similar to fig1 and shows a rotor mast 12 , with a film 13 on the outside , the film 13 having recesses to improve flow . unlike the rotor mast in fig1 , in the case of the rotor mast 12 with film 13 the incident laminar air 16 has a significantly longer laminar section , so the transition points 14 are displaced in the flow direction . as shown in fig1 , the transition points are behind the maximum diameter of the rotor mast 12 , so that the flow is subject to very low friction levels until then . the turbulent flow 15 can only form after this . unlike the example shown in fig1 , the region of turbulent flow 15 is significantly smaller , so that wind power units behind are influenced significantly less . it is therefore possible to set up individual wind power units in a wind farm at shorter distances from each other , resulting in better surface utilization and a higher energy yield per unit of area . fig1 shows a schematic view of a wind power unit , the surface of which at least partly has recesses to improve flow . the wind power unit , referred to as a whole as 17 , essentially comprises a mast 12 , a rotor with several rotor blades 18 , a gondola 19 to accommodate the generator and a spinner 20 , which covers the hub region of the rotor . the regions of the surface of the individual components of the wind power unit 17 which have recesses are shown hatched in fig1 . the rotor mast 12 is provided in its entirety , apart from its lower section , with recesses to improve flow . the entire surfaces of the gondola 19 and spinner 20 are also provided with recesses . the rotor blades 18 have strip - shaped regions running longitudinally along their upper and lower sides , which are provided with recesses . unlike the known sharkskin effect , with which friction can be reduced by around 10 %, first preliminary trials have shown that an improvement of around 30 % can be expected with the wind power unit . | 8 |
referring now in more detail to the drawings , the invention will now be described in more detail . using a sensor device which varies its output as a particular point on the circumference of the tire enters and exits the contact patch lends itself to digital values with respect to time . tire deflection can then be calculated using the ratio of time spent in the contact patch to time spent traveling around the circumference of the tire . a digitized electrical signal also provides the number of tire rotations per unit of time ( rotational frequency ) as well as the total number of tire revolutions over the life of the tire . using tire deflection and the tire rotational frequency , the tire speed can be calculated and monitored to verify tire operations within an acceptable load , speed and life cycle regime . in addition , tire deflection / speed / revolution measurements can be made using a relatively short monitoring time which can be repeated every few minutes . tire deflection and speed can be combined with a count of total tire revolutions to provide a more useful measure of tire carcass fatigue life using deflection , speed and time or deflection , speed and revolution count relationships . additionally , this sensor may also be used to measure the severity of the tire operating environment by developing algorithms which convert the magnitude and frequency of load , pressure and speed oscillations to the severity of tire service . the length of the contact patch varies in relation to the inflation pressure of a pneumatic tire under a constant vehicle load in that , to an extent , increasing the inflation pressure shortens the contact patch . the total outer tread circumference of a loaded tire in contact with the ground surface has a length fixed by the length of the relatively rigid belt plies below the tire &# 39 ; s tread portion . the outer tread circumference has a contact patch portion and a free portion not making contact with a ground surface . the total length of these two portions when added together remains essentially constant with a changing inflation pressure within the tire and / or when changing the load on the tire . however , the relative length of these two portions changes . the contact patch is that portion of the tire tread circumference which is in contact with the ground surface . the load on a pneumatic tire at a constant inflation pressure changes the length of the tire &# 39 ; s contact patch in that , to an extent , increasing the load lengthens the contact patch . the length of the contact patch is further lengthened by decreasing the inflation pressure . the illustration of fig1 a shows the tire 10 in contact with a ground surface 30 . a contact length cl of the contact area 13 must fall within an acceptable range for the pneumatic tire to function properly . the larger the contact length the more the tire is being deflected . for optimal performance , contact length should be adjusted by varying inflation pressure for a given load and tire rotational speed w conditions . the inflation pressure within a loaded tire is inversely proportional to the percentage of time that a reference point 20 on the outer surface 12 of the tire tread spends in contact with the ground surface 30 . a relationship can be formulated as follows : where tc is the period of time a reference point on the tread &# 39 ; s circumference is free from contact with a ground surface ; tp is the period of time a reference point on the tread &# 39 ; s circumference is in contact with a ground surface ; tc / tp is a ratio as further discussed in this description ; and k is a constant of proportionality for the tire used and is a nonlinear function of the load and pressure . increasing the load transferred through the rim 18 or decreasing the inflation pressure results in an increased percentage of the time that the reference point 20 on the surface of the tire &# 39 ; s tread spends in contact with the ground surface during one revolution of the tire . a sensor device 50 used to provide a signal for calculating tire contact patch length tl can comprise one of several different types , including but not limited to : 1 ) a piezoelectric polymer , which consists of a piece of polymer which was manufactured in such a way as to contain aligned dipolar molecules which cause an electrical charge potential when the polymer is strained ; 2 ) a photorestrictive fiber optic cable connecting a light emitting diode and a photocell , which modulates the amount of light received by the photocell when the fiber optic cable is bent normal to its longitudinal axis ; 3 ) a variable capacitor made from aluminized mylar , whose capacitance changes as a function of pressure ; and 4 ) a variable inductor sensor , consisting of an inductive coil whose inductance changes or whose coupling between two inductive coils changes as a result of sensor strain . the preferred embodiment of the sensor device consists of the piezoelectric polymer which strains as a result of the tread bending or flexing as it enters and exits the contact patch . fig3 is a diagram of an exemplary electronic signal curve 100 which may be obtained from a sensor device of the above types for lightly as well as heavily deflected tires . there are large deformations of the sensor device as the reference point enters contact with the ground surface . the strain of these first deformations produces an electrical signal having a maximum value 102 followed by a minimum value 104 before the tread surface becomes flat on the ground surface 30 . the characteristic time period tf between maximum and minimum signal values corresponds to a characteristic frequency of the tire . as the reference point leaves the contact area 13 the sensor device is again strained and a second deformation produces another electrical signal having another maximum value and another minimum value . the electrical signal as the reference point exits the contact patch is essentially the same as that illustrated in fig3 . the first and second deformations of the sensor device as the reference point enters and exits the contact patch defines very well the contact length cl ( fig1 a ). the evolution of tf for a known load , speed and pressure is also an indication of the tire &# 39 ; s wear . the position of the sensor device within the tire is critical to the proper generation of electrical signals . a tire cross - section taken along line a -- a in fig1 a is illustrated in fig1 b . the sensor device 50 is positioned near the radial plane r -- r of the tire on an inside surface 16 of the tire 10 . preferably the sensor device 50 is protected by a rubber patch 52 on the inside surface 16 of the tire . the reference point 20 is adjacent the sensor device on the external surface 12 of the tire &# 39 ; s tread at the radial plane . sensor device electrical signals are monitored as disclosed in the following discussions . in fig2 a simplified block diagram of the tire monitoring system is illustrated in accordance with the preferred embodiments of this invention . fig2 shows the general electronic requirements for electrical signal conditioning , transmission , and processing to carry out this invention . as the sensor device 20 strains , the piezoelectric polymer of the sensor device generates a continuous electrical signal which can be amplified and converted to digital electrical pulses by a digital monitoring device 62 . a logic circuit of the monitoring device monitors the electrical signals from the sensor device to define first and second electrical signals . first electrical signals are generated when the reference point 20 is not contained within the contact area 13 . second electrical signals are generated when the reference point is contained within the contact area . the digital monitoring device further includes a digital clock device and counting circuit to provide a system monitoring time and frequency . first and second electrical signals are converted to first and second electrical clock pulses respectfully . electrical clock pulses are generated in accordance with a monitoring frequency to give a plurality of pulses per revolution of the tire . electrical pulses have a magnitude difference only as required to distinguish the first electrical pulses from the second electrical pulses . the electrical pulses are used as input into a digital counting circuit and the logic circuit of the monitoring device . the digital counting circuit uses the converted sensor electrical pulses to count the number of revolutions which occur for any given monitoring time period and the number of first and second electrical pulses each revolution of the tire . the digital logic circuit uses the conditioned first and second electrical pulses and the digital clock circuit to calculate the ratio of the time that the sensor device spends in the contact patch to the time that the sensor spends outside the contact patch . this ratio is proportional to the tire deflection . in addition , the digital logic circuit will provide the time for each tire revolution , yielding the tire &# 39 ; s angular velocity ( wheel speed ). information from the digital logic circuit and the counter values from the digital clock counter circuit are recorded by an interface memory device 64 and stored in random access memory ( rom ) 65 . this information is periodically transmitted by a passive radio frequency ( rf ) transceiver when needed . the transceiver has a transmitter 82 within the tire and a receiver 84 within the vehicle . the passive rf transceiver would only transmit when activated by a rf interrogation signal external to the tire . this affords the in - tire passive rf transceiver minimum power consumption . this allows the electronic package and the sensor device to be powered by a long - life battery or a rechargeable battery which can preferably be charged by the motion of the tire . the electronics package , including the digital monitoring device 62 , plus the memory device 64 , the rom 65 and the transmitter 82 may contain electrical components which have a low tolerance to the cyclic stress and strain of the rotating tire . these components are positioned near the bead area 14 of the tire as illustrated in fig1 b . the bead area provides a stable environment to limit cyclic fatigue of these components remote from the sensor device . a lead wire 54 electrically connects the sensor device with these low life - cycle components . other connection means are also within the scope of this invention , including wireless connections . an antenna 61 for radio frequency transmissions may also be positioned near the bead area 14 . the illustration of fig4 shows a generalized plot of the sensor device electrical signal as a function of the angle around the tire . the cure 110 representing the electrical signal has one set of values when the reference point is with the contact patch or area and another set of values when the reference point is in a angular location where the tire has a normal radius . the normal radius corresponds to the reference point not being in the contact area . the zero angular reference location is at the top of the rolling tire with the center of the contact patch being at 180 degrees . in this example , the contact is between 149 degrees and 212 degrees . the percentage of the tire &# 39 ; s circumference in the contact patch is 100 ×( 212 - 149 )/ 360 = 18 percent of the total circumference of the tire . this percentage is very sensitive to the tire &# 39 ; s deflection . the contact patch length cl is somewhat larger than the peak to peak distance cm of the electrical signal 110 . the relationship between cl and cm can be obtained and stored in the memory device for different tires to be used in determining an accurate contact length in obtaining an optimum percentage or ratio . in another embodiment of the present system and method the electrical signals from the sensor device can be processed by a frequency processing circuit within the electronics package to determine a characteristic frequency of the tire in use . for example , this may be a wheel hop frequency or a radial natural resonant frequency of the tire . this characteristic frequency can provide an additional system parameter to be used to determine what part of the tire &# 39 ; s deflection is attributed to inflation pressure and what part is attributed to the load on the tire . the addition of this information would eliminate the need for the operator of the vehicle to input information on wheel loads into the computer . the rf receiver 84 mounted in the vehicle will periodically interrogate the rf transmitter 82 in the tire . the revolution count , vehicle speed , and tire deflection data ( load and inflation pressure ) can them be computed and displayed by an on - board vehicle computer . the computer or microprocessor would control overall performance of the monitoring system and could be programmed with algorithms to take advantage of the revolution count , vehicle speed and tire deflection data including but not limited to : ( b ) individual or average wheel revolution counts over a given period of time ; and ( c ) filtered individual and average wheel deflection acceptable operating range of wheel deflection for a given wheel angular velocity . this information can be displayed in the vehicle cabin for the driver &# 39 ; s immediate use , or as a warning in the case of a low pressure , high load and high speed situations , or as an input into a vehicle central tire inflation system ( ctis ) 90 . since the tire monitoring system circuitry would contain each tires unique identification number permanently stored in read only memory ( rom ) 65 , the in - cab microprocessor system or computer could download individual tire data to another external computer for fleet - wide tracking of tire usage . the preferred embodiment of this invention has been described using specific terms , such description is for illustrative purposes only , and it is to be understood that changes and variations may be made without departing from the spirit of scope of the following claims . | 1 |
fig1 shows a system for an inflatable light weight solar cooker ( 100 ) with a sun ( s ). additional figures and descriptions in this disclosure detail the structure and function of the inflatable light weight solar cooker ( 100 ). also shown is a sun ( s ). fig2 shows certain components of an inflatable light weight solar cooker ( 200 ). shown in fig2 are an inflatable light weight solar cooker ( 200 ) comprising an inflatable upper chamber ( 205 ), a lower chamber ( 210 ), and a cooking chamber ( 215 ). also shown is a sun ( s ). as will be described , the inflatable upper chamber ( 205 ) functions as a three - stage primary solar concentrator so that a majority of sunlight striking the inflatable upper chamber ( 205 ) is concentrated through the inflatable light weight solar cooker ( 100 ). in some embodiments , the solar radiation from the sun ( s ) could be concentrated to as much as ten suns into the cooking chamber ( 215 ). fig3 provides additional details about the structure and function of the inflatable upper chamber ( 205 ). the lower chamber ( 210 ) functions as an additional two - stage solar concentrator for the inflatable light weight solar cooker ( 100 ) to ( a ) direct solar radiation into the cooking chamber ( 215 ) that exits the inflatable upper chamber ( 205 ) but does not enter the cooking chamber ( 215 ), and ( b ) functions as a barrier against convective heat escape by trapping hot air within the lower chamber ( 210 ). the lower chamber ( 210 ) thus assures more heat is delivered to the cooking chamber ( 215 ). fig5 provides additional details about the structure and function of the lower chamber ( 210 ). fig3 shows certain details of an inflatable upper chamber ( 300 ). shown in fig3 are an inflatable upper chamber substantially transparent refractive upper lens ( 305 ), a substantially conical outer wall ( 310 ), a substantially reflective inner wall ( 315 ), a substantially transparent lower lens ( 320 ), and at least one gas passage nozzle ( 325 ). the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) receives sunlight and refracts the sunlight into the interior of the inflatable upper chamber ( 300 ). this is the first stage of the inflatable upper chamber ( 300 ) as a three - stage primary solar concentrator for the inflatable light weight solar cooker ( 100 ). the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) must be sufficiently pliable and have sufficient tensile strength to be inflatable . in addition , the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) must be substantially transparent to allow sunlight to pass through and into the interior of the inflatable upper chamber ( 300 ). lastly , the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) must have at least a marginal refractive index to refract sunlight into the interior of the inflatable upper chamber ( 300 ). in some embodiments , the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) may be clear polyester film , including that sold under the mylar ® brand . the substantially conical outer wall ( 310 ) is a structural component providing a conical shape to the inflatable upper chamber ( 300 ), and may be opaque , partially transparent , or wholly transparent . the substantially conical outer wall ( 310 ) similarly must be sufficiently pliable and have sufficient tensile strength to be inflatable . in some embodiments , the substantially conical outer wall ( 310 ) may also be polyester film . the conical shape of the substantially conical outer wall ( 310 ) is one - half of the second stage of the inflatable upper chamber ( 300 ) as a three - stage primary solar concentrator for the inflatable light weight solar cooker ( 100 ). the substantially reflective inner wall ( 315 ) reflects sunlight striking the substantially reflective inner wall ( 315 ) from the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) so that the sunlight is directed further along the substantially conical outer wall ( 310 ). in some embodiments , the substantially reflective inner wall ( 315 ) may comprise a polyester film , including mylar ®, metalized or with a reflective coating , film or other reflective structure integrated or affixed to fulfill the reflective function . in some embodiments , the substantially reflective inner wall ( 315 ) may comprise a polyethylene ( pe ) film or polyethylene terephthalate ( pet ) film . in some embodiments , the substantially reflective inner wall ( 315 ) may comprise an aliphatic polyamide film , including nylon , metalized or with a reflective coating , film or other reflective structure integrated or affixed to fulfill the reflective function . in some embodiments , the substantially reflective inner wall ( 315 ) may comprise an aluminum coating on a flexible substrate . in some embodiments , the substantially reflective inner wall ( 315 ) may be a polyvinyl chloride ( pvc ) reflective film . in some embodiments , the substantially reflective inner wall ( 315 ) may be integrated with the substantially conical outer wall ( 310 ). in some embodiments , the substantially reflective inner wall ( 315 ) may be subsurface , i . e ., a layer , between the substantially conical outer wall ( 310 ) and a substantially transparent layer within the inflatable upper chamber ( 300 ). the substantially reflective inner wall ( 315 ) is the second - half of the second stage of the inflatable upper chamber ( 300 ) as a three - stage primary solar concentrator for the inflatable light weight solar cooker ( 100 ). the substantially reflective inner wall ( 315 ) must be sufficiently pliable and have sufficient tensile strength to be inflatable . the substantially transparent lower lens ( 320 ) receives sunlight from the substantially reflective inner wall ( 315 ) and the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) and refracts the sunlight into the adjacent structures . the substantially transparent lower lens ( 320 ) is the third stage of the inflatable upper chamber ( 300 ) as a three - stage primary solar concentrator for the inflatable light weight solar cooker ( 100 ). the substantially transparent lower lens ( 320 ) must be substantially transparent to allow sunlight to pass out of the inflatable upper chamber ( 300 ). in some embodiments , the substantially transparent lower lens ( 320 ) has a refractive index greater than one . as described in fig4 , there is a mathematical relationship of the substantially transparent lower lens ( 320 ) to the inflatable upper chamber substantially transparent refractive upper lens ( 305 ). in simplest terms , the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) is about three times wider than the substantially transparent lower lens ( 320 ). this mathematical relationship is not required for use , but rather , provides for optimum efficiency of the inflatable light weight solar cooker ( 200 ). the substantially transparent lower lens ( 320 ) must be sufficiently pliable and have sufficient tensile strength to be inflatable . in some embodiments , the substantially transparent lower lens ( 320 ) may be clear polyester film , including that sold under the mylar ® brand . altogether , the inflatable upper chamber substantially transparent refractive upper lens ( 305 ), the substantially conical outer wall ( 310 ) and the substantially transparent lower lens ( 320 ) make the inflatable upper chamber ( 300 ) function as a cone shape sunlight concentrator . the at least one gas passage nozzle ( 325 ) is a port for the passage of a transparent gas into , out of , or into and out of the inflatable upper chamber ( 300 ) so the inflatable upper chamber ( 300 ) may be inflated , deflated , or inflated and deflated . in some embodiments , there may be one gas passage nozzle ( 325 ). other embodiments may have a plurality of gas passage nozzles ( 325 ). a plurality of gas passage nozzles ( 325 ) may be required in an embodiment in which one or more of the inflatable upper chamber substantially transparent refractive upper lens ( 305 ), the substantially conical outer wall ( 310 ), the substantially reflective inner wall ( 315 ), or the substantially transparent lower lens ( 320 ) is inflated either separated , or as a separate set from one or more of the structures of the inflatable upper chamber ( 300 ). the at least one gas passage nozzle ( 325 ) is flexible in some embodiments so that all structures of the inflatable upper chamber ( 300 ) might be made of the same material . the at least one gas passage nozzle ( 325 ) is flexible in some embodiments so that the inflatable upper chamber ( 300 ) might be deflated and compressed for storage and not risking damage , which might occur if the at least one gas passage nozzle ( 325 ) were a non - flexible material . fig4 provides details about a mathematical relationship of the shape of the inflatable upper chamber ( 400 ) to have a high optical efficiency . for purposes of fig4 , the inflatable upper chamber ( 400 ) is presumed to have a true trapezoid shape . shown in fig4 as a presumably true trapezoid , is a inflatable upper chamber solar radiation entrance ( 405 ), which is dimensioned as ‘ a ’. in the fig3 inflatable upper chamber ( 300 ), the inflatable upper chamber substantially transparent refractive upper lens ( 305 ) is connected to the inflatable upper chamber ( 300 ) along this side . also shown in fig4 is a inflatable upper chamber solar radiation exit ( 410 ) which is dimensioned as ‘ b ’. in the fig3 inflatable upper chamber ( 300 ), the substantially transparent lower lens ( 320 ) is connected to the inflatable upper chamber ( 300 ) along this side . as sides of a true trapezoid , the inflatable upper chamber solar radiation entrance ( 405 ) and the inflatable upper chamber solar radiation exit ( 410 ) are parallel to each other . also shown in fig4 are sides ( 415 ) of the inflatable upper chamber which are dimensioned as ‘ h ’ and form an angle θ (“ theta ”) against a right angle formed by side a , or side b and a perpendicular line to side a , or side b . since every time the sunlight reflects at the inner surface of the upper balloon , a percentage of solar energy is lost . an optimized solar concentrator will have all sunlight entering “ a ” reach exit “ b ” with minimal number of reflection . that is : for the inflatable upper chamber ( 300 ) to have a high optical efficiency , height h should satisfy equation ( 4 ) to maximize concentrating the sunlight entering the inflatable upper chamber solar radiation entrance ( 405 ) and leaving the inflatable upper chamber solar radiation exit ( 410 ). in effect , side ‘ a ’, the dimension of the inflatable upper chamber solar radiation entrance ( 405 ) should not be greater than three times of dimension “ b ”, the inflatable upper chamber solar radiation exit ( 410 ), i . e ., fig5 a and 5 b shows an embodiment of an lower chamber ( 500 ). in this embodiment , the lower chamber ( 500 ) models a semi - hollow cylinder comprising an inflatable outer wall ( 505 ), a inner chamber ( 510 ) and at least one gas passage nozzle ( 515 ). the inflatable outer wall ( 505 ) provides support for the lower chamber ( 500 ) to stage semi - right when inflated . as with the upper chamber , the inflatable outer wall ( 505 ) may be polyester film , including that sold under the mylar ® brand . in other embodiments , the inflatable outer wall ( 505 ) might be a polyvinyl chloride ( pvc ) film , polyester film , polyethylene ( pe ) film , polyethylene terephthalate ( pet ) film . the inflatable outer wall ( 505 ) could be opaque , transparent , or have partial transparency . the lower chamber ( 500 ) may serve a plurality of purposes . in some embodiments , the lower chamber ( 500 ) is a secondary solar concentrator to the inflatable upper chamber . in these embodiments , the inner chamber ( 510 ) comprises a reflective inner surface . as with the upper chamber , the reflective inner surface may be clear polyester film , including that sold under the mylar ® brand . in other embodiments , the reflective inner surface might be reflective polyvinyl chloride ( pvc ) film . in other embodiments , the reflective inner surface might be aluminum metalized coating . the inner chamber ( 510 ) also serves a holding reservoir for cooking or heating foodstuff , heating beverages , or both . in some embodiments , the lower chamber is integrated with the cooking chamber . while the foodstuff or beverage would typically be placed in a separate container to preserve cleanliness of the foodstuff or beverage , the inner chamber ( 510 ) might also serve as a container , for which the lower chamber ( 500 ) might have a sealed bottom ( not shown ). the at least one gas passage nozzle ( 515 ) is a port for the passage of a transparent gas into , out of , or into and out of the lower chamber ( 500 ) so the lower chamber ( 500 ) may be inflated , deflated , or inflated and deflated . in some embodiments , there may be one gas passage nozzle ( 515 ). other embodiments may have a plurality of gas passage nozzles ( 515 ). the at least one gas passage nozzle ( 515 ) is flexible in some embodiments so that all structures of the lower chamber ( 500 ) might be made of the same material . the at least one gas passage nozzle ( 515 ) is flexible in some embodiments so that the lower chamber ( 500 ) might be deflated and compressed for storage and not risking damage , which might occur if the at least one gas passage nozzle ( 515 ) were a non - flexible material . in some embodiments , the lower chamber ( 500 ) may also comprise a lower chamber transparent cover ( 520 ) for trapping heated air within the lower chamber ( 500 ). in this embodiment , the lower chamber ( 500 ) is a two - stage solar concentrator . in some embodiments , the lower chamber transparent cover ( 520 ) may be clear polyester film , including that sold under the mylar ® brand . fig6 shows another embodiment of an lower chamber ( 600 ). in this embodiment , the lower chamber ( 600 ) models a toroid semi - circle comprising an outer surface ( 605 ), an at least partially open inner chamber ( 610 ) and at least one gas passage nozzle ( 615 ). this embodiment of the lower chamber ( 600 ) presents certain advantages in that the toroid semi - circle shape , when deflated , folds into a smaller size than some other shapes . in this embodiment , the lower chamber ( 600 ) may cradle a food container and provide a base for the inflatable upper chamber as well . in some embodiments , the outer surface ( 605 ) may be a polyester film , including that sold under the mylar ® brand . in other embodiments , the outer surface ( 605 ) might be polyvinyl chloride ( pvc ) film . in some embodiments , the outer surface ( 605 ) may be clear . in some embodiments , the outer surface ( 605 ) may be reflective . in other embodiments , the outer surface ( 605 ) might be aluminum metalized coating . if reflective , the lower chamber ( 600 ) would assist in heating the food or beverage within the inflatable light weight solar cooker . the at least partially open inner chamber ( 610 ) may be small or large as designed to accommodate whatever cooking container is used , if one is used . in some embodiments , the at least partially open inner chamber ( 610 ) may have a sealed bottom so that a flexible cooking container , perhaps made of a flexible plastic , such as a polyethylene bag , or even a paper bag , may be placed on the at least partially open inner chamber ( 610 ) for heating and cooking . the at least one gas passage nozzle ( 615 ) is a port for the passage of a transparent gas into , out of , or into and out of the lower chamber ( 600 ) so the lower chamber ( 600 ) may be inflated , deflated , or inflated and deflated . in some embodiments , there may be one gas passage nozzle ( 615 ). other embodiments may have a plurality of gas passage nozzles ( 615 ). the at least one gas passage nozzle ( 615 ) is flexible in some embodiments so that all structures of the lower chamber ( 600 ) might be made of the same material . the at least one gas passage nozzle ( 615 ) is flexible in some embodiments so that the lower chamber ( 600 ) might be deflated and compressed for storage and not risking damage , which might occur if the at least one gas passage nozzle ( 615 ) were a non - flexible material . fig7 shows another embodiment of an lower chamber ( 700 ). in this embodiment , the lower chamber ( 700 ) models a torus comprising an outer surface ( 705 ), an at least partially open inner chamber ( 710 ) and at least one gas passage nozzle ( 715 ). as with the embodiment in fig6 . this embodiment of the lower chamber ( 600 ) presents certain advantages in that the toroid shape , when deflated , folds into a smaller size than some other shapes . in this embodiment , the lower chamber ( 700 ) is deeper for cradling larger food container and provides a base for the inflatable upper chamber as well . in some embodiments , the outer surface ( 705 ) may be a polyester film , including that sold under the mylar ® brand . in other embodiments , the outer surface ( 705 ) might be polyvinyl chloride ( pvc ) film . in some embodiments , the outer surface ( 705 ) may be clear . in some embodiments , the outer surface ( 705 ) may be reflective polyester film or reflective polyvinyl chloride ( pvc ) film in other embodiments , the reflective inner surface might be aluminum metalized coating . if reflective , the lower chamber ( 700 ) would assist in heating the food or beverage within the inflatable light weight solar cooker . the at least partially open inner chamber ( 710 ) may be small or large as designed to accommodate whatever cooking container is used , if one is used . in some embodiments , the at least partially open inner chamber ( 710 ) may have a sealed bottom so that a flexible cooking container , perhaps made of a flexible plastic , such as a polyethylene bag , or even a paper bag , may be placed on the at least partially open inner chamber ( 710 ) for heating and cooking . the at least one gas passage nozzle ( 715 ) is a port for the passage of a transparent gas into , out of , or into and out of the lower chamber ( 700 ) so the lower chamber ( 700 ) may be inflated , deflated , or inflated and deflated . in some embodiments , there may be one gas passage nozzle ( 715 ). other embodiments may have a plurality of gas passage nozzles ( 715 ). the at least one gas passage nozzle ( 715 ) is flexible in some embodiments so that all structures of the lower chamber ( 700 ) might be made of the same material . the at least one gas passage nozzle ( 715 ) is flexible in some embodiments so that the lower chamber ( 700 ) might be deflated and compressed for storage and not risking damage , which might occur if the at least one gas passage nozzle ( 715 ) were a non - flexible material . fig8 shows an embodiment of an inflatable light weight solar cooker ( 800 ) with an inflatable upper chamber ( 805 ) having an inner reflective surface as previously described , a lower chamber ( 810 ) with reflective inner surface ( 815 ), a lower chamber transparent cover ( 820 ), a supporting stand ( 825 ) and supporting strap ( 830 ). the lower chamber ( 810 ) is similar to other embodiments . the distinction of inflatable light weight solar cooker ( 800 ) is that the lower chamber ( 810 ) with reflective inner surface ( 815 ) is typically not inflatable . in some embodiments , the lower chamber ( 810 ) with reflective inner surface ( 815 ) may include a lower chamber transparent cover ( 820 ) for trapping heated air within the lower chamber ( 810 ) with reflective inner surface ( 815 ). in some embodiments , the lower chamber transparent cover ( 820 ) may be clear polyester film , including that sold under the mylar ® brand . in some embodiments , the lower chamber ( 810 ) may be integrated with the cooking chamber . in some embodiments , the lower chamber transparent cover ( 820 ) may be polyethylene ( pe ) film or polyethylene terephthalate film . another distinction of the inflatable light weight solar cooker ( 800 ) is that a supporting stand ( 825 ) may be present . supporting stand ( 825 ) aids in keeping inflatable upper chamber ( 805 ) pointed at the sun ( s ) without assistance . as inflatable upper chamber ( 805 ) is lightweight , supporting stand ( 825 ) does not have to support much weight . in some embodiments , supporting stand ( 825 ) may be comprise polyvinyl tubing , which is beneficial in being lightweight , inexpensive , easy to cut to size , and easy to assemble with off - the shelf supplies . another distinction of the inflatable light weight solar cooker ( 800 ) is that a supporting strap ( 830 ) may be present . as with the supporting stand ( 825 ), the supporting strap ( 830 ) aids in keeping inflatable upper chamber ( 805 ) pointed at the sun ( s ) without assistance . similarly , supporting strap ( 830 ) may be made from lightweight , off the shelf materials , even bungee cords . fig9 shows an embodiment of an inflatable light weight solar cooker ( 900 ) with an inflatable upper chamber ( 905 ) having an inner reflective surface as previously described , a cowling with inner reflective surface ( 910 ), a lower chamber ( 915 ), a cooking chamber ( 920 ), a supporting stand ( 925 ) and a supporting strap ( 930 ). the inflatable light weight solar cooker ( 900 ) is similar to other embodiments of the inflatable light weight solar cooker , with the exception of the cowling with inner reflective surface ( 910 ). in other embodiments , the inflatable upper chamber of the inflatable light weight solar cooker is typically resting on or within the lower chamber ( 915 ). if the lower chamber is open , i . e ., without a transparent cover , heat may escape , while debris and contaminants may enter the cooking chamber ( 920 ). the cowling with inner reflective surface ( 910 ) aids in both trapping heat in , and blocking debris and contaminants from entering the cooking chamber ( 920 ). the cowling with inner reflective surface ( 910 ) is also helpful when the sun ( s ) is low in the sky with the cowling with inner reflective surface ( 910 ) reflecting concentrated light from the inflatable upper chamber ( 905 ) into the lower chamber ( 915 ). in some embodiments , the cowling with inner reflective surface ( 910 ) may be flexible . in some embodiments , the cowling with inner reflective surface ( 910 ) may be integrated with the lower chamber ( 915 ). fig1 shows a method for delivering thrice - concentrated sunlight into a cooking chamber . the method ( 1000 ) comprises : step 1010 : concentrating sunlight by refraction through an inflatable upper chamber substantially transparent refractive upper lens ( 305 ) and passing the concentrated sunlight into an inflatable upper chamber ( 300 ), step 1020 : concentrating the sunlight a second time in the inflatable upper chamber ( 300 ) with a substantially reflective inner wall ( 315 ), step 1030 : passing the sunlight through a substantially transparent lower lens ( 320 ) to concentrate the sunlight a third time by refraction , and step 1040 : delivering the thrice - concentrated sunlight into a cooking chamber . these descriptions and drawings are embodiments and teachings of the disclosure . all variations are within the spirit and scope of the disclosure . this disclosure is not to be considered as limiting the claims to only the embodiments illustrated or discussed . certain changes can be made in the subject matter without departing from the spirit and the scope of this invention . it is realized that changes are possible within the scope of this invention and it is further intended that each structure or element recited in any of the claims is to be understood as referring to all equivalent structure or elements . the following claims are intended to cover the invention as broadly as possible in whatever form it may be used . | 5 |
fig1 is a perspective schematic view of one embodiment of an electrical system having an electronic assembly mounted therein . fig1 a is a perspective assembly schematic view of a mounting location of the system with a board . the figures will be described in reference to each other . an electronic system 2 generally has one or more electronic assemblies 4 a , 4 b , 4 c ( generally “ 4 ”) coupled to a communication bus 6 , where the assemblies are sometimes referred to herein as “ boards ”. the term “ board ” is used broadly and encompasses electronic assemblies , regardless of shape and function , that are part of an electronic system to perform a one or more functions , including but not limited to , processing , communication , or other functions generally found in electronic systems . in at least one embodiment , the boards can be the same board used at multiple locations , for example , to communicate on different aspects of the system &# 39 ; s status . the term “ communication bus ” is used broadly and includes any system or method of communication between multiple electronic assemblies in an electronic system . the communication bus provides an interconnectivity between multiple portions of the electronic system and enables the electronic system to perform its intended function . in at least one embodiment , the system 2 is designed to accept the boards at predetermined mounting locations 8 a , 8 b , 8 c ( generally “ 8 ”) and provide mounts , so that the boards can be mounted therewith . in at least one embodiment , the system 2 includes one or more system mounts 10 . the system mounts are in a constant spacing relative to each other . similarly , the board 4 has a plurality of board mounting openings 12 to align with the system mounts 10 . alignment between the mounts 10 and the openings 12 is a constant . while in at least one embodiment , the mounts are on the system and the openings are formed in the boards , it is understood that the mounts can be formed on the board and the openings on the system , or a combination thereof . generally , the arrangement of the mounts 10 and the openings 12 will be asymmetric , so that the board can be mounted in only one orientation relative to the mounts . this single alignment further reduces needed instructions and operator error . at least one conductive fastener 14 can couple the board 4 with the system 2 by use of the mounts 10 and openings 12 . the term “ fastener ” is used broadly and includes any device or system that can be used to couple two elements together . for example , a fastener can be a screw , wire , clasp , protrusion , receiver , or other coupling device , whether conductive or non - conductive . in some embodiments , a conductive standoff 18 , also shown in fig3 , can be used . the conductive fastener also forms a mounting conductive path between the board 4 and the system 2 . in a preferred embodiment , the indicated location and / or function of the board 4 ( the “ identity ” of the board ) to the system depends simply on which opening ( s ) in the board and mounts of the system are used to couple therebetween . further , in at least one embodiment , the conductive fastener can assist is forming a ground connection between the board and the system . multiple conductive fasteners can be used , such as at diagonals , but it is believed such will complicate the mounting and thus complicate the easily established identity of the board with the system . to change the indicated identity of the board 4 to the system 2 , the conductive fastener 14 can be simply moved to a different board mounting opening 12 in conjunction with the corresponding system mount 10 relative to other mounts at that location 8 . the board and / or system recognizes the different location of the mounting conductive path and establishes a different identity for the board relative to the system . in at least one embodiment , the position of the board can be uniquely identified by only one mounting conductive path , for example , if the board is mountable in only one orientation . further , in at least one embodiment , other board mounting opening ( s ) 12 and the corresponding system mount ( s ) can be coupled by non - conductive fastener ( s ) 16 and / or non - conductive standoff ( s ) 20 . fig2 is a top perspective schematic view of one embodiment of the electronic assembly . fig3 is a top perspective schematic view of the electronic assembly of fig2 , illustrating an arrangement of standoffs between the board 4 and the system 2 . the figures will be described in conjunction with each other . the board 4 generally has a plurality of board mounting openings 12 . the coupling of a particular board mounting opening 12 in conjunction with a corresponding system mount 10 , shown in fig1 a , can be used to establish the identity of the board with the system 2 . to assist in maintaining proper orientation of the board 4 , the board mounting openings 12 can be asymmetric to allow only one mounting orientation relative to the system mounts 10 . in at least one embodiment , the same board 4 can be used in multiple locations in the system 2 ( fig1 ). however , different mounting positions of a conductive fastener 14 through the use of different board mounting openings 12 and corresponding system mounts 10 establishes different identities for the board in different locations . other board mounting openings 12 can be used to couple the board 4 to the system 2 with other corresponding system mounts 10 through one or more non - conductive fasteners 16 . in general , standoffs can be used with the fasteners to separate the board 4 from unintentional contact with the system 2 . for example , a conductive standoff 18 will generally be used with the conductive fastener 14 and a non - conductive standoff 20 will generally be used with a non - conductive fastener 16 . thus , a combination of non - conductive standoffs 20 and conductive standoffs 18 on the board in conjunction with different board mounting openings and their corresponding system mounts can affect the identity of the board . when the arrangement of the conductive path is known by use of fasteners and / or standoffs , no complicated instructions or onsite changes are necessary . generally , the factory designs the system 2 with one or more appropriate locations of the board 4 in the system . system mounts 10 are formed in the system at the appropriate locations to receive the boards 4 . in at least one embodiment , the factory advantageously provides conductive and non - conductive standoffs preassembled to the system mounts 10 that correspond to the appropriate arrangement and intended identity of the board 4 for that location . alternatively , the factory can provide the standoffs preassembled to the board in the proper arrangement to assist in establishing an identity for the board . further , the standoffs can be provided separately with instructions such as a diagram of the proper arrangement of standoffs for the particular location of the board relative to the system . still further , standoffs need not be used , if additional contact between the board and the system will not adversely affect the identity of the board . minimal directions need be given to the installer to couple the board with the system . the same board can be used in multiple locations , where the installer can install a conductive fastener to couple the board 4 with the system 2 using the proper opening . the proper opening can be readily identified by the presence and / or absence of the conductive standoff ( s ), if provided , or by a diagram or other indicia indicating the intended location of the fastener ( s ) for the particular board identity relative with the system . the particular arrangement of standoffs and / or fasteners when the board 4 is coupled to the system 2 establishes the board identity in the system . fig4 is a top perspective schematic view of the electronic assembly of fig2 , illustrating an alternative arrangement of a mounting conductive path between the board and the system . for example , the mounting conductive path can be made through the conductive fastener 14 in conjunction with a different mount relative to the other mounts at a location . the different relative mount compared to the mount used by the conductive fastener in fig2 establishes a different identity for the electronic assembly at that location . in this disclosure , the board 4 can be the same board as in fig2 and 3 and even perform the same function , including but not limited to , monitoring , communicating , sensing the status of system components at different locations . by the term “ same ”, the multiple boards have the same critical mounting configuration and generally the same critical hardware , firmware , and / or circuitry , even though some differences , such as notches , colors , accessories , and markings can be present . however , the identification of the board in the system generally can be established by the simple location of the mounting conductive path between the board and the system . various basics of the invention have been explained herein . the various techniques and devices disclosed represent a portion of that which those skilled in the art would readily understand from the teachings of this application . variations are possible and contemplated and are limited only by the claims . details for the implementation thereof can be added by those with ordinary skill in the art . such details may be added to the disclosure in another application based on this provisional application and it is believed that the inclusion of such details does not add new subject matter to the application . the accompanying figures may contain additional information not specifically discussed in the text and such information may be described in a later application without adding new subject matter . additionally , various combinations and permutations of all elements or applications can be created and presented . all can be done to optimize performance in a specific application . the various steps described herein can be combined with other steps , can occur in a variety of sequences unless otherwise specifically limited , various steps can be interlineated with the stated steps , and the stated steps can be split into multiple steps . unless the context requires otherwise , the word “ comprise ” or variations such as “ comprises ” or “ comprising ”, should be understood to imply the inclusion of at least the stated element or step or group of elements or steps or equivalents thereof , and not the exclusion of any other element or step or group of elements or steps or equivalents thereof . further , any documents to which reference is made in the application for this patent as well as all references listed in any list of references filed with the application are hereby incorporated by reference . however , to the extent statements might be considered inconsistent with the patenting of this invention such statements are expressly not to be considered as made by the applicant ( s ). also , any directions such as “ top ,” “ bottom ,” “ left ,” “ right ,” “ upper ,” “ lower ,” and other directions and orientations are described herein for clarity in reference to the figures and are not to be limiting of the actual device or system or use of the device or system . the device or system may be used in a number of directions and orientations . | 8 |
the preferred embodiment illustrated is not intended to be exhaustive or to limit the invention to the precise form disclosed . it is chosen and described in order to best explain the principles of the invention and its application and practical use to thereby enable others skilled in the art to best utilize the invention . as shown in the drawings , lock 10 is used in an article 12 . article 12 is fitted with a flexible cover 14 . the flexibility of cover 14 is allowed by hinged tambour slats 16 . slats 16 are continuous on one side 18 . the other side 20 of slats 16 is bevelled to form openings 22 therebetween . cover 14 is fitted at each end into a track 24 formed within spaced end walls 25 of article 12 . article 12 can be a storage or similar cabinet . track 24 includes a guide channel part 27 . lock 10 includes a keyed actuator 26 which forms a part of a lock cylinder 28 . cylinder 28 is inserted into a bore 30 formed in one end wall 25 of article 12 . cylinder 28 has a spring biased , retractable latch 32 . a pin 36 extends transversely from cylinder 28 of lock 10 . pin 36 extends through a transverse slot 38 in wall 25 and intersects track 24 in the wall . pin 36 is shiftable longitudinally within slot 38 and track 24 upon movement of cylinder 28 as seen in fig4 and 5 . a spring 34 is fitted into bore 30 between cylinder 28 and wall 25 to urge the cylinder from its retracted or locking position shown in fig4 into its extended or open position shown in fig5 . a pin 40 extends through wall 25 in front of latch 32 . to lock , cylinder 28 is pushed into bore 30 compressing spring 34 until latch 32 springs into an enlarged portion 31 of bore 30 behind pin 40 . pin 36 carried by cylinder 28 is now located within track 24 . to open , a key is inserted into actuator 26 and turned to withdraw latch 32 from bore portion 31 and allow spring 34 to move the cylinder to its open position and to shift pin 36 from track 24 . this allows free movement of cover 14 within the track . pin 36 prevents cylinder 28 from being removed entirely from end wall bore 30 . to lock cover 14 in a predetermined position , cylinder 28 is shifted into its locked position so that pin 36 fits within a selected opening 22 between slats 16 of cover 14 . as shown in fig6 pin 36 can also be positioned to prevent the leading edge 15 of cover 14 from passing along track 24 . it is to be understood that the invention is not to be limited to the preceding description , but may be modified within the scope of the appended claims . | 8 |
the preferred embodiment of the present invention will be discussed hereinafter in detail with reference to the accompanying drawings . in the following description , numerous specific details are set forth in order to provide a thorough understanding of the present invention . it will be obvious , however , to those skilled in the art that the present invention may be practiced without these specific details . in other instance , well - known structures are not shown in detail in order to unnecessary obscure the present invention . at first , the first embodiment of the present invention will be described . fig1 is a block diagram showing a structure according to the first embodiment and the second embodiment . referring to fig1 the first embodiment of the present invention comprises a user terminal device 10 , a map information providing device 20 , and a network 30 such as the internet for connecting both with each other . the user terminal device 10 is an information processing device , for example , like a personal computer , which comprises an access / input unit 11 such as a keyboard or a pointing device for entering necessary information through access to the map information providing device 20 , a display unit 12 such as a liquid crystal display for receiving and displaying the information sent from the map information providing device 20 , and a destination identification information storing unit 13 for temporarily storing the identification information of a destination a user selects from retrieved list information . the map information providing unit 20 is an information processing device , for example , such as a workstation server , which comprises a destination identification information retrieving unit 21 , a destination identification information storing unit 22 , a billing checking unit 23 , a billing processing unit 24 , a map information creating / sending unit 25 , a map information database 26 , a pay destination database 27 , and a user billing information database 28 . the destination identification retrieving unit 21 retrieves the identification information of a destination from the map information database 26 according to a retrieval condition of the destination sent from the user terminal device 10 . the retrieval condition sent from the user terminal device 10 may be specified , for example , by a single item of the name ( company name , shop name , and the like ), address , zip code , area , and business type , or by a combination of some items ( a combination of xx department store and tokyo or a combination of indian restaurant and sinjuku ). the identification information of a destination retrieved according to the above retrieval condition is the information including , for example , the name of a destination , the address , and the telephone number . when xx department store ginza , shibuya , and ikebukuro are found as the result of retrieval according to the retrieval condition of xx department store and tokyo , the name , the address , and the telephone number of each shop are sent to the user terminal device 10 as the identification information of the retrieval result . the destination identification information storing unit 22 receives and stores the identification information of the destination a user selects after the identification information of the retrieval result is sent to the user terminal device 10 by the destination identification information retrieving unit 21 . the billing checking unit 23 retrieves the pay destination database 27 based on the identification information of the destination a user selects , and checks whether the destination is a pay destination or a free destination . when it is a pay destination , it retrieves the user billing information database 28 based on a user id number received from the user terminal device 10 , so to check whether or not this user is under a contract of monthly fixed charge , thereby deciding whether the map display this time should be charged or not . the free destination means the public facilities and the shops and companies paying for the contract fee , while the pay destination means the destination a map information provider originally adds to a map . the billing processing unit 24 bills a user under a contract of monthly fixed charge once a month ( for example , at the end of a month ), and bills some other user for a predetermined charge every time providing him or her with the map information of a pay destination . in this case , a charge may be fixed , depending on the number of the pay destinations or regardless of the number of the pay destinations . the details of the payment from a user &# 39 ; s account of a financial institute are well known , and the description thereof is omitted because it is not the purpose of the present invention . the map information creating / sending unit 25 retrieves the map information database 26 according to the identification information of the destination sent from the user terminal device 10 , to receive the map information corresponding to the destination , and provides it to the user terminal device 10 . the map information database 26 stores map image data in correspondence with the map number and the coordinate number , as the map information , and stores the name of each pay destination and free destination displayed on a map , in correspondence with the items of address , zip code , area , and business type , as well as with the map number and the coordinate number . as the map image data , that one including the pay destinations ( the destinations a map information provider originally adds to a map ) and the free destinations ( public facilities , and the shops and companies paying for the contract fee ) is created and stored in the map information database 26 . the pay destination database 27 stores the identification information of the pay destinations ( the name of a destination , the address , the telephone number , and the like ). this information is decided by a map information provider and registered into the pay destination database 27 in advance . on the contrary to the free destinations that are the shops and the companies with which a map information provider makes a contact to be published on a map and which pay for the contract fee , the pay destinations are destinations which a map information provider originally adds to a map , without making a contact with anyone or without income of the contract fee , and instead , a charge of use can be collected from a user when providing the user with the map information of a pay destination . thus , a map information provider can improve income and a user can find his or her destination more easily in the wider range of the retrieval objects . the user billing information database 28 stores the respective billing information corresponding to the user id number for every user . the billing information means the information whether or not the billing for a user &# 39 ; s receiving the map information of a pay destination is under a contract of monthly fixed charge and the settlement information including the account number of a financial institution and the amount of a bill . this time , an operation according to the first embodiment of the present invention will be described with reference to fig1 and fig2 . fig2 is a flow chart showing the operation of the first embodiment of the present invention . in the following description , assume that the network 30 is the internet . a user gains access to the home page opened by a map information provider on the network 30 from the access / input unit 11 and enters the retrieval condition of a destination whose map information a user wants to display ( step a 1 of fig2 ). the destination identification information retrieving unit 21 of the map information providing device 20 receives the retrieval condition entered in step a 1 , retrieves the identification information of the destination from the map information database 26 according to the retrieval condition , and sends the list information of the retrieval result to the user terminal device 10 ( step a 2 ). a user selects the destination he or she wants , from the list information of the received retrieval result , through the access / input unit 11 of the user terminal device 10 , and stores the selected identification information into the destination identification information storing unit 13 ( step a 3 ). when the selection of the destination is finished , the user enters the user id number through the access / input unit 11 ( step a 4 ) and pushes , for example , a complete button on the home page , hence to send the identification information of the destination stored in the destination identification information storing unit 13 in step a 3 and the user id number entered in step a 4 to the map information providing device 20 , before deleting the identification information of the destination identification information storing unit 13 ( step a 5 ). since the user id number is the number to be given to every user after a billing contract with a user to receive a map information service of the pay destinations , a user who is not under the contract cannot enter anything at this time . therefore , on the home page , there is displayed a message to the effect that a user who has not made a billing contract to receive the map information service of the pay destinations doesn &# 39 ; t have to enter the user id number . the billing checking unit 23 of the map information providing device 20 temporarily stores the identification information of the received destination into the destination identification information storing unit 22 , and retrieves the pay destination database 27 to check whether the identification information of the received destination corresponds to a pay destination . then , it stores the destination identification information with specification of a free destination or a pay destination , into the destination identification storing unit 22 ( step a 6 ). when the destination proves to be a pay destination as the retrieval result in step a 6 , the billing checking unit 23 confirms whether the user id number has been sent from the user terminal device 10 ( step a 7 ), and when it is a free destination , this step will be advanced to step a 20 . when it proves that the user id number has been sent in step a 7 , this step will be advanced to step a 15 , while when it has not been sent , contract screen information for the map information service of the pay destinations is sent to the user terminal device 10 ( step a 8 ). the contract screen information is displayed on the user terminal device 10 , and there is displayed a message to the effect that a billing contract is necessary because the destination a user selects is a pay destination ( step a 9 ). this induces a user to select whether or not to make a billing contract to receive the map information service of the pay destinations ( step a 10 ). when a user selects that he or she doesn &# 39 ; t make a billing contract in step a 10 , the user enters the contract data through the access / input unit 11 ( step a 11 ). the contract data means the information whether billing for receiving a map information service of the pay destinations is under a contract of a monthly fixed charge and the settlement information including the account number of a financial institution for drawing a charge . the billing checking unit 23 creates a user id number newly by receiving the contract data from the user terminal device 10 and sends the same number to the user terminal device 10 ( step a 12 ). the user terminal device 10 displays the sent user id number ( step a 13 ), thereby enabling a user to use this user id number at the next access to the map information providing device 20 and the later . continuously to step a 12 , the billing checking unit 23 registers the contract data sent from the user terminal device 10 into the user billing information database 28 in correspondence with the user id number ( step a 14 ). thereafter , the billing checking unit 23 checks the necessity of billing , referring to the contract data including the information whether the billing for receiving the map information service of the pay destinations is under a contract of a monthly fixed charge ( step a 15 ). in the case of the contract of the monthly fixed charge , it decides that the billing is not necessary because it should not be required every time , and this step is advanced to step a 20 . on the other hand , when the billing is not under a contract of a monthly fixed charge , it decides that the billing is necessary because it should be required every time , and sends a message to the effect that you are charged , for example , your charge is δδ yen , to the user terminal device 10 ( step a 16 ). the user terminal device 10 displays the message to the effect that you will be charged ( step a 17 ), and a user enters whether he or she pays for the charge or not ( step a 18 ). when the user selects no in step a 18 , the connection is broken ; when the user selects yes , the billing checking unit 23 registers a predetermined charge in the user billing information database , as the data on the amount of a bill corresponding to the user id number of this user , and passing the user id number to the billing processing unit 24 , asks the unit 24 for the billing processing . the billing processing unit 24 performs the billing processing for drawing a charge from a user &# 39 ; s account with reference to the user billing information database 28 ( step a 19 ). since this drawing processing of a charge from a user &# 39 ; s account of a financial institution is well known and it is not the purpose of the present invention , the detailed description is omitted here . the map information creating / sending unit 25 retrieves the map information of a destination from the map information database according to the identification information of the destination temporarily stored in the destination identification information storing unit 22 , continuously to steps a 6 , a 15 , and a 19 , sends it to the user terminal device 10 , and thereafter , deletes the identification information of the destination temporarily stored in the destination identification information storing unit 22 ( step a 20 ). the user terminal device 10 displays the map information of the destination on the display unit 12 ( step a 21 ). the second embodiment of the present invention will be described in detail with reference to the drawings . this embodiment is different from the first embodiment of the present invention in that a plurality of destinations are displayed on the same map . in the first embodiment , since each destination is displayed one by one , if a user selects no payment for the charge of a pay destination , the connection will be broken . in the second embodiment , however , if a user selects no payment for the charge , the map information excluding the pay destinations from a plurality of destinations will be provided , differently from the first embodiment . the structure of the second embodiment is almost the same as that of the first embodiment shown in fig1 . in detail , however , the following points are added to the map information creating / sending unit 25 and the map information database 26 . when a user selects no payment for the charge of a pay destination , the map information creating / sending unit 25 provides the user terminal device 10 with the map information excluding the display of the pay destinations . as described later , the pay destinations are distinguishable from the free destinations , for example , in the color of display and the form of a character . accordingly , the data corresponding to the above can be deleted distinguishably , thereby providing the user terminal device 10 with the map information excluding the pay destinations . the map information creating / sending unit 25 includes processing means ( function ) for retrieving each map number or each map coordinate number of the respective map information in the identification information of a plurality of destinations from the map information database and calculating each map number or map coordinate number including all the map information . for example , when the map coordinate number of the first destination is x2 / y3 and the map coordinate number of the second destination is x4 / y5 , it derives x2 to x4 / y3 to y5 . therefore , the unit 25 sends the map information of a rectangular area ranging from x2 to x4 in the horizontal axis and from y3 to y5 in the vertical axis to the user terminal device 10 , and a user can see the map information including both the first and the second destinations . the map information database 26 creates and stores the map information including both the pay destinations and the free destinations , and the pay destinations are displayed in a distinguishable way from the free destinations , for example , in the color of display and the form of a character . the operation of the second embodiment of the present invention will be described with reference to fig1 to 3 . fig3 is a flow chart showing the operation of the second embodiment of the present invention . the operation of the second embodiment in fig3 is different from that of the first embodiment in fig2 in that in fig3 step b 4 and step b 20 are added to fig2 . the others are almost the same . for the sake of preventing the overlap of the description , the different portions are described here . the reference marks ( a 1 ), ( a 2 ), and the like in fig3 indicate the respective steps corresponding to those in fig2 and for example , the case of b 1 ( a 1 ) shows that step b 1 in fig3 corresponds to step a 1 in fig2 . in the added step b 4 , whether or not there is any other destination to be retrieved is checked . if there is , the operation of steps b 1 to b 3 ( corresponding to steps a 1 to a 3 in fig2 ) is repeated . thus , the identification information of several destinations selected is stored in the destination identification storing unit 13 . in step b 7 , whether all the received destinations are out of charge or not is checked , and if there is even only one pay destination , this step will be advanced to step b 8 . in step b 20 , the map information creating / sending unit 25 creates the map information excluding the pay destinations and sends the same information to the user terminal device 10 when a user answers that he or she doesn &# 39 ; t make a contract for use in step b 11 or when a user answers that he or she doesn &# 39 ; t pay for the charge in step b 19 . at this time , the map information creating / sending unit 25 retrieves each map number or each map coordinate number of the respective map information from the map information database 26 , out of the identification information of the free destinations stored in the destination identification information storing unit 22 , calculates the map numbers or the map coordinate numbers including all the map information , and receives the map information including all the free destinations from the map information database 26 . for example , by deleting the data indicated in the color of display or the form of a character used for displaying the pay destinations , from the map information , the map information excluding the pay destinations is created . in step b 22 , the map information creating / sending unit 25 creates the map information excluding all the destinations and sends the same information to the user terminal device 10 . at this time , the map information creating / sending unit 25 retrieves each map number or each map coordinate number of the respective map information from the map information database 26 , out of the identification information of the pay destinations and the free destinations stored in the destination identification information storing unit 22 , calculates the map numbers or the map coordinate numbers including all the map information , receives the map information including all the destinations from the map information database 26 , and sends the same information to the user terminal device 10 . the third embodiment of the present invention will be described in detail with reference to the drawings . this embodiment is different from the second embodiment of the present invention in that the information of a reference point such as a user &# 39 ; s house and a user &# 39 ; s current position is further added and that the reference point and one or several destinations are displayed on the same map . [ 0144 ] fig4 is a block diagram showing a structure of the third embodiment . the structure of this embodiment is different from the first embodiment shown in fig1 in that a reference point registering unit 14 is further added to the user terminal device 10 of fig1 . according to this , the information of the reference point is respectively added to the destination identification information retrieving unit 21 and the destination identification information storing unit 22 of fig1 which are changed to the destination / reference point identification information retrieving unit 21 a and the destination / reference point identification storing unit 22 a . an operation according to the third embodiment of the present invention will be described with reference to fig4 to 6 and fig3 . at first , the registering operation of a reference point will be described in detail with reference to fig5 . fig5 is a flow chart showing the registering operation of a reference point in the third embodiment of the present invention . a user gains access to the home page opened by a map information provider on the network 30 , through the access / input unit 11 from the user terminal device 10 a and enters the address information or the retrieval condition of the reference point whose map information the user wants to display ( step k 1 of fig5 ). the destination / reference point identification information retrieving unit 21 a of the map information providing device 20 a receives the address information or the retrieval condition entered in step k 1 , retrieves the identification information of a reference point from the map information database 26 according to this address information or retrieval condition , and sends the list information of the retrieval result to the user terminal device 10 a ( step k 2 ). a user selects a reference point he or she wants from the list information of the received retrieval result , through the access / input unit 11 of the user terminal device 10 a , and stores the selected identification information into the reference point registering unit 14 ( step k 3 ). thereafter , if there is a reference point the user wants to register , step k 1 to step k 3 will be repeated ( step k 4 ). this time , the operation of the third embodiment of the present invention will be described in detail with reference to fig4 to fig6 . fig6 is a flow chart showing the operation of the third embodiment of the present invention . the operation of the third embodiment in fig6 is different from the operation of the second embodiment in fig3 in that , in fig6 step c 5 is added to fig3 . the others are almost the same and therefore , in fig6 only the portion different from that of fig3 will be described . the reference marks ( b 1 ), ( b 2 ), and the like in fig6 indicate the respective steps corresponding to those in fig3 and for example , the case of c 1 ( b 1 ) indicates that step c 1 in fig6 corresponds to step b 1 in fig3 . in the added step c 5 , the identification information of a reference point a user wants is selected from the identification information of the reference points previously registered in the reference point registering unit 14 by the registering operation shown in fig5 . thereafter , the user id number is entered in step c 6 , and the reference point , the identification information of the destination , and the user id number are sent to the map information providing device 20 a in step c 7 . in creating the map information in step c 21 and c 23 , the map information creating / sending unit 25 creates the map information including both the reference point and the destination . the fourth embodiment of the present invention will be described in detail with reference to the drawings . [ 0156 ] fig7 is a block diagram showing a structure of the fourth embodiment of the present invention , which comprises a computer 40 and a recording medium 50 . the structure of the computer 40 is fundamentally the same as that of the map information providing device 20 of fig1 described in the first embodiment of the present invention . the recording medium 50 stores a map information providing program . the recording medium 50 may be realized by a magnetic disk , an optical recording disk , a semiconductor memory , or the other recording medium . the map information providing program is read by the computer 40 from the recording medium 50 , and the same operation as that of the first embodiment of the present invention can be realized by controlling the computer 40 . the fifth embodiment of the present invention will be described in detail with reference to the drawings . [ 0158 ] fig7 is a block diagram showing a structure of the fourth and the fifth embodiments of the present invention , which comprises the computer 40 and the recording medium 50 . the structure of the computer 40 is fundamentally the same as that of the map information providing device 20 of fig1 described in the second embodiment of the present invention . the recording medium 50 stores the map information providing program . the recording medium 50 may be realized by a magnetic disk , an optical recording disk , a semiconductor memory , or the other recording medium . the map information providing program is read by the computer 40 from the recording medium 50 , and the same operation as that of the second embodiment of the present invention can be realized by controlling the computer 40 . the sixth embodiment of the present invention will be described in detail with reference to the drawings . [ 0160 ] fig8 is a block diagram showing a structure of the sixth embodiment of the present invention , which comprises a computer 60 and a recording medium 70 . the structure of the computer 60 is fundamentally the same as that of the map information providing device 20 a of fig4 described in the third embodiment of the present invention . the recording medium 70 stores a map information providing program . the recording medium 70 may be realized by a magnetic disk , an optical recording disk , a semiconductor memory , or the other recording medium . the map information providing program is read by the computer 60 from the recording medium 70 , and the same operation as that of the third embodiment of the present invention can be realized by controlling the computer 60 . in the above - mentioned first to sixth embodiments , although the pay destination database 27 is provided separately from the map information database 26 , the pay destination database 27 may be deleted , and the information of the pay destinations and the free destinations may be attached to the identification information of the map information database 26 . in the above - mentioned first to sixth embodiments , the registration of the user id number may be performed as soon as a user gains access to the home page from the user terminal device 10 . in the above - mentioned first to sixth embodiments , although any mark ( marking ) is not attached to the destinations and the reference points on the map information , the map information creating / sending unit 25 may be provided with means ( function ) of attaching the marking data to the map information , thereby providing the map information convenient for a user to see . further , in the above - mentioned second , third , fifth , and sixth embodiments , the map information including the free destinations and the pay destinations distinguishable from each other in the color of display and the form of a character is created and stored as the map information in the map information database 26 , and the map information creating / sending unit 25 controls the delete of the data about the pay destinations . otherwise , two kinds of the map information ; one including both the data of the pay destinations and the free destinations and the other excluding the data of the pay destinations may be stored in the map information database 26 , although its capacity becomes large , and the map information creating / sending unit 25 may select one of them . in the above - mentioned second , third , fifth , and sixth embodiments , the retrieval whether a destination is the pay destination or the free destination may be also performed in step b 2 of fig3 and in step c 2 of fig6 and when a user selects a destination in step b 3 of fig3 and step c 3 of fig6 and the destination is the pay destination , a message to this effect may be displayed , so as to inform it to a user in advance . in the description of the above - mentioned third and sixth embodiments , although the registration of a reference point is performed in advance , as illustrated in fig5 the retrieval of a reference point may be performed every time continuously to the destination retrieval of fig6 instead of selecting one from the reference points previously registered like in step c 5 of fig6 . according to the present invention , not only the destinations of the shops and the companies from which a map information provider receives the contract fee , are provided free of charge , but also the destinations the map information provider originally adds , are provided with a charge . therefore , it is effective in that a map information provider can expect an increasing income and that a user can find a destination more easily according to the wider range of the retrieval objects . according to the present invention , since a plurality of destinations are displayed on the map , it is effective in that a user can grasp the distance and positional relation more easily . according to the present invention , since a plurality of destinations , a user &# 39 ; s current position , and a reference point such as a user &# 39 ; s house are displayed on the same map , it is effective in that a user can grasp the distance and positional relation more easily . although the invention has been illustrated and described with respect to exemplary embodiment thereof , it should be understood by those skilled in the art that the foregoing and various other changes , omissions and additions may be made therein and thereto , without departing from the spirit and scope of the present invention . therefore , the present invention should not be understood as limited to the specific embodiment set out above but to include all possible embodiments which can be embodies within a scope encompassed and equivalents thereof with respect to the feature set out in the appended claims . | 6 |
in the prior art construction of fig1 and the inventive construction of fig2 the cylindrical valve chamber 2 or 4 is in the form of a cylindrical circular bore of casing surface 6 , 8 of a rotary piston compressor and is directed parallel to the rotation axis thereof . a plurality of uniformly spaced , slot - like valve intakes 14 , 14 &# 39 ; in the form of an axially directed row pass into the valve chamber 2 or 4 , as indicated by broken lines 14 , 14 &# 39 ; in fig3 from the surface path 10 or 12 of the compressor and / or from its compression chamber . it is obvious that a single intake can replace said plurality of intakes . when the valve is closed each intake 14 , 14 &# 39 ; is covered by the circumferential region of a circular spring leaf 16 or 18 , which sealingly engages in the area of the inner wall of valve chamber 4 surrounding the openings . a comparison of fig1 and 2 shows that in the prior art construction , the spring leaf 16 engages with a relatively larger circumference of the chamber inner wall , this necessarily resulting from the use of a spring leaf 16 which is flat in the untensioned state and which only assumes a circular configuration through its mounting in the cylindrical valve chamber . the free oppositely directed ends 20 , 22 are supported on the cylindrical chamber inner wall or in the hook - shaped ends 24 , 26 of a ω - shaped lift guard 28 , so that they are directed at an angle to a tangent of the chamber inner wall . it has been found that through the engagement of said spring leaf 16 with a relatively large circumferential region of the chamber inner wall there is support on the latter under the restoring force of the spring leaf and as a result said leaf cannot deflect in an unhindered manner under the pressure of the inflowing medium , so that the deflection is limited to a relatively narrow circumferential region in the vicinity of an intake 14 , as indicated by broken line 30 in fig1 . line 30 shows the valve is in its maximum open position in which a further deflection of the spring leaf 16 is limited by the lift guard 28 . the inward deflection in a narrow circumferential region leading at this point to a concave shape of the spring leaf causes increased bending stress at points 32 , 34 where the spring leaf curvature passes from a convex into a concave shape , resulting in early fatigue failure in the case of prolonged alternating loading when used on a compressor . to make this clearer , the deflection in accordance with line 30 and the maximum open position of the valve have been shown in an exagerated form . however , said overstressing even occurs with deflections of fractions of a millimeter . after the spring leaf in the region of intake 14 has lifted from the chamber inner wall under the pressure of the compressed medium , the latter can flow radially into valve chamber 2 or 4 , whereby it is axially deflected so that it flows through the chamber to an outlet located at one end thereof and which can have the cross - sectional size of the valve chamber . the axial flow takes place in part in the gap between the chamber inner wall and the spring leaf , as well as radially past the laminations 16a to 16e or 18a to 18e of the spring leaf 16 or 18 to the central area of the valve chamber , before finally being axially led away to the outlet . the dividing up of the valve intake into a plurality of slot - like intakes 14 , 14 &# 39 ; arranged in rows and the gaps 36 between the individual laminations permit the flowing in of the medium to the central area of the valve chamber even when the valve has a relatively large axial extent . in the prior art construction of fig1 it is obvious that lateral slot - like openings 38 , 40 are provided in lift guard 28 through which extend in an arcuate manner the individual laminations of spring leaf 16 . the valve according to the invention of fig2 fundamentally operates in the same way as that of fig1 but it has a differently shaped and dimensioned spring leaf 18 , having a different deformation behaviour . even in the untensioned state , i . e . before incorporating into the cylindrical valve chamber 4 , the spring leaf 18 is shaped like a cylindrical sleeve with an axial slit bounded by the oppositely directed leaf ends 42 , 44 . however , when uncoiled flat the spring leaf 18 can have the same shape as the spring leaf 16 of the valve of fig1 as shown in fig3 . in the fitted state , the axial slit is expanded somewhat , so that the leaf ends 42 , 44 embrace under pretension a web - shaped projection 46 of a spacer 48 fixed to the inner wall of valve chamber 4 diametrically opposite to the row of openings 14 &# 39 ;. the outer circumferential surface of leaf ends 42 , 44 engage with limited pretension on the surfaces 50 , 52 of spacer 48 running on both sides to the web - like projection 46 and with this pretension the area of the spring leaf facing the axial slit sealingly engages on the rim 54 surrounding openings 14 &# 39 ; and therefore on the inner wall of the chamber . as soon as a pressure acts in intakes 14 which is greater than the pressure in the valve chamber 4 and the contact pressure of the spring leaf , the latter rises from rim 54 , so that it is only in contact with spacer 48 . it is not possible to prevent the deformation of the circular spring leaf due to engagement on the chamber inner wall , because the spring leaf diameter is smaller than the cylindrical valve chamber diameter . in fig2 the shape of the spring leaf 18 when the valve is open is indicated by a broken line . a lift stop is not necessary because in the case of too great a deformation of the spring leaf , the latter is supported on the chamber inner wall on two opposite sides and the arcuate spring leaf portion between the support points forms a high resistance to further deformations . it is obvious that in the untensioned state , the spring leaf can have different circular shapes and the valve chamber can also have different cross - sectional shapes , such as e . g . elliptical , oval , etc . it is important that the spring leaf only engages with the chamber inner wall along the opening rim 54 permitting an elastic deformation of the spring leaf which is not impeded by the chamber inner wall . this reliably obviates the disadvantages of a valve according to fig1 . although it is not necessary , a lift stop can also be used in the valve according to the invention . the spring leaf can be made from steel sheet material , whose thickness is such that over the intakes 14 &# 39 ; it does not deform in a non - circular shape . | 8 |
reference is now made to fig1 which is a simplified conceptual illustration of system for model - driven application development , constructed and operative in accordance with an embodiment of the present invention . in the system of fig1 , a model , generally designated 100 and bounded by dashed lines , is shown . model 100 is typically constructed using a model builder 102 employing any known modeling technology , such as the unified modeling language ( uml ), that supports classes , such as of an enterprise it infrastructure or other system , and associations between the classes . model 100 is configured to facilitate the automatic generation of one or more resources , such as by a resource generator 110 , for use by one or more computer - executable applications . such resources may be associated with what is referred to in modeling as the persistence layer , which includes schema elements including tables , columns , foreign keys , and indexes , or may be associated with the api , as is known in the art . model 100 is divided into a principal model 104 , a decoration model 106 , and a model map 108 that maps between principal model 104 and decoration model 106 . principal model 104 is configured to include anything that , when added to , deleted from , or modified within principal model 104 subsequent to automatically generating the resources , would again require the automatic generation of the resources in order to effect the change for use by an application . conversely , decoration model 106 is configured to include anything that , when added to , deleted from , or modified within decoration model 106 subsequent to automatically generating the resources , would not require the automatic generation of the resources in order to effect the change for use by an application . model 100 is preferably stored in a model storage 112 , which may be computer memory , magnetic storage , or any other suitable information storage medium . model 100 may be stored in storage 112 in any suitable format , such as in a relational database ( rdb ) or object - oriented database ( oodb ). any of the elements shown in fig1 are preferably executed by or otherwise accessible to a computer 114 . principal model 104 preferably includes elements for storing decoration model 106 , such as a via “ decorationmodel ” class representing a package of the items in decoration model 106 . there is preferably one model partition per package , and each decoration model is preferably serialized , such as an xml document . reference is now made to fig2 , which is a simplified illustration of an exemplary implementation of model 100 of fig1 , constructed and operative in accordance with an embodiment of the present invention . in fig2 , a principal model 200 is shown having various modeled items . a corresponding item is created in a decoration model 202 for one or more of the items in principal model 200 . one or more items may then be attached to any of the items in decoration model 202 , rather than in principal model 200 , where their addition to , modification in , and / or subsequent deletion from decoration model 202 will not require that resources that were previously automatically generated using principal model 200 be subsequently regenerated due to the addition , modification , and / or deletion . direct association links are preferably used for navigating from items in decoration model 202 to items in principal model 200 , whereas a model map 206 is preferably used for navigating in the opposite direction . reference is now made to fig3 , which is a simplified illustration of an exemplary implementation of decoration model 106 of fig1 , constructed and operative in accordance with an embodiment of the present invention . in fig3 a decoration model is shown for aspects of a gui interface in which classes and associations / attributes are decorated by detailed gui presentation definitions , such as where there is one per user role , application / service - level constraints , and analysis logic definitions . for the sake of clarity , dpackage and dpackageguidef are not shown . dclass and dstructuralfeature are shown having been generated for each corresponding eclass / estructuralfeature of a corresponding principal model . instantiation of various concepts may be optional in a given decoration model , such as where a dclass has no dclassguidef for a certain userrole and will therefore be invisible in the gui layer for a user with that role . items in the decoration model of fig3 may be created , edited and deleted without affecting a related principal model and without requiring regeneration of resources defined by the principal model . for example , a user may set a different display name for a class or attribute in the decoration model , although dclass and dstructuralfeature items in the decoration model that correspond to eclass / estructuralfeature items in the principal model ought not be deleted . the following guidelines may be employed when deciding what model items should be included in a principal model and what model items should be included in a decoration model . model items that generally have , and should have , impact on resources that are generated based on a model should be included in a principal model , whereas model items that generally do not , or should not , have impact on resources that are generated based on a model should be included in a decoration model . model builder 102 ( fig1 ) may be configured to recognize model items that do not impact generated resources and automatically place such items into a decoration model . these guidelines may be understood by way of example with regard to the persistence layer of an application environment in which database schema and an o / r mapping are generated using a model . in this example , model items that do not impact the generation of these resources include annotations that control display and business logic , and thus these items may be included within a decoration model . model items that do impact the generation of these resources include classes , references , attributes , and annotations that control aspects of the persistence layer , such as indexes . some model items may be included within a decoration model although they would otherwise impact resource generation , such as classes , references and attributes whose instances or values can be derived from other data . thus , for example , where the attribute person . fullname can be derived from person . firstname and person . lastname , the derived attribute may be included within a principal model , such as where the attribute values for person . fullname are meant to be stored in a database . the responsibility to insert and update the values for person . fullname would lie with the applications that populate person data . although including person . fullname in a principal model may be convenient for authors of reporting applications , doing so results in data redundancy , performance costs owing to insertion time and table size , as well as the need to regenerate the schema and upgrade instances when the name or type of person . fullname is changed . alternatively , by placing person . fullname in a decoration model , the responsibility for calculating the values for person . fullname lie with applications that retrieve person data . reference is now made to fig4 , which is a simplified flowchart of an exemplary method of using a decoration model in an application environment , operative in accordance with an embodiment of the present invention . in the method of fig4 , once model 100 of fig1 has been prepared , and its principal model used to generate resources as described hereinabove , the decoration model is read from where it is stored and is instantiated for use by one or more computer - executable applications , such as may be hosted by computer 114 . when an application wishes to access an instance “ eobject ” of an item of the principal model , if the item has a corresponding item in the decoration model , the application accesses the corresponding instance “ dobject ” of the decoration model instead . calls to methods that are defined in eobject are passed through to eobject , while calls to methods that are defined in dobject are handled by dobject . for example , getrepresentation ( ): string will return a representation based on which attribute is defined as “ representation attribute ” of the corresponding dobject &# 39 ; s class in the decoration model . reference is now made to fig5 , which is a simplified flowchart of an exemplary method of hot - deploying decoration model changes , operative in accordance with an embodiment of the present invention . in the method of fig5 , once model 100 of fig1 has been prepared , and its principal model has been used to generate resources as described hereinabove , the decoration model is read from where it is stored and is instantiated for use by one or more computer - executable applications , such as may be hosted by computer 114 . the instantiated decoration model is preferably made globally accessible . for each request by an application to access an object associated with either the principal model or the decoration model , a new thread is preferably created to handle the request . the decoration model is preferably assigned to a thread - local variable in the new thread , and all thread - internal code function calls to access the decoration model do so via the thread - local variable of its thread . changes may be made to the decoration model while applications that use the model are executed . the decoration model changes may be committed without impacting currently - running applications , since the previously - instantiated decoration model was globally accessible and was reused by all request threads prior to the changes being made . the changed decoration model may be made available to new threads by starting a new thread that reads the changed decoration model , instantiates the changed decoration model , and deserializes it into its own thread - local variable . this may be done without affecting other currently - running threads . the globally accessible decoration model may then be replaced by the changed model . this is preferably done using synchronization and isolation techniques , where new incoming requests are forced to wait until the globally accessible decoration model is replaced . thereafter , all new requests will have the new decoration model assigned to their thread - local variable . older requests that are still running using the old decoration model need not be disrupted , and may return and present results according to the older decoration model in their thread - local variable . users may be warned when a model change occurs by checking for pointer equality between a thread - local variable and the globally accessible decoration model during the post - processing of a request . if the pointers are not the same , a warning may be displayed recommending that the user resubmit the request . if the server hosting the applications is restarted at any point after the decoration model is changed , the changed decoration model will preferably be in effect for all new and restarted applications . any of the elements and steps described hereinabove are preferably executed by or otherwise accessible to computer 114 ( fig1 ) having been configured for such purpose . it is appreciated that one or more of the steps of any of the methods described herein may be omitted or carried out in a different order than that shown , without departing from the true spirit and scope of the invention . while the methods and apparatus disclosed herein may or may not have been described with reference to specific computer hardware or software , it is appreciated that the methods and apparatus described herein may be readily implemented in computer hardware or software using conventional techniques . while the present invention has been described with reference to one or more specific embodiments , the description is intended to be illustrative of the invention as a whole and is not to be construed as limiting the invention to the embodiments shown . it is appreciated that various modifications may occur to those skilled in the art that , while not specifically shown herein , are nevertheless within the true spirit and scope of the invention . | 6 |
referring now to the drawings , fig3 a - 3e show , in cross section view , some structures which may be heated during ion implantation according to the method of this invention . fig3 a shows ion implant 370 being applied to partially completed fet 380 in bulk semiconductor 390 , where partially completed fet 380 comprises conductive gate 400 on gate dielectric 410 over channel region 420 separating s / d regions 430 . fig3 b shows ion implant 370 being applied to partially completed fet 450 in semiconductor - on - insulator layer 460 on box layer 470 on base substrate 480 , where partially completed fet 450 comprises conductive gate 490 on gate dielectric 500 over channel region 510 separating s / d regions 520 . the conditions of ion implant 370 would typically be selected so that at least some of s / d regions 430 and 520 would be implanted while gates 400 and 490 would protect channel regions 420 and 510 from being implanted . fig3 c shows ion implant 550 being applied to semiconductor - on - insulator substrate 560 comprising semiconductor - on - insulator layer 570 on box layer 580 on base substrate 590 . in this case , the conditions of ion implant 550 might be selected to provide a peak concentration of implanted species in base substrate 590 under box layer 580 rather than in semiconductor - on - insulator layer 570 on top of box layer 580 . such implant conditions may be useful for fabricating certain back - gated devices in which the semiconductor directly under the box functions as a back gate . fig3 c thus provides an example of how heated implants in the range from 70 ° c . to 900 ° c . may be used in fabricating fet devices in a bulk semiconductor or semiconductor - on - insulator layer so that at least some features in addition to the fet &# 39 ; s source / drain regions are implanted , since with heated implants it becomes possible to implant a high concentration of dopants into base substrate 590 without running the risk of amorphizing semiconductor - on - insulator 570 . fig3 d shows ion implant 600 being applied to partially completed fet 610 in bulk semiconductor 620 , where partially completed fet 610 comprises conductive gate 630 on gate dielectric 640 over channel region 650 separating semiconductor s / d regions 660 . semiconductor s / d regions 660 are strained and formed from a different material than channel region 650 . the conditions of ion implant 600 might be selected to provide a light doping of s / d regions 660 , but no amorphization . for example , channel region 650 might comprise si and s / d regions 660 might comprise strained sige . the force of s / d regions 660 on channel region 650 is indicated by arrows 670 . fig3 e shows the semiconductor - on - insulator analog of fig3 d . ion implant 600 is now being applied to partially completed fet 700 in semiconductor - on - insulator layer 710 on box layer 720 on base substrate 730 , where partially completed fet 700 comprises conductive gate 740 on gate dielectric 750 over semiconductor - on - insulator channel region 760 separating strained semiconductor s / d regions 770 , where arrows 780 indicate the stress exerted on channel region 760 by s / d regions 770 . patterned masking layers may be used in these hot implant processes . ideally , patterned masking layers not remaining in the final device ( i . e ., disposable masking layers ) would be formed prior to the hot implantation step and removed after the hot implantation step . these patterned masking layers would typically define first source / drain ( or other ) regions that would be subjected to the hot implantation and second source / drain ( or other ) regions that would be protected from the hot implantation . these disposable masking layers are preferably easily patterned , thermally stable , and easy to remove without damaging the underlying substrate . an example of a mask material meeting these requirements is amorphous carbon with a hydrogen content less than about 15 atomic %. this material is thermally stable and may be patterned ( as well as removed ) by oxygen - based plasma etching without damage to underlying oxide , nitride , and / or silicon substrate layers . while oxide and nitride layers are also thermally stable and perhaps more easily patterned than amorphous carbon , such materials are harder to remove selectively with respect to the substrate . multilayer masks comprising one or more upper oxide and / or nitride layers on a base layer of amorphous carbon may provide the optimum compromise between ease of patterning and selective removal . in a second embodiment of the invention , ion implantation is combined with ex situ heat treatments in a “ divided - dose - anneal - in - between ” ( ddab ) scheme . in this embodiment , the desired total dose is divided into smaller sub - doses , each of which is below the threshold for amorphizing the entire thickness of the s / d regions ( for the case of utsoi ) or generating significant strain relief ( for the case of strained s / d regions ). annealing performed after each implant restores the s / d regions to their pre - implant levels of crystallinity and / or strain before the accumulated damage reaches a level that is irreversible . depending on the implantation conditions ( species , energy , dose , ion angle of incidence , substrate temperature , etc . ), some to none of the thickness of the implanted s / d regions may be amorphized . for high - dose implants producing an amorphous layer , the between - implant anneals restore the initial crystallinity by solid phase epitaxy ; for low - dose , non - amorphizing implants , the between - implant anneals remove the incipient nucleation sites for strain - relieving dislocations before they fully develop . selecting a substrate including a semiconductor layer ; defining first semiconductor layer regions that will be subjected to at least two subsequent ion implantation steps and second semiconductor layer regions that will be protected from said at least two subsequent ion implantation steps ; subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a first ion implantation ; subjecting the substrate to a first anneal ; subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a final ion implantation ; and subjecting the substrate to a final anneal ; wherein residual damage left in the first semiconductor layer regions ( as measured by strain loss and / or defect density ) after the final anneal is less than the residual damage that would be left in the first semiconductor layer regions if the above process steps were performed without the first anneal . applying a masking layer defining the first and second semiconductor layer regions in the substrate before each implant step and removing the masking layer from the substrate before each annealing step ; or applying a masking layer defining the first and second semiconductor layer regions in the substrate before the first implant step and not removing the masking layer from the substrate until after the final implant step . the ddab method may contain any number of implant and anneal steps to achieve the desired dopant dose and profile with sufficiently low damage to the semiconductor layer regions being implanted . for more than two implant steps , the basic ddab method above would further include one or more cycles of supplemental implant and annealing steps comprising subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a supplemental ion implantation ; and subjecting the substrate to a supplemental anneal ; the cycles performed after the first anneal and before the final implant , wherein residual damage left in the first semiconductor layer regions ( as measured by strain loss and / or defect density ) after the final anneal is less than the residual damage that would be left in the first semiconductor layer regions if the above process steps were performed without the first and the supplemental annealing steps . the ddab method of ion implantation may also be implemented without regard to the final levels of semiconductor layer damage , in accord with the previously described steps of selecting a substrate including a semiconductor layer ; defining first semiconductor layer regions that will be subjected to at least two subsequent ion implantation steps and second semiconductor layer regions that will be protected from said at least two subsequent ion implantation steps ; subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a first ion implantation ; subjecting the substrate to a first anneal ; subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a final ion implantation ; and subjecting the substrate to a final anneal ; in combination with the step of applying a masking layer defining the first and second semiconductor layer regions in the substrate before the first implant step , the masking layer remaining in place until after the final implant step . this version of the ddab method may also include one or more cycles of supplemental implant and annealing steps comprising subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a supplemental ion implantation ; and subjecting the substrate to a supplemental anneal ; suitable materials for masks used with ddab are similar to those described above for hot implants . in addition , between - implant anneal temperatures of 230 ° c . and below are expected to be compatible with many patterned photoresist layers . if higher temperatures are needed ( as expected ), one may strip the resist before each annealing step and reapply it before each implant step . fig4 shows the steps of a ddab method applied to the fabrication of a utsoi fet in a cmos circuit . fig4 a shows partially completed fets 800 and 810 in utsoi layer 820 disposed on box layer 830 disposed on base substrate 840 . one of partially completed fets 800 and 810 might be an n - channel fet ( nfet ) and the other of fets 800 and 810 might be a p - channel fet ( pfet ). fets 800 and 810 comprise gates 850 and 852 and gate dielectrics 860 and 862 disposed on channel regions 880 and 882 separating s / d regions 870 and 872 . fets 800 and 810 are separated by shallow trench isolation regions 890 . fig4 b shows the structure of fig4 a after application of patterned masking layer 900 to protect fet 810 from one or more subsequent ion implants . fig4 c shows the structure of fig4 b being subjected to a first ion implant 910 which amorphizes an upper portion of s / d regions 870 of fet 800 to form amorphized s / d regions 920 which do not extend all the way down to box layer 830 . the structure of fig4 c is then annealed , allowing amorphized s / d regions 920 to recrystallize by solid phase epitaxy to form recrystallized s / d regions 930 , as shown in fig4 d . patterned masking layer 900 may remain in place during the anneal , or be removed before the anneal and replaced after the anneal . fig4 e shows the structure of fig4 d being subjected to a final ion implant 940 which may be the same as or different from first ion implant 910 . typically ion implant 940 would be the same as or very similar to ion implant 910 , with the sum of the doses of implants 910 and 940 equal to the total desired implant dose . ion implant 940 again amorphizes an upper portion of s / d regions 870 of fet 800 to form amorphized s / d regions 920 ′ which do not extend all the way down to box layer 830 . the structure of fig4 e is then annealed , allowing amorphized s / d regions 920 ′ to recrystallize by solid phase epitaxy to form recrystallized s / d regions 930 ′. activation annealing may be included in the recrystallization anneal , or performed separately . patterned masking layer 900 is removed before or after these last annealing steps to produce the structure of fig4 g . fig5 shows the steps of a ddab method applied to the fabrication of a strain - engineered fet in a cmos circuit , where the strain - engineered fet has channel strain induced by embedded s / d regions . fig5 a shows partially completed fets 1000 and 1010 in semiconductor layer 1020 disposed on box layer 1030 disposed on base substrate 1040 . one of partially completed fets 1000 and 1010 might be an nfet and the other of fets 1000 and 1010 might be a pfet . fets 1000 and 1010 comprise gates 1050 and 1052 and gate dielectrics 1060 and 1062 disposed on channel regions 1080 and 1082 separating s / d regions 1070 and 1072 . fets 1000 and 1010 are separated by shallow trench isolation regions 1090 . fig5 b shows the structure of fig5 a after s / d regions 1020 of fet 1000 have been replaced by embedded s / d regions 1100 , according to prior art methods illustrated in fig2 a - 2c . embedded s / d regions 1100 are strained and exert a stress on channel region 1080 . fig5 c shows the structure of fig5 b after application of patterned masking layer 1110 to protect fet 1010 from one or more subsequent ion implants . fig5 d shows the structure of fig5 c being subjected to a non - amorphizing first ion implant 1120 to produce lightly damaged s / d regions 1130 including many small defects indicated by circles 1140 . it is believed that defects 1140 represent damage regions that are too small or otherwise insufficient to nucleate stacking faults or other strain - relieving dislocations . the structure of fig5 d is then annealed to produce repaired s / d regions 1150 , as shown in fig5 e . patterned masking layer 1110 may remain in place during the anneal , or be removed before the anneal and replaced after the anneal . fig5 f shows the structure of fig5 e being subjected to a non - amorphizing final ion implant 1160 which may be the same as or different from first ion implant 1120 . typically ion implant 1160 would be the same as or very similar to ion implant 1120 , with the sum of the doses of implants 1120 and 1160 equal to the total desired implant dose . ion implant 1160 again produces lightly damaged s / d regions 1130 ′ including many small defects indicated by circles 1140 ′. the structure of fig5 f is then annealed to produce repaired s / d regions 1150 which still has all or most of their initial strain , as shown in fig5 g . activation annealing may be included in the recrystallization anneal , or performed separately . patterned masking layer 1110 is removed before or after these last annealing steps to produce the structure of fig5 h . another aspect of the invention provides at least one fet device in a semiconductor layer , the fet device comprising source / drain regions subjected to ion implantation while the semiconductor - on - insulator is held at an elevated temperature in the range from 70 ° c . to 900 ° c . while the temperature is held at an elevated temperature the temperature takes into account the temperature rise of the semiconductor - on - insulator due to self heating during ion implantation , which typically is in the range from 0 ° c . to 50 ° c . typically , temperature increases encountered without deliberate wafer cooling are less than 25 ° c ., but may be as high as 50 ° c . for high does , high current implants . this invention also provides an fet device in a semiconductor layer , the fet device comprising source / drain regions is subjected to a divided - dose - anneal - in - between ( ddab ) method of ion implantation comprising the steps of selecting a substrate including a semiconductor layer ; defining first semiconductor layer regions that will be subjected to at least two subsequent ion implantation steps and second semiconductor layer regions that will be protected from said at least two subsequent ion implantation steps ; protecting the second semiconductor layer regions from exposure to ion implantation ; subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a first ion implantation ; subjecting the substrate to a first anneal ; subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a final ion implantation ; and subjecting the substrate to a final anneal ; wherein residual damage left in the first semiconductor layer regions ( as measured by strain loss and / or defect density ) after the final anneal is less than the residual damage that would be left in the first semiconductor layer regions if the above process steps were performed without the first anneal . this invention also provides fet devices subjected to ddab methods of ion implantation with multiple implant and annealing cycles , such as , for example , multiple implant and annealing cycles comprising the above first and final implants and anneals plus one or more cycles of supplemental implant and annealing steps comprising subjecting the first semiconductor layer regions ( but not the second semiconductor layer regions ) to a supplemental ion implantation ; and subjecting the substrate to a supplemental anneal ; the cycles performed after the first anneal and before the final implant , wherein residual damage left in the first semiconductor layer regions ( as measured by strain loss and / or defect density ) after the final anneal is less than the residual damage that would be left in the first semiconductor layer regions if the above process steps were performed without the first and the supplemental annealing steps . the fets of this invention may be combined with other fets to form complementary metal - oxide - semiconductor ( cmos ) or other circuits . the semiconductor layers described in this invention may comprise bulk semiconductors ; semiconductor - on - insulator layers ; or a combination of bulk and semiconductor - on - insulator layers such that at least part of the semiconductor layer is bulk and at least part of the semiconductor layer is disposed on an insulator ; the semiconductor layers comprising one or more of si , sic , ge , gec , sige and sigec ; these materials in layered combinations ; these materials strained , partially strained ( or partially relaxed ) and / or unstrained ( or fully relaxed ). the semiconductor layer may comprise , for example , a silicon - on - insulator layer with a thickness less than 30 nm and / or fets comprising semiconductor s / d regions separated by a semiconducting channel region , wherein said s / d regions and said channel regions comprise different semiconductor materials , and wherein said s / d regions are strained , partially strained , or unstrained . particularly favored examples of the fets to which the hot implant and ddab methods of this invention may be applied include ( i ) fets comprising a semiconducting channel region of si and s / d regions of a strained sige alloy having a ge content equal to or greater than 25 atomic percent , and ( ii ) fets comprising a semiconducting channel region of si and s / d regions of a strained sic alloy having a c content greater than 0 . 5 atomic percent . the semiconductor layers may comprise of a single crystal orientation such as ( 100 ) or two or more single crystal orientations ( as typified by hybrid orientation substrate technology ) such as regions of ( 100 ) and ( 110 ). the elevated temperatures for the heated implants of this invention would typically be in the range from 70 to 900 ° c ., preferably be in the range from 150 to 550 ° c ., and most preferably be in the range from 200 - 350 ° c . annealing for the ddab method would typically include any annealing process known to the art , including furnace annealing , rapid thermal annealing , and laser annealing , for time and temperature ranges known to the art , e . g ., temperatures in the range from 150 to 1350 ° c . and times in the range from 24 hours to sub - milliseconds . gas ambients may be selected from those known to the art , typically n 2 or ar with or without additional additives selected from the group nh 3 , h 2 o , h 2 , o 2 , no , n 2 o , etc . the ion implantation of this invention may be performed with any ion known to the art , including atomic ions , molecular ions , singly - charged ions , and multiply - charged ions . particularly favored ions include the ions of as , b , b 1 , bf 2 , ge , p and sb . the conditions for the individual implants comprising the ddab method may be the same or different in one or more particulars ( for example , first and final implants might utilize the same species and energy but be different in angle of incidence ). three examples of the invention will now be described . in the first , it is shown that in situ heating during ion implantation can prevent the amorphization of soi layers that would occur if the same implants were performed at room temperature such as in the range from 20 ° c . to 25 ° c . in the second example , we show how the dependence of amorphization depth on as implant dose may be used to calculate an optimum implementation of the ddab technique in a semiconductor - on - insulator layer . in the third example , we show how the hot implant and ddab techniques may be used to preserve the strain in pseudomorphic sige layers grown on si . the example shows that in situ heating during ion implantation can prevent the amorphization of soi layers that would occur if the same implants were performed at room temperature . soi layers 28 nm in thickness were implanted at 26 , 150 , or 300 ° c . with 3 × 10 15 / cm 2 50 kev as + , an implant that has an average projected range ( rp ) of about 340 å and would ordinarily completely amorphize the soi layer . the reflectance vs . wavelength data of fig6 indicates that the soi layer has indeed been amorphized in the 26 and 150 ° c . samples ( curves b and c , respectively ), but remains crystalline ( with a reflectance curve nearly identical to curve a of the unimplanted control sample ) for the 300 ° c . implant ( curve d ). the sheet resistance ( rs ) measurements of table i corroborate these results : after annealing in n 2 at 900 ° c . for 1 min , the 26 and 150 ° c . samples have rs in the range of 8 - 11 kohm / square , consistent with a recrystallization of the amorphous soi layer to polycrystalline si ; in contrast , the 300 ° c . sample has a rs of 790 ohm / sq , consistent with doped single - crystal si . in addition , the implanted as + is quite substantially activated even as - implanted ( rs ˜ 15 . 5 kohm / sq ) and is more activated ( with an rs of 4 . 4 kohm / sq ) after very mild annealing ( 500 ° c ./ 1 min ) than the 26 and 150 ° c . samples are after 900 ° c ./ min . table i shows rs measurements ( ohm / sq ) of samples implanted with 3 × 10 15 / cm 2 50 kev as + . table i anneal / implant temperature 26 ° c . 150 ° c . 300 ° c . as - implanted & gt ; 1000 k & gt ; 1000 k 15 . 5 k 500 ° c ./ 1 min & gt ; 1000 k & gt ; 1000 k 4 . 4 k 900 ° c ./ 1 min 10 . 7 k 8 . 2 k 790 in the second example ; we show how one may use the dependence of amorphization depth on implant dose to calculate an optimum implementation of the ddab technique in a semiconductor - on - insulator layer disposed on a buried oxide ( box ). soi layers 160 nm in thickness were implanted at room temperature with 100 kev as + ( rp about 71 nm ) at doses of 1 . 25 , 2 . 5 , and 5 . 0 × 10 15 / cm 2 to produce surface amorphous layers having thicknesses of 91 , 111 , and 117 nm respectively . none of these doses were sufficient to amorphize the entire 160 nm thickness of the soi layer . however , soi layers thinner than about 110 nm in thickness would be expected to totally amorphize at doses higher than 2 . 5 × 10 15 / cm 2 , form polycrystalline si upon activation annealing . dividing the 2 . 5 × 10 15 / cm 2 dose into two doses of 1 . 25 × 10 15 / cm 2 would leave a residual crystalline layer between the 91 nm amorphization depth and the top of the box after each implant . annealing between the implants allows the crystallinity of the sample to be restored ( by spe templating from the residual crystalline layer ) before the next implant and results in a crystalline material after a final activation anneal . in the third example , we show how the hot implant and ddab techniques may be used to preserve the strain in pseudomorphic sige layers grown on si . fig7 - 9 show high resolution x - ray diffraction ( hrxr - d ) ( 004 ) rocking curves ( rcs ) of a structure comprised by 40 - nm - thick si 0 . 70 ge 03 . 0 layers epitaxially grown on ( 100 ) si substrate , taken before and after implantation with as + to a dose below the amorphization threshold dose . in fig7 - 9 , the ordinate represents the intensity of diffracted x - ray in counts / second and the abscissa represents delta rocking angle omega in unity of seconds of degree , having the scale origin set at the si substrate diffraction peak . the sige peak ( at negative angles in fig7 - 9 ) typically comprises a main peak bordered by weaker satellite peaks ( thickness fringes or pendellosung oscillations ) whose spacing allows a precise estimate of the sige thickness . the intensities of the main peak and the satellite peaks are highest when the sige is perfectly ordered and defect - free , and decrease with increasing film disorder . the angular separation of the sige diffraction peak from that of si substrate correlates with the magnitude of the compressive strain in the epi - layer . fig7 demonstrates the utility of hot implants by comparing the rcs of an as - grown sample ( curve a ) to samples implanted with 2 × 10 13 / cm 2 , 50 kev as + at 0 ° tilt at 300 ° c . ( curve b ) or room temperature ( curve c ). the as - grown sample has a strain of 1 . 17 % and very distinct thickness fringes ; the hot implanted sample has nearly identical thickness fringes ( indicating negligible implant damage ) and very slightly increased strain ( 1 . 20 %). in contrast , the sample implanted at room temperature shows no main peak and thickness fringes in the noise , a clear indication of severe damage . fig8 shows the rcs of samples of fig7 after an anneal at 1080 ° c . for 1 s ( using a 5150 ° c ./ s heating ramp rate ). rc ( curve a ) for the unimplanted sample shows a strain of 1 . 14 %, indicating that the initial strain is not significantly decreased by annealing alone . rc ( curve b ) for the hot implanted sample shows a strain of 1 . 09 %, again very close to the pre - implant , pre - anneal value . rc ( curve c ) for the sample implanted at room temperature shows a restoration of the sige peak ( indicative of substantial damage repair ), but much reduced strain 110 ( 0 . 65 %). fig7 and 8 thus demonstrate that implant temperature is the key factor in determining whether a given implant energy / dose and subsequent activation anneal will preserve the initial strain or very substantially reduce it . fig9 illustrates the strain - preserving features of the ddab technique . rc ( curve a ) shows the as - grown sample of fig7 a , which had an initial strain of 1 . 17 %. rc ( curve b ) shows a sample subjected to a single - step - implant / anneal sequence comprising a room temperature implant of 2 × 10 13 / cm 2 , 50 kev as + followed by an anneal at 650 ° c . for 110 min , resulting in a final strain of 0 . 88 % ( a significant loss ). rc ( curve c ) shows the contrasting results of the ddab technique using a double - step - implant / anneal sequence in which the 2 × 10 13 / cm 2 as + dose is evenly divided into two doses of 1 × 10 13 / cm 2 , with each implant followed by an anneal at 650 ° c . for 110 min . the strain in this case is 1 . 12 %, very close to the original value of 1 . 17 %, very clearly indicating the benefits of the ddab technique . it should be noted that the ddab technique of course involves a tradeoff between the process time for the additional implant and annealing steps and the benefits of further subdivision in implant dose ( as measured by a decrease in strain loss ). in many cases , the double - step - implant / anneal sequence may be selected optimal . however , the optimal number of subdivisions is likely to be higher for the case of sige with a high ge content and / or materials requiring high implant doses . while several embodiments of the invention , together with modifications thereof , have been described in detail herein and illustrated in the accompanying drawings , it will be evident that various further modifications are possible without departing from the scope of the invention . for example , ( i ) multiple hot implants differing in dose , species , and / or energy might be performed with the same masking layer , and / or ( ii ) the individual implants comprising the ddab method might include some in situ heating during implantation . nothing in the above specification is intended to limit the invention more narrowly than the appended claims . the examples given are intended only to be illustrative rather than exclusive . | 7 |
the schemes shown below schematically depict a method whereby the pyridine monocarboxylate compounds of this invention may be prepared from compounds which are known in the art . starting with a pyridinedicarboxylate compound such as those described in european patent publication no . 133 , 612 , the dicarboxylic acid chloride is prepared by treating with a chlorinating agent such as pcl 5 or socl 2 . the or 5 - amino - monocarboxylate is then prepared from the 3 - or 5 - chlorocarbonyl compound by treatment with nan 3 followed by a curtis rearrangement . the 3 - or 5 - amino compound so produced is then transformed into a 3 - or 5 - halogen substituted pyridinemonocarboxylate or a compound in which the atom linked to the pyridine ring at the 3 - or 5 - position is a nitrogen atom as shown in schemes 2 , 3 and 4 . reference to the examples will provide greater detail about the steps shown in schemes 1 - 4 . ## str11 ## preparation of further compounds of this invention will become clear by reference to the scheme in conjunction with the following examples . as used throughout the specification , including the examples , the following abbreviations have the following meanings : as used in the following examples , the terms &# 34 ; workup as usual &# 34 ;, or &# 34 ; normal workup &# 34 ;, or equivalent language refer to the process of washing the organic extract with brine , drying by pouring through a cone of anhydrous sodium sulfate , and concentrating in vacuo . 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - isobutyl - 2 -( trifluoromethyl )-, ethyl ester . six grams ( 15 . 1 mmol ) of product of example 32 of european patent application no . 133 , 612 published feb . 27 , 1985 , was added to 0 . 95 g of 89 % potassium hydroxide ( 15 . 1 mmol ) and 35 ml of ethanol and was stirred at room temperature for 1 day . the reaction mixture was poured into 135 ml of water , washed with ether ( 2 × 20 ml ) and acidified with concentrated hydrochloric acid . the product was extracted into ether ( 2 × 50 ml ), which was worked up as usual to afford 4 . 91 g ( 88 %) of the desired mono - acid as an off - white solid suitable for further transformation . this was refluxed overnight with thionyl chloride ( 25 ml ). the excess thionyl chloride was removed in vacuo and the resulting acid chloride was added dropwise to a rapidly - stirred slurry of 1 . 8 g of sodium azide in 15 ml of 4 : 1 acetone : water . this was stirred at room temperature for the weekend , then diluted with 75 ml of water and extracted with ether 3 × 20 ml . workup as usual afforded 4 . 66 g ( 91 % overall yield ) of product as a tan solid . recrystallization from cyclohexane gave analytically pure material , mp 68 °- 70 ° c . ______________________________________elemental analysis c h n______________________________________calculated 49 . 41 5 . 04 8 . 23found 49 . 23 4 . 97 8 . 26______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 35 . 0 g ( 0 . 103 mol ) of product of example 55 of european patent application no . 133 , 612 published feb . 27 , 1985 , and 60 ml of thionyl chloride was refluxed overnight . the excess thionyl chloride was removed in vacuo , and the acid chloride was diluted with 10 ml of acetone and added to a slurry of 14 . 3g of nan 3 25 ml of h 2 o and 90 ml of acetone . an exothermic reaction occurred with vigorous gas evolution . after the reaction mixture cooled to room temperature , 300 ml of water was added and the product was extracted into chloroform . normal workup gave 30 . 9 g ( 96 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 92 °- 94 ° c . ______________________________________elemental analysis c h n______________________________________calculated 46 . 16 4 . 20 8 . 97found 46 . 08 4 . 23 8 . 94______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -( methoxycarbonyl ) amino ]- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a mixture of 13 . 7g ( 0 . 037 mol ) of ethyl 6 -( difluoromethyl )- 5 -( chlorocarbonyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl ) - 3 - pyridinecarboxylate prepared by methods shown in european patent application no . 133 , 612 published feb . 27 , 1985 , and 40 ml of thionyl chloride was stirred at reflux for 7 hours , then was concentrated in vacuo . the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 13 . 4g ( 93 %) of the corresponding acid chloride as a yellow oil . to a 0 ° c . solution of 5 . 0 g ( 0 . 013 mol ) of this acid chloride in 50 ml of chloroform was added dropwise a solution of 1 . 03 g ( 0 . 013 mol ) of pyridine and 14 . 5 ml 0 . 0149 mol ) of 1 . 025 m hydrazoic acid in chloroform . after the addition was complete , the reaction mixture was stirred 30 min at room temperature , diluted with 20 ml of methanol and heated on a hot plate until gas evolution ceased . this was then poured into 100 ml of water and extracted with chloroform ( 3 × 40 ml ). normal workup afforded 5 . 03 g ( 97 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 109 °- 110 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 25 4 . 81 7 . 03found 48 . 03 4 . 76 7 . 21______________________________________ 3 - pyridinecarboxylic acid , 5 -([ bis ( 1 - methylethyl ) amino ] carbonylamino )- 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a mixture of 13 . 7g ( 0 . 037 mol ) of ethyl 6 -( difluoromethyl )- 5 -( chlorocarbonyl )- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate prepared by methods shown in european patent application no . 133 , 612 published feb . 27 , 1985 , and 40 ml of thionyl chloride was stirred at reflux for 7 hours , then was concentrated in vacuo . the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 13 . 4g ( 93 %) of the corresponding acid chloride as a yellow oil . a 0 ° c . solution of 5 . 0 g ( 0 . 013 mmol ) of this acid chloride in 50 ml of chloroform was added dropwise to a solution of 1 . 03 g ( 0 . 013 mol ) of pyridine and 14 . 5 ml ( 0 . 015 mol ) of 1 . 025 m hydrazoic acid in chloroform . after the addition was complete , it was stirred at room temperature for 30 min . then 20 ml of diisopropylamine was added causing an exothermic reaction to occur . the reaction was allowed to cool to room temperature and diluted with 100 ml of water . the product was extracted into chloroform ( 3 × 40 ml ). normal workup afforded 5 . 54 g 91 ) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 137 °- 139 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 53 . 96 6 . 47 8 . 99found 53 . 91 6 . 46 8 . 95______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . a mixture of 45 . 0g ( 0 . 132 mol ) of methyl 5 - carboxy - 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl ) - 3 - pyridinecarboxylate prepared by methods shown in european patent application no . 133 , 612 published feb . 27 , 1985 , 8 . 91g ( 0 . 135 mol ) of 85 % potassium hydroxide , 125 ml of methanol and 15 ml of water was stirred at room temperature for 24 hours . the reaction mixture was poured into water ( 500 ml ), washed with chloroform ( 2 × 200 ml ), and then was acidified with concentrated hydrochloric acid . extraction with ethyl acetate ( 3 × 150 ml ) followed by workup as usual afforded 38 . 2g ( 88 %) of the corresponding carboxylic acid as a white solid . a solution of 38 . 2g ( 0 . 117 mol ) of this acid and 50 ml of thionyl chloride was refluxed for 3 h . the excess thionyl chloride was removed in vacuo and the remaining acid chloride was dissolved in acetone ( 15 ml ). this was added to a rapidly stirred slurry of 17 . 8 g ( 0 . 27 mol ) of sodium azide , 30 ml of water and 100 ml of acetone , resulting in an exothermic reaction with vigorous gas evolution . after 2 h , the reaction mixture was diluted with 200 ml of water and extracted with chloroform ( 3 × 70 ml ). normal workup afforded 33 . 0 g ( 86 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 92 °- 93 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 30 3 . 72 9 . 39found 44 . 59 3 . 83 9 . 16______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxycarbonyl ] amino ]- 2 -( trifluoromethyl ) -, ethyl ester . a solution of 5 . 0 g ( 0 . 015 mol ) of product of example 28 of european patent application no . 133 , 612 published feb . 27 , 1985 , and 15 ml of thionyl chloride was refluxed overnight . the excess thionyl chloride was then removed in vacuo and the resulting acid chloride was diluted with 25 ml of methylene chloride and cooled to 0 ° c . to this stirred solution was added dropwise a mixture of 1 . 16 g of pyridine and 16 ml of 1 . 0 m hydrazoic acid in chloroform . after the addition was complete , the reaction mixture was warmed to room temperature for 10 min . then , 35 ml of methanol was added and the reaction mixture was warmed on a hot plate until gas evolution ceased . this was then diluted with 100 ml of water and extracted with chloroform ( 3 × 40 ml ). normal workup afforded 5 . 6 g ( quantitative ) of product as an off - white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 84 °- 86 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 41 4 . 08 7 . 51found 45 . 17 4 . 08 8 . 14______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl ]- 5 - l ( trifluoroaoetyl ) amino ]- 2 - itrifluoromethyl )-, ethyl ester . to a slurry of 1 . 08 g ( 0 . 027 mol ) of 60 % sodium hydride and 10 ml of anhydrous tetrahydrofuran was added a solution of 8 . 0 g ( 0 . 023 mol ) of product of example 1 in 10 ml of tetrahydrofuran . this was refluxed for 2 h , then stirred overnight at room temperature . to this was added 5 . 5 g ( 0 . 026 mol ) of trifluoroacetic anhydride dropwise . this was stirred for 1 h then poured into 100 ml of 5 % hydrochloric acid and extracted with chloroform ( 3 × 50 ml ). normal workup afforded 11 . 0 g of brown solid . recrystallization from ethyl acetate / cyclohexane afforded 9 . 53 g ( 90 %) of product as a white solid , mp 102 °- 104 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 05 3 . 70 6 . 42found 44 . 45 3 . 76 6 . 44______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - isobutyl - 6 - itrifluoromethyl )-, ethyl ester . to a mixture of 2 . 96 g ( 0 . 022 mol ) of cupric chloride , 2 . 26 g ( 0 . 018 mol ) of t - butyl nitrite and 40 ml of acetonitrile is added dropwise to a solution of 5 . 0 g ( 0 . 015 mol ) of product of example 1 in 10 ml of acetonitrile . this was stirred overnight at room temperature , then poured into 100 ml of 2 . 5 m hydrochloric acid . the product was extracted into 3 × 50 ml of ether . workup as usual afforded 5 . 26 g of dark brown oil . this was chromatographed on the prep - 500 using 2 % ethyl acetate / cyclohexane as elution solvent . fraction 1 afforded 2 . 14 g ( 41 %) of product as a colorless oil material ; n d 25 1 . 456 ______________________________________elemental analysis : c h n cl______________________________________calculated 46 . 75 4 . 20 3 . 89 9 . 86found 46 . 82 4 . 24 3 . 86 9 . 90______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 - isobutyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 012mol ) of product of example 1 , 2 . 16 g ( 0 . 012 mol ) of 48 % fluoroboric acid and 30 ml of acetonitrile was added 1 . 34 g ( 0 . 013 mol ) of t - butyl nitrite . this was allowed to stir at 0 ° c . for 30 min , then it was added to a solution of 30 g potassium iodide in 150 ml of water . after stirring for 30 min , the reaction mixture was extracted with chloroform ( 4 × 40 ml ). the chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 50 ml ), brine ( 50 ml ) and dried through a cone of sodium sulfate . concentration in vacuo afforded 4 . 82 g of orange oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . the first fraction contained 1 . 98 g ( 37 %) of product as a colorless oil ; n d 25 1 . 493 . ______________________________________elemental analysis : c h n______________________________________calculated 37 . 27 3 . 35 3 . 10found 37 . 55 3 . 42 3 . 13______________________________________ the second fraction contained 1 . 65 g ( 31 %) of product as a light yellow oil ; n d 25 1 . 488 . ______________________________________elemental analysis : c h n______________________________________calculated 37 . 27 3 . 35 3 . 10found 37 . 57 3 . 40 3 . 09______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, ethyl ester . to a slurry of 2 . 55 g ( 0 . 019 mol ) of cupric chloride , 2 . 48 g ( 0 . 024 mol ) of t - butyl nitrite and 70 ml of anhydrous acetonitrile was added a solution of 5 . 0 g ( 0 . 016 mol ) of product of example 2 in 5 ml acetonitrile . this was stirred at room temperature for 2 h , diluted with 200 ml of 10 % hydrochloric acid and extracted into chloroform ( 3 × 40 ml ). normal workup afforded an orange oil which was kugelrohr distilled ( 120 ° c . @ 1 . 0 torr ) to give 4 . 57 g ( 86 %) of product as a colorless liquid . ______________________________________elemental analysis : c h n cl______________________________________calculated 43 . 46 3 . 34 4 . 22 10 . 69found 43 . 44 3 . 41 4 . 30 10 . 81______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 3 . 23 g ( 0 . 024 mol ) of cupric chloride , 3 . 09 g ( 0 . 030 mol ) of t - butyl nitrite and 65 ml of acetonitrile was added to a solution of 6 . 0 g of product of example 5 in 10 ml of acetonitrile . after stirring at room temperature for 3 h , the reaction mixture was poured into 200 ml of 10 % hydrochloric acid and extracted with chloroform ( 3 × 70 ml ). normal workup afforded 6 . 32 g of an orange oil which was chromatographed on the prep - 500 using 2 % ethyl acetate / cyclohexane . workup of the first fraction afforded 4 . 12 g 66 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 62 °- 62 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 41 . 59 2 . 86 4 . 41 11 . 16found 41 . 57 2 . 79 4 . 34 11 . 18______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 5 . 09 g ( 0 . 023 mol ) of cupric bromide , 2 . 94 g ( 0 . 029 mol ) of t - butyl nitrite and 70 ml of anhydrous acetonitrile was added a solution of 6 . 0 g ( 0 . 019 mol ) of product of example 2 in 5 ml acetonitrile . this was stirred at room temperature for 2 h , then poured into 10 % hydrochloric acid ( 200 ml ) and extracted with chloroform ( 3 × 40 ml ). normal workup afforded 6 . 95 g of a light yellow oil . kugelrohr distillation ( 125 ° c . @ 1 . 0 torr ) gave 6 . 35 g ( 89 %) of product as a white solid . recrystallization from cyclohexane gave analytically pure material , mp 39 °- 41 ° c . ______________________________________elemental analysis : c h n br______________________________________calculated 38 . 32 2 . 95 3 . 72 21 . 25found 38 . 47 2 . 99 3 . 77 21 . 40______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 5 . 36 g ( 0 . 024 mol ) of cupric bromide , 3 . 09 g ( 0 . 030 mol ) of t - butyl nitrite and 6 . 5 ml of acetonitrile was added a solution of 6 . 0 g ( 0 . 020 mol ) of product of example 5 in 10 ml of acetonitrile . after stirring for 3 h at room temperature , the reaction mixture was added to 200 ml of 10 % hydrochloric acid and extracted with chloroform . normal workup afforded 7 . 05 g of brown oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the first fraction afforded 4 . 83 g ( 68 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 61 °- 62 ° c . ______________________________________elemental analysis : c h n br______________________________________calculated 36 . 49 2 . 51 3 . 87 22 . 07found 36 . 56 2 . 55 3 . 86 22 . 16______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - iodo - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 2 . 0 g ( 6 . 40 mmol ) of product of example 2 , 1 . 18 g ( 6 . 40 mmol ) of 48 % fluoroboric acid and 10 ml of acetonitrile was added to 0 . 72 g of t - butyl nitrite . this solution was stirred at 0 ° c . for 15 min then was added to a rapidly stirred solution of 12 g of potassium iodide in 100 ml of water . this was stirred for 30 min , then was extracted with chloroform ( 3 × 40 ml ). the combined chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 100 ml ), brine ( 50 ml ), and dried through a cone of sodium sulfate . concentration in vacuo afforded an orange oil which was filtered through a short plug of silica gel ( 5 % ethyl acetate / cyclohexane as eluant ) to afford 2 . 10 g ( 78 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 63 °- 65 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 34 . 06 2 . 62 3 . 31found 34 . 32 2 . 68 3 . 30______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - iodo - 2 -( trifluoromethyl )-, methyl ester . to a 0 ° c . solution of 6 . 25 g ( 0 . 021 mol ) of product of example 5 , 3 . 84 g ( 0 . 021 mol ) of 48 % fluoroboric acid and 55 ml of acetonitrile was slowly added 2 . 38 g 0 . 023 mol ) of t - butyl nitrite . this was stirred at 0 ° c . for 30 min , then added to a rapidly stirred solution of 55 g of potassium iodide in 200 ml of water . after 20 min , this was diluted with water 20 ( 200 ml ) and extracted with chloroform ( 3 × 50 ml ). this was washed with 10 % sodium thiosulfate ( 2 × 50 ml ), brine ( 100 ml ) and dried through sodium sulfate . concentration in vacuo afforded 7 . 80 g of brown oil , which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the first fraction afforded 4 . 58 g ( 56 %) of product as a white solid . recrystallization from cyclohexane afforded analytically pure material , mp 62 °- 63 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 32 . 30 2 . 22 3 . 42found 32 . 37 2 . 26 3 . 38______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred slurry of 41 . 3 g of sodium azide , 75 ml of water and 260 ml of acetone was slowly added a solution of 109 g ( 0 . 292 mol ) of product of example 47 of european patent application no . 133 , 612 published feb . 27 , 1985 , in 30 ml of acetone . an exothermic reaction took place with vigorous gas evolution . after the reaction mixture cooled to room temperature , it was diluted with water ( 500 ml ) and extracted into chcl 3 ( 3 × 150ml ). normal workup afforded 94 . 8g ( quantitative ) of product as an offwhite solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 73 °- 75 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 79 4 . 66 8 . 59______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -( ethoxymethylene ) amino ]- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 20 . 0 g ( 0 . 061 mol ) of product of example 16 , 22 . 7 g ( 0 . 153 mol ) of triethyl orthoformate and 300 mg of p - toluenesulfonic acid was heated at 110 ° c . with removal of ethanol by distillation . after 4 h , the excess orthoformate was removed in vacuo and the residue was kugelrohr distilled ( 140 ° c . @ 1 torr ) to afford 23 . 3 g ( quantitative ) of product as a colorless liquid ; n d 25 1 . 462 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 18 5 . 01 7 . 29______________________________________ 3 - pyridinecarboxylic acid , s - amino - 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 19 . 2 g ( 0 . 054 mol ) of 3 - t - butyl 5 - ethyl 4 - ethyl - 2 - methyl - 6 -( trifluoromethyl )- 3 , 5 - pyridinedicarboxylate prepared by methods shown in european patent application no . 133 , 612 , and 40 ml of 97 % formic acid was stirred overnight at 85 ° c . the reaction mixture was then concentrated in vacuo to give an orange oil which was diluted with 50 ml of thionyl chloride and refluxed for 3 h . the excess thionyl chloride was removed in vacuo and the residue was kugelrohr distilled to give 13 . 4 g ( 78 %) of the acid chloride . this was taken up in 5 ml of acetone and added to a stirred slurry of 7 . 5 g of sodium azide , 13 ml of water and 50 ml of acetone . an exothermic reaction occurred with vigouous gas evolution . after the reaction mixture cooled to room temperature , it was diluted with 200 ml of water and extracted with chloroform ( 3 × 75 ml ). normal workup afforded an oily solid which was chromatographed on silica gel using 20 % ethyl acetate / cyclohexane to give 6 . 35 ( 55 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 107 °- 109 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 52 . 17 5 . 47 10 . 14found 52 . 26 5 . 54 10 . 11______________________________________ 3 - pyridinecarboxylic acid , 4 - ethyl - 6 - methyl - 5 - nitro - 2 -( trifluoromethyl )-, ethyl ester . to a 55 ° c . slurry of 7 . 82 g of sodium perborate ( 0 . 051 mol ) and 40 ml of glacial acetic acid was added a solution of 3 . 5 g ( 0 . 013 mol ) of product of example 18 in 15 ml of glacial acetic acid . the reaction mixture was maintained at 55 ° c . for 2 h , then was poured into 150 ml of water and extracted with chloroform ( 3 × 40 ml ). workup as usual afforded a dark oil which was kugelrohr distilled ( 130 ° c . @ 1 torr ) to give 1 . 57 g of product as a light yellow oil . the residue which did not distill was chromatographed on silica gel ( 1 % etoac / cyclohexane ) to afford an additional 1 . 00 g of product to give a total of 2 . 57 % ( 66 %); n d 25 1 .% 65 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 07 4 . 28 9 . 15found 47 . 01 4 . 29 9 . 23______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - nitro - 2 -( trifluoromethyl ), ethyl ester . to a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 in 100 ml of concentrated sulfuric acid at 0 ° c . was carefully added 10 ml of 90 % hydrogen peroxide . this was slowly warmed to room temperature over a 3 - hour period and then stirred there overnight . the reaction mixture was diluted with ice ( 300 g ) and extracted with chloroform . normal workup gave a white solid which was chromatographed on silica gel using 1 % ethyl acetate / cyclohexane . workup of the first fraction gave 2 . 02 g ( 46 %) of product as a white solid , mp 44 °- 46 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 12 3 . 24 8 . 19found 42 . 28 3 . 25 8 . 15______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - nitro - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester to a 0 ° c . solution of 15 . 0 g ( 0 . 046 mol ) of product of example 16 and 360 ml of concentrated sulfuric acid was carefully added 36 ml of 90 % hydrogen peroxide . this was slowly warmed to room temperature over a 3 - hour period and stirred there overnight . the reaction mixture was quenched with ice ( 300 g ) and extracted into chloroform ( 3 × 100 ml ). workup as usual gave a white solid which was chromatographed on silica gel using 1 % ethyl acetate / cyclohexane . workup of the first fraction gave 9 . 35 g ( 57 %) of product as a white solid , mp 63 °- 65 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 43 . 83 3 . 68 7 . 86found 43 . 83 3 . 69 7 . 86______________________________________ 3 - pyridinecarboxylic acid , 2 -( trifluoromethyl ) - 4 -( 2 - methylpropyl ]- 5 - nitro - 6 -( difluoromethyl )-, ethyl ester . to a 0 ° c . solution 6 . 0 g ( 0 . 018 mol ) of product of example 1 and 135 ml of concentrated sulfuric acid was carefully added 13 . 5 ml of 90 % hydrogen peroxide , dropwise . this was slowly warmed to room temperature over a period of 3 h , then was stirred overnight . to this was added 200 g of ice chips and the resulting aqueous solution was extracted with chloroform ( 3 × 75 ml ). workup as usual gave a brown oil which was chromatographed on silica gel ( 1 % ethyl acetate / cyclohexane ). workup gave 3 . 53 g ( 54 %) of product as a white solid , mp 44 °- 46 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 41 4 . 08 7 . 57found 45 . 47 4 . 03 7 . 75______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - methyl - 5 - nitro - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 15 . 0 g ( 0 . 050 mol ) of product of example 71 and 360 ml of concentrated sulfuric acid was carefully added 36 ml of 90 % hydrogen peroxide dropwise . this was slowly warmed to room temperature over a 3 - hour period and allowed to stir there overnight . then , 300 g of ice chips were added and the product was extracted into chloroform ( 3 × 75 ml ). workup as usual afforded an off - white solid which was kugelrohr distilled ( 140 ° c . @ 1 torr ) to give 11 . 8 g ( 72 %) of product as a white solid , mp 93 °- 95 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 26 2 . 76 8 . 54found 40 . 43 2 . 75 8 . 33______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - nitro - 2 -( trifluoromethyl )-, methyl ester . to a 0 ° c . solution of 5 . 0 g ( 0 . 017 mol ) of product of example 5 and 120 ml of concentrated sulfuric acid was carefully added 12 ml of 90 % hydrogen peroxide dropwise . this was stirred at 0 ° c . for 3 h , then slowly warmed to room temperature and stirred overnight . the reaction mixture was then diluted with 200 g of ice and extracted with chloroform . workup as usual gave a white solid which was chromatographed on silica gel ( 1 % ethyl acetate / cyclohexane ). workup of the first fraction afforded 2 . 73 g ( 50 %) of product as a white solid , mp 65 °- 67 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 26 2 . 76 8 . 54found 40 . 30 2 . 76 8 . 54______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( trifluoroacetyl ) amino - 2 -( trifluoromethyl )-, ethyl ester . a solution a 4 . 0 g ( 0 . 16 mol ) of product of example 2 , 35 ml of trifluoroacetic anhydride and 20 ml of methylene chloride was stirred at room temperature for 3 h . the reaction mixture was then concentrated in vacuo ( 50 ° c . @ 20 torr ) affording 6 . 19 g ( 95 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 98 °- 100 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 41 . 19 2 . 96 6 . 86found 41 . 49 3 . 09 6 . 95______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - methyl - 5 -( trifluoroacetyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 7 . 44 g ( 0 . 025 mol ) of product of example 71 , 20 g of trifluoroacetic anhydride and 20 ml of chloroform was stirred at room temperature for 2 h . the reaction mixture was concentrated in vacuo to afford a white solid which was recrystallized from ethyl acetate / cyclohexane to give 8 . 5 g ( 90 %) of product , mp 112 °- 114 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 39 . 61 2 . 56 7 . 14found 39 . 55 2 . 58 7 . 11______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( pentafluoropropionyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g 0 . 0128 mol ) of product of example 71 , 15 ml of dichloromethane and 5 . 0 g ( 0 . 16 mol ) of pentafluoropropionic anhydride was stirred at room temperature for 1 day . the reaction mixture was then concentrated in vacuo and kugelrohr distilled ( 150 ° c . @ 5 torr ) to give 4 . 8 g ( 82 %) of product as a white solid , mp 113 °- 115 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 39 . 32 2 . 64 6 . 11found 39 . 72 2 . 68 6 . 17______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( pentafluoropropionyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 0 g ( 0 . 010 mol ) of product of example 5 , 9 ml of pentafluoropropionic anhydride and 14 ml of chloroform was stirred at room temperature for 3 h . the reaction mixture was concentrated in vacuo affording a white solid . recrystallization from ethyl acetate / cyclohexane gave 4 . 07 g ( 92 %) of product as a white solid , mp 96 °- 98 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 37 . 85 2 . 27 6 . 31found 38 . 10 2 . 41 6 . 50______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -( formylamino )- 4 - methyl - 2 - itrifluoromethyl ) -, ethyl ester . to 43 . 2 g ( 0 . 42 mol ) of acetic anhydride at 0 ° c . was added 24 . 4 g ( 0 . 53 mol ) of formic acid . this was warmed to room temperature , then heated at 50 ° c . for 15 min . this was then immediately cooled to 0 ° c . and 4 . 68 g 0 . 016 mol ) of product of example 71 was added . after stirring at room temperature for 40 min , the reaction mixture was concentrated in vacuo and the resulting solid was recrystallized from ethyl acetate to give 3 . 51 g ( 67 %) of product as a white solid , mp 151 °- 152 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 18 3 . 40 8 . 59found 44 . 11 3 . 43 8 . 57______________________________________ 3 - pyridinecarboxylic acid , 5 -[( α - chloroacetyl ) amino - 6 -( difluoromethyl ]- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 0128 mol ) of product of example 2 , 1 . 50 g ( 0 . 013 mol ) of chloroacetyl chloride and 10 ml of acetonitrile was stirred overnight at room temperature . a small amount of starting material remained , as determined by gas chromatography , so another 75 mg of chloroacetyl chloride was added and the reaction was stirred another 4 h . concentration of the reaction mixture in vacuo gave 5 . 10 g ( quantitative ) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 104 °- 106 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 43 . 26 3 . 63 7 . 21 9 . 12found 43 . 40 3 . 67 7 . 26 9 . 10______________________________________ 3 - pyridinecarboxylic acid , 5 -[( α , α - dichloropropionyl ) amino ]- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 0128 mol ) of product of example 2 , 2 . 42 g ( 0 . 015 mol ) of 2 , 2 - dichloropropionyl chloride , 1 . 18 g ( 0 . 015 mol ) of pyridine and 10 ml of acetonitrile was refluxed for 24 h . the reaction mixture was then poured into 50 ml of 1m hydrochloric acid and extracted with chloroform . normal workup afforded a dark solid which was kugelrohr distilled ( 160 ° c . @ 1 torr ) to give 4 . 52 g ( 81 %) of product as an off - white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 145 °- 146 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 41 . 21 3 . 46 6 . 41 16 . 22found 41 . 26 3 . 46 6 . 37 16 . 15______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0 g ( 0 . 0168 mol ) of product of example 71 , 7 . 0 g of triethyl orthoformate and 100 mg of p - toluenesulfonic acid was heated at 110 ° c . with removal of ethanol by distillation . after 3 h , the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . @ 1 torr ) to afford 5 . 10 g ( 86 %) of product as a colorless liquid ; n d 25 1 . 46s . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 47 4 . 29 7 . 89______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 5 . 7 g ( 0 . 038 mol ) of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 2 h with removal of the ethanol formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 86 g ( 82 %) of product as a colorless oil ; n d 25 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 78 4 . 62 7 . 51______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxymethylene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 4 . 0 g ( 0 . 038 mol ) of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 2 h , removing the methanol formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to afford 3 . 90 g ( 86 %) of product a colorless oil ; n d 25 1 . 463 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 67 4 . 36 7 . 86______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl )- 5 -[( ethoxymethylene ) amino ]- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 75 g ( 0 . 011 mol ) of product of example 1 , 4 . 90 ( 0 . 033 mol ) of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 2 h , removing the ethanol which formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 83 g ( 88 %) of product as a colorless liquid ; n d 25 1 . 464 . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 52 5 . 34 7 . 07found 51 . 80 5 . 48 7 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 - methyl - 2 -{ trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 71 , 4 . 2 g ( 0 . 040 mol ) of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 2 h , removing the methanol which formed by distillation . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 4 . 01 g ( 88 %) of product as a light yellow oil ; n d 25 1 . 463 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 89 3 . 85 8 . 23found 45 . 89 3 . 94 8 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( methoxymethylene ) amino ]- 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 50 g ( 0 . 012 mol ) of product of example 5 , 3 . 82 g ( 0 . 036 mol ) of trimethyl orthoformate and 30 mg of p - toluenesulfonic acid was stirred at reflux for 2 h , then concentrated in vacuo . the residue was kugelrohr distilled ( 145 ° c . @ 1 torr ) to give 3 . 47 g ( 84 %) of product as a colorless oil which slowly solidified , mp 29 °- 30 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 89 3 . 85 8 . 23found 46 . 04 3 . 82 8 . 11______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 0 g ( 0 . 0092 mol ) of product of example 16 , 10 ml of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 2 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 135 ° c . ° c . @ 1 torr to give 3 . 13 g ( 92 %) of product as a colorless oil ; n d 25 1 . 465 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 66 4 . 57 7 . 33______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 10g ( 0 . 012 mol ) of product of example 1 , 7 ml of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred overnight at 100 ° c . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr to give 4 . 07 g ( 89 %) of product as a colorless oil ; n d 25 1 . 457 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 16 5 . 19 7 . 01______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxymethylene ) amino ]- 2 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 1 , 10 ml of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . for 3 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . ° c . @ 1 torr ) to give 4 . 18 g ( 88 %) of product as a colorless oil ; n d 25 1 . 463 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 41 4 . 29 7 . 80______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( 2 - methylpropoxy ] methylene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g (. 012 mol ) of product of example 16 , 10 ml of tri - i - butyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 110 ° c . for 16 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . ° c . @ 1 torr ) to afford 4 . 6 % ( 81 %) of product as a colorless oil ; n d 25 1 . 503 . ______________________________________elemental analysis : c h n______________________________________calculated 52 . 68 5 . 65 6 . 83found 52 . 65 5 . 69 6 . 82______________________________________ 3 - pyridinecarboxylic acid , 5 -[( n - butoxymethylene ) amino ]- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 8 . 7 g of tri - n - butyl orthoformate , 4 . 0 g ( 0 . 013 mol ) of product of example 2 and 70 mg of p - toluenesulfonic acid was heated at 110 ° c . for 18 h . the reaction was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . ° c . 1 torr ) to give a yellow oil . chromatography on silica gel ( 2 % ethyl acetate / cyclohexane ) afforded 1 . 98 g ( 39 %) of product as a colorless oil ; n d 25 1 . 500 . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 52 5 . 34 7 . 07found 51 . 76 5 . 42 7 . 00______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[[ n - propoxymethylene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0 g ( 0 . 016 mol ) of product of example 2 , 10 ml of tri - n - propyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 110 ° c . for 1 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . ° c . @ 1 torr ) to give 4 . 25 g ( 69 %) of product as a light yellow oil ; n d 25 1 461 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 24 5 . 02 7 . 30______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 2 - methylpropoxy ) methylene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 10 ml of triisobutyl orthoformate and 70 mg of p - toluenesulfonic acid was heated to 110 ° c . for 18 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . ° c . @ 1 torr ) to afford 3 . 8 g ( 75 %) of product as a light yellow oil , which slowly crystallized , mp 34 °- 34 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 51 5 . 34 7 . 07found 51 . 37 5 . 35 7 . 01______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( n , n - dimethylamino ) methylene ] amino }- 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a slurry of 5 . 0 g ( 0 . 168 mol ) of product of example 71 , 4 . 0 g ( 0 . 34 mol ) of dimethylformamide dimethylacetal and 100 mg of p - toluenesulfonic acid was heated at reflux for 1 h . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 150 ° c . ° c . @ 1 torr ) to give 5 . 20 g ( 88 %) of product as a white solid , mp 70 °- 71 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 50 4 . 57 11 . 89found 47 . 61 4 . 43 11 . 64______________________________________ 3 - pyridinecarboxylic acid , 5 -[( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 6 -( difluoromethyl )- 4 - methyl - 2 - itrifluoromethyl )-, ethyl ester . a mixture of 4 . 0 g ( 0 . 010 mol ) of product of example 26 and 2 . 11 g ( 0 . 010 mol ) of phosphorous pentachloride was heated to 140 ° c . and stirred there for 16 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 130 ° c .° c . @ 1 torr ) to give 3 . 24 g of product as a colorless oil ; n d 25 1 . 435 . ______________________________________elemental analysis : c h n cl______________________________________calculated 37 . 84 2 . 20 6 . 79 8 . 59found 38 . 15 2 . 26 6 . 82 8 . 63______________________________________ 3 - pyridinecarboxylic acid , 5 -( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino - 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 33 . 5 g ( 0 . 082 mol ) of product of example 25 and 17 . 08 g ( 0 . 082 mol ) of phosphorous pentachloride was heated at 140 ° c . for 18 h . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 31 . 7 g ( 91 %) of product as a colorless oil ; n d 25 1 . 436 ______________________________________elemental analysis : c h n cl______________________________________calculated 39 . 41 2 . 60 6 . 57 8 . 31found 39 . 81 2 . 65 6 . 59 8 . 35______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( 1 - ethoxy - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . to an ethanolic sodium ethoxide solution , prepared from 0 . 25 g ( 0 . 011 mol ) of sodium metal and 5 ml of absolute ethanol , was added a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 in 5 ml of ethanol . a white precipitate formed immediately . after stirring for 15 min the reaction mixture was poured into water and extracted with chloroform . workup gave a light yellow oil which was kugelrohr distilled ( 130 ° c . ° c . @ 1 torr ) to give 3 . 67 ( 89 %) of product as a colorless oil ; n d 25 1 . 440 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 05 3 . 70 6 . 42found 44 . 46 3 . 76 6 . 48______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( 1 - methoxy - 2 , 2 ,- 2 - trifluoroethylidine ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a methanolic sodium methoxide solution , prepared from 0 . 23 g ( 0 . 010 mol ) of sodium metal and 4 ml of methanol was added a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 in 5 ml of methanol . a white precipitate formed immediately . after 15 min , the reaction mixture was poured into water and extracted with chloroform . workup as usual gave a yellow oil which was kugelrohr distilled ( 130 ° c . @ 1 torr ) to give 3 . 63 g ( 91 %) of product as a colorless oil which slowly solidified , mp 49 °- 51 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 67 3 . 34 6 . 63found 43 . 03 3 . 39 6 . 65______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[ 1 -( ethylthio )- 2 , 2 , 2 - trifluoroethylidine ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a slurry of 0 . 38 g ( 0 . 0094 mol ) of 60 % sodium hydride in 10 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere was added 0 . 59 g ( 0 . 0094 mol ) of ethanethiol . after gas evolution ceased , a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 , 5 ml of tetrahydrofuran was added dropwise . after 15 min , the reaction mixture was poured into water and extracted with chloroform . workup as usual gave a yellow oil which was kugelrohr distilled ( 135 ° c . @ 1 torr ) to give 3 . 87 g ( 91 %) of product as a colorless liquid ; n d 25 1 . 464 . ______________________________________elemental analysis : c h n s______________________________________calculated 42 . 48 3 . 57 6 . 19 7 . 09found 42 . 86 3 . 64 6 . 24 7 . 24______________________________________ 3 - pyridinecarboxylic acid , 5 -{[ 1 -( diethoxyphosphinyl )- 2 , 2 , 2 - trifluoroethylidene ] amino }- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 2 . 5 g ( 0 . 0059 mol ) of product of example 47 and 0 . 98 g of triethylphosphite was heated at 160 ° c . for 30 min . the reaction mixture was then cooled to room temperature where solidification occurred . trituration of this solid with cyclohexane gave 3 . 03 g ( quantitative ) of product as a light yellow solid , mp 73 °- 75 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 92 4 . 01 5 . 30found 40 . 72 4 . 00 5 . 19______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )- 5 -[ 5 -( trifluoromethyl ) - 1h - tetrazol - 1 - yl ]-, ethyl ester . to a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 and 0 ml of tetrahydrofuran was added 0 65 g ( 0 . 01 mol ) of sodium azide . this was stirred at room temperature and 4 ml of water was added . the reaction mixture became warm immediately . after 5 min , the reaction mixture was diluted with water ( 25 ml ) and extracted with chloroform ( 3 × 20 ml ). workup as usual afforded a thick oil which was kugelrohr distilled ( 150 ° c . ° c . @ torr ) to give 3 . 83 g ( 94 %) of product as a light yellow oil ; n d 25 1 . 444 . ______________________________________elemental analysis : c h n______________________________________calculated 38 . 81 2 . 56 16 . 16found 39 . 12 2 . 68 15 . 92______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )- 5 -{[ 1 -( trifluoromethyl ) ethylidene ] amino }-, ethyl ester . to a solution of 2 . 3 g ( 0 . 0054 mol ) of product of example 47 in 5 ml of anhydrous tetrahydrofuran at 0 ° c . under a dry nitrogen atmosphere was added dropwise 1 . 7 ml ( 0 . 0054 mol ) of 3 . 2 m methyl magnesium bromide in ether . this was stirred at 0 ° c . for 30 min , then was poured into 10 ml of saturated ammonium chloride . the reaction mixture was suction filtered and the filtrate was extracted with ether ( 3 × 25 ml ). workup as usual gave an oil which was chromatographed on silica gel using 5 % ethyl acetate / cyclohexane . workup of the first fraction afforded 1 . 0 g ( 46 %) of product as a colorless oil ; n d 25 1 . 500 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 35 3 . 47 6 . 89found 43 . 35 3 . 40 6 . 70______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - isocyanato - 2 -( trifluoromethyl )-, ethyl ester . the product of example 46 ( 50 . 4g , 0 . 14 mol ) of european patent application no . 133 , 612 published feb . 27 , 1985 , was added to 17 . 3 g of azidotrimethyl silane ( 0 . 15 mol ) and 100 ml of carbon tetrachloride and heated at reflux until gas evolution ceased (˜ 4 h ). the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . @ 1 torr ) to give 35 . 2 g ( 74 %) of product as a light yellow oil ; n d 25 1 . 457 . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 16 3 . 28 8 . 28found 45 . 88 3 . 40 8 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 - isocyanato - 2 -( trifluoromethyl )-, methyl ester . methyl 5 - chlorocarbonyl - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate ( 84 . 1 g , 0 . 243 mol ) was added to 150 ml of carbon tetrachloride and 30 g ( 0 . 26 mol ) of azidotrimethyl silane and stirred overnight at 55 ° c . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled to give 57 . 3 g ( 72 %) of product as a white solid , mp 55 °- 57 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 46 2 . 80 8 . 64found 44 . 32 2 . 94 8 . 77______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - isocyanato - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . ethyl 5 - chlorocarbonyl - 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate ( 64 . 1 g , 0 . 165 mol ) was added to 21 . 06 ( 0 . 182 mol ) of azidotrimethyl silane and 120 ml of carbon tetrachloride and heated at reflux for 4h , at which time , gas evolution ceased . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 100 ° c . @ 1 torr to give 29 . 4 g ( 65 %) of product as a light yellow oil ; n d 25 1 . 455 . ______________________________________elemental analysis : c h n______________________________________calculated 49 . 19 4 . 13 7 . 65found 48 . 95 4 . 02 7 . 77______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( ethylthio ] carbonyl ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 4 . 5 g ( 0 . 013 mol ) of product of example 54 and 20 ml of methylene chloride was added 15 ml of ethanethiol . to this was added 30 mg of potassium t - butoxide causing an exotherm . the reaction mixture was allowed to stir overnight then was concentrated in vacuo affording a light yellow solid . recrystallization from ethyl acetate / cyclohexane gave 4 . 63 g ( 90 %) of product as a white solid , mp 124 °- 126 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 45 . 00 4 . 28 7 . 00 8 . 01found 44 . 73 4 . 14 6 . 80 7 . 83______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( ethylthio ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . to a slurry of 0 . 49 g ( 0 . 012 mol ) of 60 % sodium hydride in 10 ml of anhydrous tetrahydrofuran was added a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 55 in 25 ml of anhydrous tetrahydrofuran . this was stirred at room temperature for 1 h then 50 ml of water was added and the product was extracted into ethyl acetate ( 3 × 25 ml ). workup as usual gave 3 . 95 g ( 83 %) of product as a white solid , mp 143 °- 145 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 43 . 52 3 . 91 7 . 25 8 . 30found 43 . 42 3 . 97 7 . 21 8 . 38______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( methylthio ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . a solution of 15 . 0 g ( 0 . 046 mol ) of product of example 55 and 50 ml of tetrahydrofuran was cooled to 0 ° c . and 10 g of methanethiol was added . to this mixture was added 100 mg of potassium t - butoxide . the reaction mixture was slowly warmed to room temperature and stirred overnight . the reaction mixture was concentrated in vacuo and the residue taken up in chloroform ( 100 ml ). workup as usual afforded 15 . 21 % ( 89 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 134 °- 135 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 41 . 94 3 . 52 7 . 52 8 . 61found 42 . 01 3 . 53 7 . 57 8 . 57______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( ethylthio ) carbonyl ] amino }- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 3 . 50 g ( 0 . 0095 mol ) of product of example 56 , 0 . 93 g ( 0 . 015 mol ) of ethanethiol and 20 ml of tetrahydrofuran was added 15 mg of potassium t - butoxide . this was stirred for 2 h at room temperature , then was concentrated in vacuo . this solid was dissolved in 75 ml of chloroform and worked up as usual to give 3 . 54 g ( 86 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 113 °- 114 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 47 . 66 4 . 94 6 . 54 7 . 48found 47 . 65 4 . 96 6 . 52 7 . 56______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxycarbonyl ) amino ]- 4 - ethyl - 2 -( trifluoro - methyl )-, methyl ester . a solution of 4 . 1 g ( 0 . 013 mol ) of product of example 55 , 25 ml of chloroform and 25 ml of ethanol was stirred at reflux for 15 min . the reaction mixture was concentrated in vacuo to give 4 . 53 g ( 97 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 100 °- 101 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 41 4 . 08 7 . 75found 45 . 31 4 . 11 7 . 63______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 1 - methylethoxy ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g (. 012 mol ) of product of example 55 , 25 ml of chloroform and 25 ml of 2 - propanol was refluxed for 15 min . the reaction mixture was concentrated in vacuo to give 4 . 63 g ( 85 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 130 °- 132 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 88 4 . 46 7 . 29found 46 . 67 4 . 47 7 . 37______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 1 - methylethylthio ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . to a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 55 , 5 . 0 g ( 0 . 066 mol ) of 2 - propanethiol and 20 ml of tetrahydrofuran was added 20 mg of potassium t - butoxide . the reaction mixture was stirred at room temperature for 2 hours then concentrated in vacuo to give a white solid . recrystallization from ethyl acetate / cyclohexane afforded 4 . 37 ( 89 %) of product as a white solid , mp 139 °- 140 ° c . ______________________________________elemental analysis : c h n s______________________________________calculated 45 . 00 4 . 28 7 . 00 8 . 01found 45 . 04 4 . 30 7 . 00 8 . 06______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -({[( 1 , 1 - dimethylethyl ) thio ] carbonylamino )- 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 60 g ( 0 . 011 mol ) of product of example 55 , 20 ml of chloroform and 20 ml of t - butanol was stirred at reflux for 15 min . the reaction mixture was concentrated in vacuo and the resulting solid was recrystallized from ethyl acetate / cyclohexane to give 4 . 01 g ( 91 %) of product as a white solid , mp 99 °- 100 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 25 4 . 81 7 . 03found 48 . 31 4 . 93 7 . 00______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( methoxycarbonyl ) amino ]- 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 0 g ( 0 . 0093 mol ) of product of example 55 , 20 ml of chloroform and 20 ml of methanol was stirred at reflux for 15 min , then concentrated in vacuo . the resulting solid was recrystallized from ethyl acetate / cyclohexane to give 3 . 08 g ( 93 %) of product as a white solid , mp 111 °- 113 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 43 . 83 3 . 68 7 . 86found 44 . 21 3 . 75 8 . 12______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) carbonyl ] amino }- 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 3 . 0 g ( 0 . 0093 mol ) of product of example 55 , 20 ml of dioxane was added 10 ml of 26 % aqueous dimethylamine . this was stirred at 60 ° c . for 10 min , then was poured into 100 ml of water and extracted with chloroform ( 3 × 40 ml . workup as usual afforded 3 . 06 g ( 89 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 177 °- 178 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 53 4 . 37 11 . 38found 45 . 64 4 . 41 11 . 29______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( n - methylamino ) carbonyl ] amino }- 2 -( trifluoromethyl )-, methyl ester . to a solution of 3 . 57 g ( 0 . 011 mol ) of product of example 55 and 20 ml of dioxane was added 7 ml of 40 % aqueous methylamine . a white preciptiate formed immediately . this was stirred at 50 ° c . for 10 min , cooled to room temperature , and suction filtered . air drying afforded 3 . 56 g ( 91 %) of product as a white solid , mp 202 °- 203 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 43 . 95 3 . 97 11 . 83found 43 . 82 4 . 02 11 . 78______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( 4 , 5 - dihydro - 5 - oxo - 1h - tetrazol - 1 - yl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 54 and 2 . 72 g 0 . 024 mol ) of azidotrimethyl silane was refluxed for 1 . 5 days then was concentrated in vacuo . the reaction mixture slowly solidified over a period of 3 days . trituration with ethyl acetate / cyclohexane gave 2 . 20 g ( 49 %) of product as a white solid , mp 139 °- 141 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 95 3 . 17 18 . 37found 40 . 88 3 . 21 18 . 33______________________________________ 3 - pyridinecarboxylic acid , 5 -{[( 2 - chloroethoxy ) carbonyl ] amino ]- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 12 mol ) of product of example 54 , 9 ml of chloroform and 9 ml of 2 - chloroethanol was heated at reflux for 1 . 5 days . the reaction mixture was concentrated in vacuo and the residue slowly solidified over 3 days . trituration with ethyl acetate / cyclohexane gave 3 . 27 g ( 66 %) of product as a white solid , mp 102 °- 103 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 43 . 02 3 . 85 6 . 69 8 . 47found 43 . 21 3 . 87 6 . 68 8 . 50______________________________________ 3 - pyridinecarboxylic acid , 5 -{[( diethoxyphosphinyl ) carbonyl ] amino }- 6 -( difluoromethyl )- 4 - ethyl - 2 -( trifluoromethyl )-, methyl ester . to a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 55 and 3 drops of triethylamine in 20 ml of toluene was added 1 . 70 g of diethyl phosphite . this was heated at 80 ° c . for 1 . 5 day , then was concentrated in vacuo . the residue was dissolved in chloroform , washed with water 20 ml , 1 m hydrochloric acid ( 20 ml ) and brine ( 20 ml ). workup as usual afforded 5 . 1 g ( 90 %) of product as a white solid , mp 91 °- 94 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 41 . 57 4 . 36 6 . 06found 41 . 24 4 . 28 6 . 29______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 - methyl - 2 - itrifluoromethyl )-, ethyl ester . to a slurry of 50 g of sodium azide , 90 ml of water and 315 ml of acetone was added 0 . 474 mol of ethyl 5 - chlorocarbonyl - 6 -( difluoromethyl )- 4 - methyl - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate in 35 ml of acetone with rapid stirring . an exothermic reaction resulted with vigorous gas evolution . after the reaction mixture cooled to room temperature , it was diluted with 200 ml of water and extracted with chloroform . normal workup afforded 86 . 3 g ( 82 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane afforded analytically pure material , mp 71 °- 72 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 30 3 . 72 9 . 39found 44 . 30 3 . 73 9 . 40______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a rapidly - stirred solution of 21 g of sodium azide , 35 ml of water and 140 ml of acetone was added a solution of 0 . 096 mol of product of example 44 of european patent application no . 133 , 612 published feb . 27 , 1985 , in 20 ml of acetone . an exothermic reaction followed with gas evolution . after the reaction mixture cooled to room temperature , it was diluted with water ( 300 ml ) and extracted with chloroform ( 3 × 100 ml ). normal workup afforded 28 . 4 g ( 91 %) of product as a tan solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 56 °- 58 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 92 4 . 68 8 . 58______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 3 . 76 g ( 0 . 028 mol ) of cupric chloride , 3 . 61 g ( 0 . 035 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added a solution of 7 . 0g ( 0 . 023 mol ) of product of example 71 in 7 ml of acetonitrile . this was stirred at room temperature for 90 min , then poured into 200 ml of 1 m hydrochloric acid and extracted with chloroform . normal workup afforded an orange oil which was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . concentration in vacuo afforded 5 . 92 g ( 81 %) of product as a colorless liquid ; n d 25 1 . 452 . ______________________________________elemental analysis : c h n cl______________________________________calculated 41 . 59 2 . 86 4 . 41 11 . 16found 41 . 60 2 . 87 4 . 39 11 . 15______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 6 . 25 g ( 0 . 028 mol ) of cupric bromide , 3 . 61 g ( 0 . 035 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added a solution of 7 . 0 g ( 0 . 023 mol ) of product of example 71 in 7 ml of acetonitrile . this was stirred at room temperature for 1 . 5 h , then poured into 200 ml of 10 % hydrochloric acid and extracted with chloroform ( 3 × 50 ml ). normal workup gave a yellow oil which was filtered through a short silica gel column ( 2 % ethyl acetate / cyclohexane ) to give 7 . 54 g ( 91 %) of product as a colorless liquid ; n d 25 1 470 . ______________________________________elemental analysis : c h n br______________________________________calculated 36 . 49 2 . 51 3 . 87 22 . 07found 36 . 47 2 . 53 3 . 86 21 . 99______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 7 . 0 g ( 0 . 023 mol ) of product of example 71 , 4 . 21 g 0 . 023 mol ) of 48 % fluoroboric acid and 60 ml of acetonitrile was added 2 . 61 g of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 1 h , then added to a rapidly stirred solution of 60 g of potassium iodide in 200 ml of water . after 15 min , the reaction mixture was diluted with 200 ml of water and extracted with chloroform ( 3 × 100 ml ). the chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 50 ml , brine ( 50 ml ) and dried through sodium sulfate . concentration in vacuo afforded an orange oil which was filtered through a short plug of silica gel . the resulting oil was kugelrohr distilled ( 150 ° c . @ 1 torr ) to afford 1 . 73 g ( 18 %) of product as a white solid , mp 41 °- 43 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 32 . 30 2 . 22 3 . 42found 32 . 51 2 . 12 3 . 60______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a mixture of 2 . 69 g ( 0 . 02 mol ) of cupric chloride , 2 . 58 g ( 0 . 025 mol ) of t - butyl nitrite and 40 ml of acetonitrile was added a solution of 5 . 44 g ( 0 . 017 mol ) of product of example 72 in 7 ml of acetonitrile . this was stirred at room temperature for 1 . 5 h , poured into 150 ml of 1 m hydrochloric acid and extracted into chloroform ( 3 × 50 ml ). normal workup gave 5 . 73 g of a brown oil which was passed through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 140 ° c . @ 2 torr ) of the resulting oil afforded 4 . 32 g ( 75 %) of product as a colorless liquid ; n d 25 1 . 457 . ______________________________________elemental analysis : c h n cl______________________________________calculated 45 . 17 3 . 79 4 . 05 10 . 26found 45 . 31 3 . 81 4 . 06 10 . 28______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 4 . 47 g ( 0 . 020 mol ) of cupric bromide , 2 . 58 g ( 0 . 025 mol ) of t - butyl nitrite and 40 ml of acetonitrile was added a solution of 5 . 49 g ( 0 . 17 mol ) of product of example 72 in 7 ml of acetonitrile . this was stirred at room temperature for 1 . 5 h , poured into 150 ml of 1 m hydrochloric acid and extracted with chloroform ( 3 × 75 ml ). normal workup afforded a brown oil which was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 140 ° c . @ 2 torr ) of the resulting oil afforded 5 . 13 g ( 78 %) of product as a colorless liquid ; n d 25 1 . 473 . ______________________________________elemental analysis : c h n br______________________________________calculated 40 . 02 3 . 36 3 . 59 20 . 48found 40 . 05 3 . 38 3 . 57 20 . 40______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 6 . 0 q 0 . 018 mol ) of product of example 72 , 3 . 29 g 0 . 018 mol ) of 48 % fluoroboric acid and 45 ml of acetonitrile was added 2 . 04 g ( 0 . 02 mol ) of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 15 min , then was added to a rapidly stirred solution of 60 g of potassium iodide in 150 ml of water . the reaction mixture was stirred for 30 min , then was diluted with water ( 200 ml ) and extracted with chloroform ( 3 × 50 ml ). the chloroform extract was washed with 100 ml of 10 % sodium thiosulfate , 100 ml of brine , and dried though sodium sulfate . concentration in vacuo afforded a red - orange oil that was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 160 ° c . @ 2 torr ) of the resulting oil afforded 4 . 3 g ( 55 %) of product as a light yellow oil ; n d 25 1 . 498 . ______________________________________elemental analysis : c h n i______________________________________calculated 35 . 72 3 . 00 3 . 20 29 . 03found 35 . 83 3 . 00 3 . 15 28 . 94______________________________________ 3 ™ pyridinecarboxylic acid , 5 - chloro - 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a slurry of 4 . 97 g ( 0 . 037 mol ) of cupric chloride , 4 . 84 g ( 0 . 047 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added a solution of 10 . 0 g ( 0 . 031 mol ) of product of example 16 in 10 ml of acetonitrile . gas evolution occurred immediately . after the reaction was stirred at room temperature for 90 min , it was poured into 250 ml of 1 m hydrocholoric acid and extracted with chloroform . normal workup afforded 10 . 45 g of a brown oil which was filtered through a short silica gel column ( 2 % ethyl acetate / cyclohexane ) and kugelrohr distilled 130 ° c . @ 2 torr ) to afford 7 . 33 g ( 68 %) of product as a colorless liquid ; n d 25 1 . 454 . ______________________________________elemental analysis : c h n cl______________________________________calculated 45 . 17 3 . 79 4 . 05 10 . 26found 45 . 19 3 . 81 4 . 02 10 . 34______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 8 . 26 g ( 0 . 037 mol ) of cupric bromide , 4 . 84 g ( 0 . 047 mol ) of t - butyl nitrite and 80 ml of acetonitrile was added 10 . 0 g ( 0 . 031 mol ) of product of example 16 in 10 ml of acetonitrile , resulting in immediate gas evolution . after 90 min the reaction mixture was poured into 250 ml of 1m hydrochloric acid . extraction with chloroform ( 3 × 75 ml ) and workup as usual afforded 11 . 81 g of a brown oil . this material was filtered through a short silica gel column ( 2 % ethyl acetate / cyclohexane ), then kugelrohr distilled ( 135 ° c . @ 1 . 5 torr ) to afford 8 . 7 g ( 72 %) of product as a colorless oil ; n d 25 1 . 467 . ______________________________________elemental analysis : c h n br______________________________________calculated 40 . 02 3 . 36 3 . 59 20 . 48found 40 . 14 3 . 38 3 . 58 20 . 58______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - iodo - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 10 . 0 g 0 . 031 mol ) of product of example 16 , 5 . 67 g of 48 % fluoroboric acid 0 . 031 mol ) and 55 ml of acetonitrile was added 3 . 50 g ( 0 . 034 mol ) of t - butyl nitrite dropwise . after 20 min at 0 ° c ., the reaction mixture was added to a rapidly - stirred solution of 80 g of potassium iodide in 175 ml of water . this was stirred for 45 min , diluted with 200 ml of water and extracted with chloroform ( 3 × 75 ml ). the chloroform extract was washed with 10 % sodium thiosulfate ( 2 × 50 ml ), brine ( 100 ml ) and dried through sodium sulfate . normal workup afforded 12 . 8 g of an oily brown solid which was filtered through a short silica gel column with 2 % ethyl acetate / cyclohexane . kugelrohr distillation ( 140 ° c . at 1 . 5 torr ) afforded 9 . 32g ( 69 %) of product as a white solid , mp 45 °- 48 ° c . ______________________________________elemental analysis : c h n i______________________________________calculated 35 . 72 3 . 00 3 . 20 29 . 03found 35 . 77 3 . 00 3 . 17 28 . 96______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred slurry of 2 . 92 g ( 0 . 022 mol ) of cupric chloride , 2 . 80 g ( 0 . 027 mol ) of t - butyl nitrite and 50 ml of acetonitrile was added a solution of 5 . 0 g ( 0 . 018 mol ) of product of example 18 in 10 ml of acetonitrile . this was stirred at room temperature for 2 h , then was poured into 150 ml of 1 m hydrochloric acid and extracted with chloroform ( 3 × 75 ml ). workup as usual afforded a brown oil that was kugelrohr distilled ( 120 ° c . @ 1 torr to give 4 . 73 g ( 88 %) of product as a yellow liquid ; n d 25 1 .% 70 . ______________________________________elemental analysis : c h n cl______________________________________calculated 48 . 74 4 . 43 4 . 74 11 . 99found 48 . 83 4 . 20 5 . 11 12 . 26______________________________________ 3 - pyridinecarobxylic acid , 5 - bromo - 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred solution of 4 . 85 g ( 0 . 022 mol ) of cupric bromide , 2 . 80 g ( 0 . 027 mol ) of t - butyl nitrite and 50 ml of acetonitrile was added a solution of 5 . 0 g ( 0 . 018 mol ) of product of example 18 in 10 ml of acetonitrile . this was stirred at room temperature for 2 h , then was diluted with 200 ml of 1m hydrochloric acid and extracted with chloroform ( 3 × 75 ml ). normal workup afforded an orange oil that was kugelrohr distilled ( 120 ° c . @ 1 torr ) to give 5 . 21 g ( 84 %) of product as a light yellow oil ; n d 25 1 . 484 . ______________________________________elemental analysis : c h n br______________________________________calculated 42 . 37 3 . 85 4 . 12 23 . 49found 42 . 43 3 . 88 4 . 11 23 . 41______________________________________ 3 - pyridinecarboxylic acid , 4 - ethyl - 5 - iodo - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 66 g ( 0 . 017 mol ) of product of example 18 , 3 . 08 g of 48 % fluoroboric acid and 35 ml of acetonitrile was added 1 . 91 g ( 0 . 019 mol ) of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 25 min , then was added to a rapidly stirred solution of 40 g of potassium iodide in 120 ml of water . after 30 min , 120 ml of water was added and the reaction mixture was extracted with chloroform ( 3 × 70 ml ). the chloroform extracts were washed with 10 % sodium thiosulfate ( 2 × 50 ml , brine ( 50 ml and dried through sodium sulfate . workup as usual afforded an orange oil that was kugelrohr distilled ( 120 ° c . @ 1 torr ) to give 4 . 88 ( 75 %) of product as a light yellow oil ; n d 25 1 . 504 . ______________________________________elemental analysis : c h n i______________________________________calculated 37 . 23 3 . 38 3 . 62 32 . 78found 37 . 35 3 . 42 3 . 55 32 . 50______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 - ethyl - 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 2 . 34 g ( 0 . 013 mol ) of 48 % fluoroboric acid and 30 ml of acetonitrile was added 1 . 46 g ( 0 . 014 mol ) of t - butyl nitrite dropwise . after 30 min , a solution of 1 . 7 g ( 0 . 026 mol ) of sodium azide in 9 ml of water was added dropwise , resulting in vigorous gas evolution . this was stirred at room temperature for 30 min , diluted with water ( 50 ml ) and extracted with chloroform ( 3 × 25 ml ). workup as usual afforded a yellow oil . chromatography on silica gel ( 2 % ethyl acetate / cyclohexane ) afforded 2 . 44 g ( 55 %) of product as a light yellow oil ; n d 25 1 . 476 . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 61 3 . 28 16 . 56found 42 . 76 3 . 33 16 . 49______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[( 1 - methylethoxy ) methylene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 2 , 10 ml of triisopropyl orthoformate and 70 mg of p - toluenesulfonic acid was heated to 100 ° c . and stirred for 4 h . the temperature was then raised to 130 ° c . and stirring was continued for another 18 hours . the reaction mixture was then concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 1 . 58 g ( 32 %) of product as a colorless oil ; n d 25 1 . 502 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 49 . 97 4 . 95 7 . 67______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( 2 - methylpropoxy ) methylene ] amino - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 1 , 10 ml of triisobutyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 18 h , then at 120 ° c . for another 18 h . the reaction mixture was concentrated in vacuo . the residue was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 1 . 93 g ( 39 %) of product as a light yellow oil ; n d 25 1 . 500 . ______________________________________elemental analysis : c h n______________________________________calculated 53 . 77 5 . 94 6 . 60found 54 . 30 6 . 00 6 . 34______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 5 -( propoxymethylene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 1 , 10 ml of tripropyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 18 h . the reaction mixture was concentrated in vacuo and the residue was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 71 g ( 56 %) of product as a colorless oil ; n d 25 1 . 458 . ______________________________________elemental analysis : c h n______________________________________calculated 52 . 68 5 . 65 6 . 83found 52 . 85 5 . 76 6 . 43______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[ 2 , 2 , 2 - trifluoro - 1 -( dimethylamino ) ethylidene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a rapidly stirred solution of 4 . 3 g ( 0 . 010 mol ) of product of example 47 in 5 ml of dioxane was added 4 . 5 ml ( 0 . 025 mol ) of 26 % aqueous dimethylamine . an exothermic reaction occurred . when the reaction cooled to room temperature , 50 ml of water was added and the product was extracted into methylene chloride ( 3 × 25 ml ). workup as usual afforded a dark oil that was kugelrohr distilled ( 130 ° c . @ 1 torr ) to give 2 . 35 g 54 %) of product as a yellow oil ; n d 25 1 . 466 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 15 3 . 94 9 . 65found 44 . 17 3 . 77 9 . 37______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -{[ 2 , 2 , 2 - trifluoro - 1 -( methylamino ) ethylidene ] amino }- 2 -( trifluoromethyl )-, ethyl ester . to a stirred solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 and 5 ml of dioxane was added 2 ml of 40 % aqueous methylamine . after 30 min , 50 ml of water was added and the product was extracted with methylene chloride . workup as usual , followed by kugelrohr distillation ( 170 ° c . @ 1 torr ) gave 3 . 07 g ( 78 %) of product as a white solid , mp 95 °- 97 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 77 3 . 59 9 . 97found 42 . 59 3 . 63 9 . 98______________________________________ 3 - pyridinecarboxylic acid , 5 -[( ethoxymethylene ) amino ]- 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 5 g 0 . 013 mol ) of product of example 18 , 10 ml of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . for the weekend . the reaction mixture was then concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 73 g ( 88 %) of product as a colorless oil ; n d 25 1 . 477 . ______________________________________elemental analysis : c h n______________________________________calculated 54 . 21 5 . 76 8 . 43found 54 . 16 5 . 80 8 . 23______________________________________ 3 - pyridinecarboxylic acid , 5 -{[( dimethylamino ) methylene ] amino }- 4 - ethyl - 6 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 3 . 70 g ( 0 . 013 mol ) of product of example 18 , 10 ml of dimethylformamide dimethyl acetal , and 70 mg of p - toluenesulfonic acid was stirred at 100 ° c . overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 ° c . @ 1 torr ) to give 3 . 55 g ( 80 %) of product as a yellow solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material as a white solid , mp 71 °- 73 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 54 . 37 6 . 08 12 . 68found 54 . 38 6 . 13 12 . 62______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 012 mol ) of product of example 1 , 2 . 16 g 0 . 012 mol ) of ( 48 %) fluoroboric acid and 40 ml of acetonitrile was added 1 . 34 g of t - butyl nitrite dropwise . this was stirred at 0 ° c . for - 20 min then a solution of 2 . 1 g of sodium azide in 11 ml of water was added slowly , causing immediate gas evolution . after 10 min , 50 ml of water was added and the product was extracted into chloroform . workup as usual afforded a yellow oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the first fraction gave 2 . 85 g ( 66 %) of product as a light yellow oil ; n d 25 1 . 470 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 91 4 . 13 15 . 30found 45 . 71 4 . 21 15 . 37______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -({ 1 -[( 1 - methylethyl ) thio ]- 2 , 2 , 2 - trifluoroethylidene } amino )- 2 -( trifluoromethyl )-, ethyl ester . to a slurry of 0 . 40g ( 0 . 010 mol ) of 60 % sodium hydride in 7 ml of anhydrous tetrahydrofuran under a nitrogen atmosphere was added 0 . 74 g ( 0 . 0097 mol ) of 2 - propanethiol . this was stirred at room temperature for 30 min , then a solution of 4 . 0 g ( 0 . 0094 mol ) of product of example 47 in 5 ml of tetrahydrofuran was added dropwise . this was stirred for 30 min , diluted with 25 ml of water and extracted with ether ( 3 × 15 ml ). workup as usual , followed by kugelrohr distillation ( 150 ° c . @ 1 torr ) afforded 2 . 92 g ( 67 %) of product as a yellow liquid ; n d 25 1 . 466 . ______________________________________elemental analysis : c h n s______________________________________calculated 43 . 78 3 . 89 6 . 01 6 . 87found 44 . 09 3 . 90 5 . 90 6 . 89______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( methylamino )- 2 -( trifluoromethyl ) ethyl ester . to 40 ml of acetic anhydride at 0 ° c . was added 20 ml of formic acid . this was warmed to room temperature , then was heated to 50 ° c . for 15 min . the flask was immediately re - cooled to 0 ° c . and 5 . 0g ( 0 . 016 mol ) of product of example 2 was added . this was stirred at room temperature for 18 hours , then was concentrated in vacuo to afford a yellow oil . this was dissolved in 15 ml of anhydrous tetrahydrofuran , and stirred at 0 ° c . under a dry nitrogen atmosphere . to this , 20 ml ( 0 . 04 mol ) of 2 . 0 m borane - dimethyl sulfide complex in tetrahydrofuran was added dropwise . after the addition was complete , the reaction mixture was stirred at 70 ° c . for 3 . 5 hours . the reaction mixture was then cooled to 0 ° c . and 10 ml of methanol was added slowly . after frothing ceased , the mixture was warmed to room temperature and stirred for 1 hour . the 7 ml of concentrated hydrochloric acid was added and the mixture was refluxed for 1 hour . the reaction mixture was concentrated in vacuo to afford a yellow solid , which was slurried with ethyl acetate and stirred with 25 ml of 10 % sodium hydroxide solution . the organic layer was separated and workup as usual gave a yellow oil . chromatography on silica gel using 5 % ethyl acetate / cyclohexane gave 2 . 77g of product as a yellow oil which slowly solidified , mp 38 °- 40 ° c . ______________________________________elemental analysi : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 88 4 . 63 8 . 56______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -[( 2 , 2 , 2 - trifluoroethyl ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 5 . 16g ( 0 . 0128 mol ) of product of example 25 in 12 ml of anhydrous tetrahydrofuran at 0 ° c . under a nitrogen atmosphere , was added 16 ml of 2 . om borane - dimethyl sulfide complex in tetrahydrofuran dropwise . the reaction mixture was heated at 70 ° c . for 3 hours . then the mixture was cooled to 0 ° c . and 10 ml of methanol was added carefully . after frothing ceased 10 ml of concentrated hydrochloric acid was added and the mixture was refluxed for 1 hour . the reaction mixture was concentrated in vacuo and the residue was slurried with 50 ml of ethyl acetate and stirred with 25 ml of 10 % sodium hydroxide . workup of the ethyl acetate solution afforded a yellow oil that was chromatographed on silica gel with 5 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 15g ( 43 %) of product as a colorless oil ; n d 25 1 . 439 . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 65 3 . 58 7 . 11found 42 . 93 3 . 58 7 . 13______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 - methyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0g 0 . 0134 mol ) of product of example 71 , 2 . 45g 0 . 0134 mol ) of 48 % fluoroboric acid and 45 ml of acetonitrile was stirred at 0 ° c . and 1 . 44g 0 . 014 mol ) of t - butyl nitrite was added dropwise . this was allowed to stir at 0 ° c . for 20 minutes , then a solution of 2 . 1 g of sodium azide in 11 ml of water was added dropwise , resulting in immediate gas evolution . after stirring for an additional 10 minutes the reaction mixture was diluted with water and extracted with chloroform . workup as usual gave a yellow oil which was chromatographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 27g ( 52 %) of product as a yellow oil ; n d 25 1 . 474 . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 75 2 . 80 17 . 28found 40 . 96 2 . 71 17 . 03______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0g ( 0 . 015 mol ) of product of example 72 , 10 ml of trimethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated to 100 ° c . and stirred for 2 hours . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 140 ° c . at 1 torr ) to afford 5 . 05g ( 90 %) of product as a colorless oil which slowly crystallized , mp 57 °- 59 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 91 4 . 66 7 . 59______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ] 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 5 . 0g ( 0 . 015 mol ) of product of example 72 , 10 ml of triethyl orthoformate and 70 mg of p - toluenesulfonic acid was heated at 100 ° c . overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 145 ° c . 1 torr ) to give 5 . 07 g 8 %) of product as a colorless oil ; n d 25 1 . 464 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 26 5 . 05 7 . 30______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) 4 - ethyl - 5 -{[( dimethylamino ) methylene ] amino ]- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 0128 mol ) of product of example 2 , 10 ml of dimethylformamide dimethyl acetal and 70 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 145 ° c . at 1 torr ) to afford 3 . 90 g ( 83 %) of product as a yellow solid , mp 50 °- 52 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 49 . 05 4 . 94 11 . 44found 49 . 02 4 . 93 11 . 33______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl - 5 -{[( dimethylamino ) methylene ] amino }- 4 -( 1 - methylethyl ) - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 25 g ( 0 . 013 mol ) of product of example 72 , 10 ml of dimethylformamide dimethyl acetal and 70 mg of p - toluenesulfonic acid was heated overnight at 100 ° c . the reaction mixture was concentrated in vacuo and the residue was chromatographed on silica gel using 5 % ethyl acetate / cyclohexane . workup of the correct fraction afforded 4 . 17 g ( 84 %) of product as a yellow oil ; n d 25 1 . 487 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 39 5 . 29 11 . 02found 50 . 33 5 . 22 11 . 28______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 6 -( difluoromethyl ) - 4 -( 1 - methylethyl )- 2 -( trifluoromethyl )-, ethyl ester . to a 0 ° c . solution of 4 . 0 g ( 0 . 012 mol ) of product of example 72 , 2 . 25 g ( 0 . 012 mol ) of 48 % fluoroboric acid and 40 ml of acetonitrile was added 1 . 40 g ( 0 . 013 mol ) of t - butyl nitrite dropwise . this was stirred at 0 ° c . for 20 minutes , then a solution of 2 . 1 g of sodium azide in 11 ml of water was added slowly , resulting in vigorous gas evolution . after stirring for 10 minutes , 100 ml of water was added and the product was extracted into chloroform ( 3 × 50 ml ). workup as usual afforded an orange oil which was chromatrographed on silica gel using 2 % ethyl acetate / cyclohexane . workup of the correct fraction gave 2 . 41g ( 56 %) of product as a slightly yellow oil ; n d 25 1 . 472 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 33 3 . 72 15 . 91found 44 . 11 3 . 72 15 . 91______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - ethyl - 5 -( sulfinylamino )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g of product of example 2 and 15 ml of thionyl chloride was stirred at reflux overnight . the excess thionyl chloride was removed in vacuo and the residue was kugelrohr distilled ( 145 ° c . at 1 torr ) to give 4 . 21 g ( 92 %) of product as a bright yellow oil ; n d 25 1 . 477 . ______________________________________elemental analysis : c h n s______________________________________calculated 40 . 23 3 . 09 7 . 82 8 . 95found 40 . 30 3 . 11 7 . 80 8 . 87______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 - isocyanato - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . the product of example 47 ( 5 . 0 g , 0 . 0134 mol ) of european patent application no . 133 , 612 published feb . 27 , 1985 , was added to 1 . 66 g ( 0 . 0144 mol ) of azidotrimethyl silane and 10 ml of carbon tetrachloride and stirred at reflux until gas evolution ceased (˜ 45 minutes ). the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 2 . 65 g ( 50 %) of product as a light yellow oil ; n d 25 1 . 459 . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 74 3 . 72 7 . 95found 47 . 74 3 . 89 7 . 80______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - propyl - 5 -[( 2 , 2 , 2 - trifluoro - 1 - methoxyethylidene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 2 . 16 g ( 0 . 01 mol ) of 25 % methanolic sodium methoxide in 5 ml of methanol was added a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 in 5 ml of methanol , resulting in the immediate formation of a white precipitate . the reaction mixture was stirred for 1 hour , then was poured into water ( 50 ml ) and extracted with ether ( 3 × 15 ml ). workup as usual afforded a colorless oil which was kugelrohr distilled ( 130 ° at 1 . 5 torr ) to give 3 . 27 g ( 82 %) of product as a colorless oil ; n d 25 1 . 438 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 05 3 . 70 6 . 42found 44 . 13 3 . 69 6 . 44______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) methylene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g ( 0 . 012 mol ) of product of example 16 , 10 ml of dimethylformamide dimethyl acetal and 70 mg of p - toluenesulfonic acid was stirred at reflux overnight . the reaction mixture was then concentrated in vacuo and the residue was kugelrohr distilled ( 165 ° c . at 1 . 5 torr to give 4 . 10 g ( 87 %) of product as a yellow oil ; n d 25 1 . 486 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 39 5 . 29 11 . 02found 50 . 50 5 . 29 10 . 99______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( trifluoroacetyl ) amino ]- 4 - propyl ™ 2 ™( trifluoromethyl )-, ethyl ester . a solution of 35 . 0 g ( 0 . 107 mol ) of product of example 16 , 100 ml of methylene chloride and 30 g ( 0 . 14 mol ) of trifluoroacetic anhydride was stirred at room temperature overnight . concentration in vacuo afforded 45 . 7 g 100 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 95 °- 97 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 67 3 . 34 6 . 63found 42 . 80 3 . 20 6 . 74______________________________________ 3 - pyridinecarboxylic acid , 5 -[( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a mixture of 39 . 58 g ( 0 . 0937 mol ) of product of example 107 and 19 . 51 g ( 0 . 0937 mol ) of phosphorous pentachloride was heated at 135 ° c . for 3 hours . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 130 ° c . at 1 torr ) to give 40 . 07 g ( 97 %) of product as a colorless oil ; n d 25 1 . 434 . ______________________________________elemental analysis : c h n cl______________________________________calculated 40 . 88 2 . 97 6 . 36 8 . 04found 40 . 53 2 . 73 6 . 26 8 . 08______________________________________ 3 - pyridinecarboxylic aoid , 5 -[[ 1 -( diethoxyphosphinyl ) - 2 , 2 , 2 - trifluoroethylidene ] amino ]- 6 -( difluoromethyl )- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . a solution of 6 . 0 g ( 0 . 0136 mol ) of product of example 108 and 2 . 26 g ( 0 . 0136 mol ) of triethyl phosphine was stirred at 160 ° c . for 30 min . the reaction mixture was then cooled to room temperature affording 7 . 35 g (˜ quant .) of product as a yellow oil ; n d 25 1 . 437 . ______________________________________elemental analysis : c h n______________________________________calculated 42 . 08 4 . 27 5 . 17found 41 . 68 4 . 29 5 . 14______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - propyl - 5 -[( 2 , 2 , 2 - trifluoro - 1 - ethoxyethylidene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a solution of 3 . 24 g ( 0 . 010 mol ) of 21 % ethanolic sodium ethoxide and 5 ml of ethanol was added a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 in 5 ml of ethanol . this was stirred at room temperature for 15 minutes during which time a white precipitate formed . the reaction mixture was poured into water ( 50 ml ) and extracted with ether . workup as usual gave a yellow oil which was kugelrohr distilled ( 150 ° at 1 . 5 torr to give 3 . 87 g ( 84 %) of product as a colorless oil ; n d 25 1 . 438 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 34 4 . 03 6 . 22found 45 . 44 4 . 00 6 . 26______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 - propyl - 2 -( trifluoromethyl )- 5 -[ 5 -( trifluoromethyl ) - 1h - tetrazol - 1 - yl ]-, ethyl ester . to a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 in 20 ml of tetrahydrofuran was added 0 . 65 g ( 0 . 01 mol ) of sodium azide followed by the addition of 4 ml of water . the reaction mixture was stirred at room temperature for 30 minutes , then was diluted with water 50 ml ) and extracted with chloroform ( 3 × 25 ml ). normal workup gave 3 . 87 g ( 86 %) of product as a white solid . recrystallization from ethyl acetate / cyclohexane gave analytically pure material , mp 66 °- 68 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 28 2 . 93 15 . 66found 40 . 07 2 . 87 15 . 77______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[ 1 -( dimethylamino )- 2 , 2 , 2 - trifluoroethylidene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 and 10 ml of dioxane was added 4 . 5 ml of 26 % aq . dimethylamine . the solution became warm immediately . this was allowed to stir for 30 minutes , then was diluted with water ( 50 ml ) and extracted with chloroform ( 3 × 25 ml ). normal workup gave an orange oil which was kugelrohr distilled ( 165 ° c . at 1 torr ) to give 3 . 77 g ( 84 %) of product as a colorless 1 . 464 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 44 4 . 26 9 . 35found 45 . 42 4 . 18 9 . 19______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[ 2 , 2 , 2 - trifluoro - 1 ( methylamino ) ethylidene ] amino }- 4 - propyl - 2 -( trifluoromethyl )-, ethyl ester . to a stirred solution of 4 . 0 g ( 0 . 0091 mol ) of product of example 108 and 10 ml of dioxane was added 2 ml of 40 % aq . methylamine . the reaction mixture became warm . this was allowed to stir for 30 minutes , then was diluted with water ( 50 ml ) and extracted with chloroform ( 3 × 25 ml ). normal workup gave a yellow oil which was kugelrohr distilled ( 165 ° c . at 1 torr ) to give 3 . 53 g ( 89 %) of product as a thick colorless oil ; n d 25 1 . 461 . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 15 3 . 94 9 . 65found 44 . 25 3 . 77 9 . 38______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 209 , 7 . 8 ml of triethyl orthoformate and 78 mg of p - toluenesulfonic acid was heated to 100 ° c . and stirred for 6 hours . the reaction mixture was concentrated in vacuo to give 5 . 39 g ( 100 %) of product as a colorless oil . chromatography on silica gel ( 1 % ethyl acetate / cyclohexane ) ave analytically pure material ; n d 25 1 . 462 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 50 5 . 09 7 . 30______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a stirred slurry of 14 . 3 g of sodium azide , 25 ml of water and 75 ml of acetone was slowly added a solution of 35 . 77 g ( 0 . 103 mol ) of methyl 5 - chlorocarbonyl - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )- 3 - pyridinecarboxylic in 20 ml of acetone . an exothermic reaction followed with vigorous gas evolution . the reaction mixture was allowed to cool to room temperature and diluted with water ( 300 ml ) and extracted into chloroform ( 3 × 100 ml ). normal workup afforded 26 . 61 g ( 82 %) of product as a light yellow solid . trituration with cyclohexane gave analytically pure material , mp 54 °- 56 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 44 . 30 3 . 72 9 . 39found 44 . 37 3 . 72 9 . 37______________________________________ 3 - pyridinecarboxylic acid , 2 -{ difluoromethyl ) - 4 - ethyl - 5 -[( methoxymethylene ) amino ]- 6 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 , 7 . 4 ml of trimethyl orthoformate and 74 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was then concentrated in vacuo and the residue kugelrohr distilled ( 150 °- 165 ° c . at 1 torr ) to give 4 . 24 g ( 98 %) of product as white solid , mp 67 °- 69 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 89 3 . 85 8 . 23found 45 . 92 3 . 85 8 . 21______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 , 7 . 8 ml of triethyl orthoformate and 78 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and the residue was kugelrohr distilled ( 150 °- 165 ° c . at 1 torr ) to give 4 . 3 g ( 0 . 012 mol ) of product as a white solid . trituration with cyclohexane gave analytically pure material , mp 68 °- 69 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 46 4 . 27 7 . 91found 47 . 37 4 . 30 7 . 90______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl )-, methyl ester . a solution of 3 . 5 g ( 0 . 011 mol ) of product of example 209 , 6 . 7 ml of trimethyl orthoformate , and 67 mg of p - toluenesulfonic acid was refluxed for 2 hours . reaction mixture was then concentrated in vacuo and the residue kugelrohr distilled ( 150 °- 160 ° c . at 1 torr ) to give 3 . 67 g ( 93 %) of product as a colorless oil ; n d 25 1 466 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 98 4 . 66 7 . 61______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a stirred solution of 3 . 41 g ( 0 . 015 mol ) of copper ( ii ) bromide and 1 . 96 g ( 0 . 019 mol ) of t - butyl nitrite in 36 ml of acetonitrile was added a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 in 7 ml of acetonitrile . the reaction was stirred at room temperature for 1 hour , then was poured into 180 ml of 20 % aqueous hydrochloric acid and extracted with ether ( 3 × 50 ml ). normal workup followed by kugelrohr distillation ( 130 °- 145 ° c . at 1 torr ) gave 3 . 63 g ( 79 %) of product as a colorless oil . chromatography of a small amount of product on silica gel ( 2 % ethyl acetate / cyclohexane ) gave an analytically pure white solid , mp 25 49 °- 51 ° c . ______________________________________elemental analysis : c h n br______________________________________calculated 36 . 49 2 . 51 3 . 87 22 . 07found 37 . 14 2 . 59 3 . 92 22 . 39______________________________________ 3 - pyridinecarboxylic acid , 5 - chloro - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a stirred solution of 2 . 05 g ( 0 . 015 mol ) of copper ( ii ) chloride and 1 . 96 g (. 019 mol ) of t - butyl nitrite in 36 ml of acetonitrile was added a solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 in 7 ml of acetonitrile . the reaction was stirred at room temperature for 1 hour . the reaction mixture was poured into 180 ml of 20 % aqueous hydrochloric acid and extracted with ether ( 3 × 50 ml ). workup as usual followed by kugelrohr distillation ( 130 °- 145 ° c .) gave 3 . 28 g ( 81 %) of product as a colorless oil . chromatography of a small amount of product on silica gel ( 2 % ethyl acetate / cyclohexane ) gave analytically pure material ; n d 25 1 . 454 . ______________________________________elemental analysis : c h n cl______________________________________calculated 41 . 59 2 . 86 4 . 41 11 . 16found 41 . 72 2 . 88 4 . 47 11 . 20______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 4 - ethyl - 5 - iodo - 6 -( trifluoromethyl )-, methyl ester . to a stirred solution of 3 . 98 g ( 0 . 013 mol ) of product of example 115 , 2 . 32 g ( 0 . 013 mol ) of 48 % fluoroboric acid and 33 ml of acetonitrile in an ice bath was slowly added 1 . 44 g 0 . 014 mol ) of t - butyl nitrite . the solution was stirred at 0 ° c . for 30 minutes and then added to a rapidly stirred solution of 33 . 17 g ( 0 . 20 mol ) of potassium iodide in 120 ml water . after 30 minutes , the reaction mixture was diluted with 120 ml of water and extracted with chloroform ( 3 × 75 ml ). the chloroform solution was washed with 10 % sodium thiosulfate solution ( 2 × 75 ml ). workup as usual followed by kugelrohr distillation ( 140 °- 165 ° c . at 1 torr ) gave 3 . 75 g ( 72 %) of product as an off - white solid , mp 63 °- 65 ° c . chromatography of a small amount of product on silica gel ( 2 % ethyl acetate / cyclohexane gave an analytically pure white solid , mp 72 °- 73 ° c . ______________________________________elemental analysis : c h n i______________________________________calculated 32 . 30 2 . 22 3 . 42 31 . 02found 32 . 12 2 . 23 3 . 37 30 . 98______________________________________ 3 - pyridinecarboxylic acid , 5 - bromo - 2 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl ) -, methyl ester . to a stirred solution of 16 . 22 g ( 0 . 072 mol ) of copper ( ii ) bromide and 9 . 32 g ( 0 . 091 mol ) of t - butyl nitrite in 170 ml of acetonitrile was added a solution of 19 . 71 g ( 0 . 060 mol ) of product of example 209 in 34 ml of acetonitrile . the reaction was stirred at room temperature for 1 hour . the reaction mixture was poured into 856 ml of 20 % hydrochloric acid and then extracted with ether . normal workup yielded 20 . 22 g ( 86 %) of product as a bright yellow oil . chromatography on silica gel ( 1 % ethyl acetate / cyclohexane ) yielded 12 . 24 g ( 52 %) of product as a colorless oil ; n d 25 1 . 472 . ______________________________________elemental analysis : c h n br______________________________________calculated 40 . 02 3 . 36 3 . 59 20 . 48found 40 . 15 3 . 37 3 . 58 20 . 42______________________________________ 3 - pyridinecarboxylic acid , 5 - amino - 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl ) -, methyl ester . to a stirred slurry of 26 . 9 g ( 0 . 414 mol ) of sodium azide , 47 ml of water and 158 ml acetone was slowly added a solution of 62 . 53 g ( 0 . 168 mol ) of methyl 5 - chlorocarbonyl - 6 -( difluoromethyl )- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )- 3 - pyridinecarboxylate in 21 ml of acetone . an exothermic reaction followed with vigorous gas evolution . the reaction was allowed to cool to room temperature and diluted with 565 ml water and extracted with chloroform ( 3 × 100 ml ). workup as usual gave 52 . 9 g ( 97 %) of product as a light yellow solid . chromatography on silica gel ( 20 % ethyl acetate / cyclohexane to elute product ) gave 37 . 25 g ( 68 %) of analytically pure material , mp 104 °- 106 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 78 4 . 68 8 . 56______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( methoxymethylene ) amino ]- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 25 g ( 0 . 01 mol ) of product of example 123 , 6 . 0 ml of trimethyl orthoformate , and 60 mg of p - toluenesulfonic acid was stirred for 28 hours at 100 ° c . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 145 °- 155 ° c . at 1 torr ) to yield 3 . 39 g ( 92 %) of product as a colorless oil . chromatography of product on silica gel ( 2 % ethyl acetate / cyclohexane ) gave analytically pure material ; n d 25 1 . 466 . ______________________________________elemental analysis : c h n______________________________________calculated 48 . 92 4 . 65 7 . 61found 48 . 84 4 . 69 7 . 61______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -[( ethoxymethylene ) amino ]- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, methyl ester . a solution of 3 . 25 g ( 0 . 010 mol ) of product of example 123 , 6 . 2 ml of triethyl orthoformate and 62 mg of p - toluenesulfonic acid was stirred at 100 ° c . for 8 hours . an additional 62 mg of p - toluenesulfonic acid was added and the reaction was complete 20 hours later . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 135 °- 145 ° c . at 1 torr ) to give 3 . 8 g ( 99 %) of product as a colorless oil ; n d 25 1 . 4655 . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 26 5 . 01 7 . 33found 50 . 32 5 . 02 7 . 23______________________________________ 3 - pyridinecarboxylic acid , 2 -( difluoromethyl ) - 5 -[[( dimethylamino ) methylene ] amino ]- 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . a stirred solution of 4 . 0 g ( 0 . 013 mol ) of product of example 115 , 10 ml of dimethylformamide dimethyl acetal , and 70 mg of p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and kugelrohr distilled ( 170 °- 185 ° c . at 1 torr ) to give 3 . 98 g of product as a yellow solid , mp 89 °- 91 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 60 4 . 56 11 . 89found 47 . 63 4 . 59 11 . 88______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) methylene ] amino ]- 4 -( 2 - methylpropyl ) - 2 -( trifluoromethyl )-, methyl ester . a stirred solution of 4 . 0 g ( 0 . 012 mol ) of product of example 123 , 10 ml of dimethylformamide dimethyl acetal , and 70 mg p - toluenesulfonic acid was refluxed overnight . the reaction mixture was concentrated in vacuo and the residue kugelrohr distilled ( 170 °- 185 ° c . at 1 torr ) to give 4 . 11 g ( 88 %) of product as yellow liquid that slowly solidified , mp 59 °- 60 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 50 . 39 5 . 29 11 . 02found 50 . 41 5 . 28 10 . 98______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[( dimethylamino ) methylene ] amino }- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a solution of 4 . 0 g of product of example 1 , 9 ml of dimethylformamide dimethyl acetal , and 91 mg of p - toluenesulfonic acid was stirred at reflux for 3 hours . the reaction mixture was concentrated in vacuo and the residue kugelrohr distilled ( 185 °- 200 ° c . at 1 torr ) to yield a brown oil . chromatography on silica gel ( 7 % ethyl acetate / cyclohexane ) gave 3 . 29 g ( 71 %) of product as a colorless oil ; n d 25 1 . 486 . ______________________________________elemental analysis : c h n______________________________________calculated 51 . 64 5 . 61 10 . 63found 51 . 73 5 . 62 10 . 61______________________________________ 3 - pyridinecarboxylic acid , 5 - azido - 2 -( difluoromethyl ) - 4 - ethyl - 6 -( trifluoromethyl )-, methyl ester . to a 0 ° c . solution of 5 . 0 g ( 0 . 016 mol ) of product of example 115 , 2 . 9 g ( 0 . 016 mol ) of 48 % fluoroboric acid , and 52 ml of acetonitrile was added 1 . 75 g ( 0 . 017 mol ) of t - butyl nitrite dropwise . the reaction mixture was stirred at 0 ° c . for 20 minutes , then a solution of 2 . 72 g 0 . 042 mol ) of sodium azide in 14 ml of water was added . vigorous gas evolution followed . the reaction was stirred for 10 minutes at room temperature , then diluted with 100 ml of water and extracted with chloroform ( 3 × 25 ml ). normal workup afforded 5 . 07 g ( 98 %) of product as an orange oil . chromatography on silica gel ( 2 % ethyl acetate / cyclohexane ) gave 2 . 61 g ( 50 %) of product as a colorless oil ; n d 25 1 . 570 . ______________________________________elemental analysis : c h n______________________________________calculated 40 . 75 2 . 80 17 . 28found 40 . 82 2 . 77 17 . 10______________________________________ 3 - pyridinecarboxylic acid , 5 -( 1 - chloro - 2 , 2 , 2 - trifluoroethylidene ) amino ]- 6 -( difluoromethyl )- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . a mixture of 37 . 65 g ( 0 . 086 mol ) of product of example 7 and 17 . 97 g ( 1 equivalent ) of pcls was stirred overnight at 130 ° c . in a flask fitted with a reflux condenser and a drying tube . the reaction mixture was concentrated in vacuo , then kugelrohr distilled at 90 ° c . to remove low - boiling impurities and finally at 130 ° c . to afford 35 . 78 g ( 0 . 078 mol ) of product as a yellow oil which gradually solidified . yield was 91 %. mp 33 . 0 °- 34 . 0 ° c . ______________________________________elemental analysis : c h n cl______________________________________calculated 42 . 26 3 . 32 6 . 16 7 . 80found 42 . 69 3 . 39 6 . 22 7 . 86______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 5 - ( 2 , 2 , 2 - trifluoro - 1 - methoxyethylidene ) amino ]- 2 -( trifluoromethyl )-, ethyl ester . to a room temperature solution of 2 . 09 g ( 0 . 010 mol ) of 25 % sodium methoxide / methanol and 5 ml of methanol was added a solution of 4 . 0 g 0 . 009 mol ) of product of example 130 in 4 . 7 ml methanol . a yellow precipitate formed immediately and the reaction mixture was stirred at room temperature for 1 hour , then diluted with 25 ml of water and extracted with ether ( 3 × 20 ml . workup as usual followed by kugelrohr distillation ( 135 ° c . at 1 torr ) gave 2 . 57 g ( 65 %) of product as a colorless oil . chromatography on silica gel ( 0 . 5 % ethyl acetate / cyclohexane ) gave 1 . 89 g ( 48 %) of pure product as a colorless oil ; n d 25 1 . 438 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 34 4 . 03 6 . 22found 45 . 32 3 . 91 6 . 25______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )- 5 -[( 2 , 2 , 2 - trifluoro - 1 - ethoxyethylidine ) amino ]-, ethyl ester . to a solution of 3 . 24 g ( 0 . 010 mol ) of 21 % sodium ethoxide / ethanol and 5 ml of ethanol was added a solution of 4 . 0 g ( 0 . 009 mol ) of product of example 130 in 5 ml ethanol . the reaction was stirred at room temperature for 15 minutes . the reaction mixture was diluted with 100 ml water and extracted with ether ( 3 × 25 ml ) which was worked up as usual . kugelrohr distillation ( 135 °- 145 ° c . at 1 torr ) gave 2 . 87 g ( 70 %) of product as a colorless oil . chromatography on silica gel ( 1 % ethyl acetate / cyclohexane ) gave 1 . 89 g ( 46 %) of product as a colorless oil ; n d 25 1 . 439 . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 56 4 . 34 6 . 03found 46 . 64 4 . 34 6 . 14______________________________________ 3 - pyridinecarboxylic acid , 5 -{[ 1 -( dimethylamino ) - 2 , 2 , 2 - trifluoroethylidene ] amino - 6 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . to a room temperature solution of 4 . 0 g ( 0 . 009 mol ) of product of example 130 and 10 ml of dioxane was added 4 . 5 ml ( 0 . 026 mol ) of 26 % aqueous solution of dimethylamine . the solution became warm and was stirred for 30 minutes . the reaction mixture was diluted with 250 ml of water and extracted with chloroform ( 3 × 30 ml ). workup as usual gave a brown oil which was kugelrohr distilled ( 165 ° c . at 1 torr ) to give 2 . 06 g ( 50 %) of product as a yellow oil ; n d 25 1 . 467 . ______________________________________elemental analysis : c h n______________________________________calculated 46 . 66 4 . 57 9 . 07found 46 . 44 4 . 56 9 . 01______________________________________ 3 - pyridinecarboxylic acid , 6 -( difluoromethyl ) - 5 -{[ 1 -( methylamino )- 2 , 2 , 2 - trifluoroethylidene ] amino }- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )-, ethyl ester . to a room temperature solution of 4 . 0 g ( 0 . 009 mol ) of product of example 130 in 10 ml dioxane was added 2 ml ( 0 . 026 mol ) of 40 % aqueous methylamine . the reaction became warm and was stirred for 30 minutes . the reaction mixture was diluted with 250 ml of water and extracted with chloroform ( 3 × 30 ml ). normal workup gave a yellow oil which was kugelrohr distilled ( 175 ° c . at 1 torr ) to yield product as a thick yellow oil ; n d 25 1 . 454 . ______________________________________elemental analysis : c h n______________________________________calculated 45 . 44 4 . 26 9 . 35found 45 . 54 4 . 27 9 . 18______________________________________ ethyl 2 , 6 - bis - trifluoromethyl )- 5 - bromo - 4 - hydroxy - 3 - pyridinecarboxylate . the precursor ethyl 2 , 6 - bis ( trifluoromethyl )- 4 - hydroxy - 3 - pyridinecarboxylate was prepared as follows : to a flame dried 3 - liter , four - necked flask equipped with nitrogen inlet , low temperature thermometer , 500 ml addition funnel and mechanical stirrer was charged 91 . 0 g ( 126 ml , 0 . 899 mol ) of diisopropylamine and 500 ml of dry tetrahydrofuran . the resulting solution was cooled to - 78 ° c . using an acetone - dry ice bath . to this was slowly added 383 ml ( 0 . 880 mol ) of 2 . 3m n - buli in hexane at such a rate that the reaction temperature was kept below - 60 ° c . after stirring at - 78 ° c . for 1 hour , a solution of 90 . 0 g ( 0 . 400 mol ) of ethyl 2 - acetyl - 3 - amino - 4 , 4 , 4 - trifluoro 2 - butenoate in 150 ml of dry tetrahydrofuran was added in such a rate that the reaction temperature was kept below - 60 ° c . the reaction mixture turned yellow and a solid suspension formed . after 1 hour of stirring at - 78 ° c ., the reaction mixture was treated with 184 . 7 g ( 155 ml , 1 . 300 mol ) of ethyl trifluoroacetate in such rate that the reaction temperature was kept below - 60 ° c . this reaction mixture was left at - 78 ° c . for 1 hour , then warmed to room temperature ( the yellow suspension disappeared and a brown solution was formed ) and stirred for 18 hours . the resulting solution was poured into 1 . 5 l of 10 % hcl ( aqueous ) and extracted 3 times with methylene chloride . the combined methylene chloride layers were dried ( mgso 4 ) and reduced in vacuo affording a thick brown oil . the residue was kugelrohr distilled at 47 pa . the earlier fraction ( pot temperature 50 ° c .) was discarded . the later fraction ( pot temperature 80 ° c .) afforded 80 . 0 g ( 66 %) of the pyridine intermediate ; mp 70 °- 77 ° c . to a solution of 5 . 0 g ( 0 . 165 mol ) of the compound prepared above in 50 ml of 10 % naoh was added 5 ml of bromine . an exothermic reaction occurred instantly . the reaction mixture was stirred for 5 minutes and poured into a mixture of 20 ml of concentrated hcl and 50 ml of water . to the above mixture was added sodium sulfite until all red bromine color disappeared . the white oil precipitate was extracted into ether . the ether solution was dried and concentrated . the residue was kugelrohr distilled at 0 . 8 mm ( pot temperature 95 ° c .) to give 5 . 7 g of an oil which was crystallized from petroleum ether at low temperature to give 3 . 5 g ( 55 . 9 %) of product , mp 30 °- 32 ° c ., which turned into a liquid upon standing , n d 25 1 . 4646 . ______________________________________elemental analysis : c h n br______________________________________calculated 31 . 44 1 . 58 3 . 67 20 . 92found 31 . 30 1 . 59 3 . 64 20 . 86______________________________________ using preparative techniques similar to those set out in detail above in examples 1 through 136 , additional compounds were prepared . these additional compounds are shown in the following table 1 , along with a physical property for each where available . table 1__________________________________________________________________________ ## str12 ## example r . sub . 1 r . sub . 2 r ra x mp (° c .) n . sub . d . sup . 25__________________________________________________________________________136 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 3 cyclobutyl 59 . 8 - 64 . 8137 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 br isobutyl 1 . 473138 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 2 ch . sub . 3 cyclobutyl139 cf . sub . 3 cf . sub . 3 och . sub . 2 ch . sub . 3 nh . sub . 2 methoxy 70 . 0 - 71 . 0140 cf . sub . 3 cf . sub . 3 och . sub . 2 ch . sub . 3 br methoxy 1 . 449141 cf . sub . 3 cf . sub . 3 och . sub . 2 ch . sub . 3 i methoxy 39 . 0 - 40 . 0142 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str13 ## isobutyl 1 . 518143 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchoch . sub . 2 ch . sub . 3 cyclopropylmethyl 1 . 480144 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str14 ## isobutyl 96 . 0 - 97 . 0145 cf . sub . 3 cf . sub . 2 h och . sub . 3 br cyclobutyl 50 . 0 - 54 . 0146 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str15 ## cyclobutyl 83 . 0 - 83 . 7147 cf . sub . 3 cf . sub . 2 h och . sub . 3 br isobutyl 1 . 471148 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 nh . sub . 2 isobutyl 94 . 0 - 96 . 0149 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 nchoch . sub . 3 isobutyl 1 . 477150 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 br isobutyl 1 . 483151 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str16 ## propyl 82 . 0 - 84 . 0152 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str17 ## cyclobutyl153 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nso propyl 1 . 476154 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str18 ## isobutyl 1 . 493155 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str19 ## isobutyl 1 . 442156 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 54 . 0 - 57 . 0157 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 1 . 497158 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nhch . sub . 3 isobutyl 1 . 473159 cf . sub . 3 ch . sub . 3 och . sub . 2 ch . sub . 3 no . sub . 2 isobutyl 1 . 465160 cf . sub . 2 h cf . sub . 3 och . sub . 3 no . sub . 2 ethyl 1 . 451161 cf . sub . 3 cf . sub . 2 h sch . sub . 3 ## str20 ## isobutyl 1 . 502162 cf . sub . 3 cf . sub . 2 h och . sub . 3 nco isobutyl 1 . 466163 cf . sub . 3 cf . sub . 2 h och . sub . 3 nso isobutyl 1 . 479164 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str21 ## propyl 64 . 0 - 66 . 0165 cf . sub . 2 h cf . sub . 3 och . sub . 3 nso isobutyl 1 . 482166 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str22 ## isobutyl 168 . 0 - 171 . 0167 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str23 ## isobutyl 1 . 418168 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nh . sub . 2 isobutyl 108 . 0 - 110 . 0169 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str24 ## isobutyl 90 . 0 - 92 . 0170 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 70 . 0 - 71 . 0171 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchoch . sub . 3 isobutyl 1 . 494172 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchoch . sub . 2 ch . sub . 3 isobutyl 1 . 492173 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nchsch . sub . 3 isobutyl 1 . 4925174 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str25 ## isobutyl 118 . 0 - 120 . 0175 cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 nso isobutyl 1 . 477176 cf . sub . 3 cf . sub . 2 h sch . sub . 3 br isobutyl 37 . 0 - 38 . 0177 ## str26 ## 177 ( cont .) cf . sub . 3 cf . sub . 2 h och . sub . 2 ch . sub . 3 ## str27 ## isobutyl178 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 3 isobutyl 1 . 493179 cf . sub . 3 cf . sub . 2 h och . sub . 3 n ( cho ). sub . 2 isobutyl 1 . 457180 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchsch . sub . 2 ch . sub . 3 isobutyl 1 . 493181 cf . sub . 2 h cf . sub . 3 och . sub . 3 ## str28 ## isobutyl 182 . 0 - 184 . 0182 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str29 ## isobutyl 1 . 488183 cf . sub . 2 h cf . sub . 3 och . sub . 3 ## str30 ## isobutyl 1 . 494184 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str31 ## isobutyl 112 . 0 - 114 . 0185 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str32 ## isobutyl 1 . 483186 cf . sub . 2 h cf . sub . 3 och . sub . 3 ## str33 ## isobutyl 160 . 0 - 161 . 0187 cf . sub . 2 h cf . sub . 3 sch . sub . 3 br isobutyl 1 . 507188 cf . sub . 3 cf . sub . 2 h sch . sub . 2 ch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 isobutyl 1 . 511189 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str34 ## isobutyl 1 . 470190 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str35 ## isobutyl 1 . 4845191 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str36 ## isobutyl 1 . 462192 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str37 ## isobutyl 1 . 477193 cf . sub . 3 cf . sub . 2 h och . sub . 3 ncfch . sub . 3 isobutyl 158 . 0 - 160 . 0194 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str38 ## isobutyl 1 . 492195 cf . sub . 3 cf . sub . 2 h och . sub . 3 ## str39 ## isobutyl 118 . 0 - 119 . 0196 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchsch . sub . 3 isobutyl 1 . 523197 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nhcoch . sub . 3 isobutyl 140 . 0 - 142 . 0198 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nh . sub . 2 cyclopropylmethyl 90 . 0 - 92 . 0199 cf . sub . 3 cf . sub . 2 h sch . sub . 3 nchn ( ch . sub . 3 ). sub . 2 cyclopropylmethyl 109 . 0 - 112 . 0200 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchoch . sub . 3 cyclobutyl 64 . 0 - 66 . 0201 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchoch . sub . 2 ch . sub . 3 cyclobutyl 48 . 0 - 52 . 0202 cf . sub . 3 cf . sub . 2 h och . sub . 3 nchn ( ch . sub . 3 ). sub . 2 cyclobutyl 86 . 6 - 88 . 4203 cf . sub . 3 cf . sub . 2 h och . sub . 3 nh . sub . 2 cyclobutyl 88 . 8 - 90 . 5204 cf . sub . 2 h cf . sub . 3 och . sub . 3 nh . sub . 2 cyclobutyl 89 . 0 - 92 . 8205 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchoch . sub . 3 cyclobutyl206 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchoch . sub . 2 ch . sub . 3 cyclobutyl207 cf . sub . 2 h cf . sub . 3 och . sub . 3 nchn ( ch . sub . 3 ). sub . 2 cyclobutyl 69 . 0 - 74 . 0208 cf . sub . 2 h cf . sub . 3 och . sub . 3 br cyclobutyl__________________________________________________________________________ pg , 85 3 - pyridinecarboxylic acid , 5 - amino - 2 -( difluoromethyl ) - 4 -( 2 - methylpropyl )- 6 -( trifluoromethyl )-, methyl ester . to a stirred slurry of 27 . 8 g of sodium azide , 50 ml of water and 164 ml of acetone was slowly added a solution of 65 . 2 g ( 0 . 183 mol ) of methyl 5 - chlorocarbonyl - 6 -( difluoromethyl )- 4 -( 2 - methylpropyl )- 2 -( trifluoromethyl )- 3 - pyridinecarboxylate in 16 ml of acetone . an exothermic reaction followed with vigorous gas evolution . the reaction mixture was allowed to cool to room temperature and diluted with water ( 500 ml ) and extracted into chloroform ( 3 × 100 ml ). normal workup afforded 51 . 93 g ( 94 %) of product as green solid . chromatography on silica gel ( 10 % ethyl acetate / cyclohexane ) gave analytically pure material , mp 48 °- 50 ° c . ______________________________________elemental analysis : c h n______________________________________calculated 47 . 86 4 . 63 8 . 59found 47 . 81 4 . 63 8 . 58______________________________________ as noted above , many of the compounds of this invention have been found to be effective as pre - emergent and post - emergent herbicides . table 2 summarizes results of tests conducted to determine the pre - emergent herbicidal activity of the compounds of this invention on common weeds . top soil is placed in aluminum pans and compacted to a depth of 0 . 95 to 1 . 27 cm . from the top of the pan . on the top of the soil is placed a predetermined number of seeds or vegetative propagules of various plant species . the soil required to level fill the pans after seeding or adding vegetative propagules is weighed into a pan . a known amount of the active ingredient applied in acetone as a solvent is thoroughly mixed with the soil , and the herbicide / soil mixture is used as a cover layer for prepared pans . in table 3 below the amount of active ingredient is equal to the rate of 11 . 2 kg / ha . after treatment , the pans are moved to a greenhouse bench where they are watered from below as needed to give adequate moisture for germination and growth . approximately 10 - 14 days ( usually 11 days ) after seeding and treating , the pans are observed and the results recorded . in some instances , a second observation is made approximately 24 - 28 days after seeding and treating , and these observations are indicated in the following tables by an asterisk (*) immediately following the example number . table 2 below summarizes the results of the pre - emergent herbicidal activity tests of compounds of this invention in weeds . the herbicidal rating is obtained by means of a fixed scale based on the percent inhibition of each plant species . the symbols in the table are defined as follows : ______________________________________ % inhibition rating______________________________________ 0 - 24 025 - 49 150 - 74 2 75 - 100 3not planted -- species planted , nno data______________________________________ the plant species usually regarded as weeds which are utilized in one set of tests , the data for which are shown in table 3 , are identified by letter headings above the columns in accordance with the following legend : ______________________________________ a - canada thistle * b - cocklebur c - velvetleaf d - morningglory e - common lambsquarters f - pennsylvania smartweed g - yellow nutsedge * h - quackgrass * i - jonhsongrass * j - downy brome k - barnyardgrass______________________________________ * grown from vegetative propagules table 2______________________________________pre - emergent activity for weedsexample no . kg / ha a b c d e f g h i j k______________________________________ 1 11 . 2 0 0 1 2 3 3 0 3 0 3 3 2 11 . 2 0 0 3 3 3 3 0 2 -- 3 3 3 11 . 2 0 0 1 2 3 2 0 3 3 1 3 4 11 . 2 0 0 0 0 1 3 0 0 3 0 1 5 11 . 2 3 2 3 3 3 3 2 2 3 3 3 6 11 . 2 0 0 3 1 3 3 0 0 3 3 3 7 11 . 2 3 0 2 3 3 2 0 0 3 2 2 8 11 . 2 0 0 0 0 0 1 0 3 3 3 3 9 11 . 2 3 0 2 3 3 3 0 1 n 3 3 10 11 . 2 3 n 2 3 3 2 1 3 3 3 3 11 11 . 2 0 1 1 3 2 2 0 3 3 3 3 12 11 . 2 3 1 1 3 3 3 0 3 -- 3 3 13 11 . 2 3 1 2 3 3 3 0 3 3 3 3 14 11 . 2 3 0 2 3 3 3 3 3 -- 3 3 15 11 . 2 1 1 3 3 3 3 2 3 3 3 3 16 11 . 2 3 0 3 3 3 3 0 2 0 2 3 17 11 . 2 -- 1 3 3 3 3 0 3 2 3 3 18 11 . 2 -- n 0 0 3 0 0 0 0 0 1 19 11 . 2 -- 0 1 2 3 3 0 3 3 3 3 20 11 . 2 -- 1 0 0 0 1 0 0 0 0 1 21 11 . 2 -- 0 0 0 0 0 0 0 0 2 0 22 11 . 2 -- 0 0 0 0 2 0 0 0 2 2 23 11 . 2 -- 1 1 0 0 1 1 0 1 0 1 24 11 . 2 -- 0 0 0 0 0 0 0 3 0 0 25 11 . 2 1 n 1 0 3 1 0 0 0 0 2 26 11 . 2 -- 0 2 0 3 2 0 0 0 1 2 26 * 11 . 2 -- 0 2 0 3 1 0 0 0 1 2 27 11 . 2 -- 0 3 3 n 3 0 0 0 0 0 28 11 . 2 -- 2 3 3 3 3 0 1 1 1 1 29 11 . 2 -- 0 0 0 2 2 0 0 0 3 3 30 11 . 2 -- 0 0 0 0 0 0 0 0 1 0 31 11 . 2 -- 2 2 0 0 3 0 0 0 1 3 32 11 . 2 -- 3 3 3 3 3 0 3 3 3 3 33 11 . 2 -- 1 3 3 3 3 0 3 3 3 3 34 11 . 2 -- 0 3 3 3 3 0 3 3 3 3 35 11 . 2 -- 2 3 3 3 3 2 3 3 3 3 36 11 . 2 -- 0 3 3 3 3 0 3 0 3 3 37 11 . 2 -- 0 3 3 3 2 0 3 0 3 3 38 11 . 2 -- 1 3 3 3 3 1 3 3 3 3 39 11 . 2 -- 2 3 3 3 3 2 3 3 3 3 40 11 . 2 -- 0 3 3 3 3 0 3 3 3 3 41 11 . 2 -- 0 0 0 3 3 0 0 n 0 3 42 11 . 2 -- 0 2 0 2 3 0 0 n 1 3 43 11 . 2 -- 0 0 0 3 3 0 0 0 3 3 44 11 . 2 -- 0 0 0 3 3 0 0 0 0 3 45 11 . 2 -- 0 1 0 3 3 0 0 0 3 3 46 11 . 2 -- 1 0 0 3 3 1 0 0 1 0 47 11 . 2 -- 0 0 2 1 3 0 1 0 3 3 49 11 . 2 -- 1 1 1 3 3 0 3 3 3 3 50 11 . 2 -- 0 0 0 1 2 0 1 2 3 3 51 11 . 2 -- 0 1 0 3 1 0 0 0 0 0 52 11 . 2 -- 0 1 1 3 3 0 2 0 3 3 53 11 . 2 -- 0 2 3 3 3 0 3 1 3 3 54 11 . 2 -- 3 3 3 3 3 1 3 1 3 3 55 11 . 2 -- 0 2 2 1 2 0 3 0 3 3 56 11 . 2 -- 0 1 3 3 3 0 2 0 3 3 57 11 . 2 -- 1 3 3 3 3 0 3 1 3 3 58 11 . 2 -- 0 2 1 3 2 0 3 0 3 3 59 11 . 2 -- 1 2 1 2 2 0 0 0 1 3 60 11 . 2 -- 0 2 1 3 3 0 0 0 3 3 61 11 . 2 -- 0 0 0 1 0 0 0 0 0 3 62 11 . 2 -- 0 0 0 0 0 0 0 0 0 2 63 11 . 2 -- 0 1 0 3 2 0 2 0 2 3 64 11 . 2 -- 0 0 0 0 1 0 3 1 0 3 65 11 . 2 -- 0 3 0 1 1 0 2 0 0 3 66 11 . 2 -- 3 0 0 0 0 0 0 3 0 0 67 11 . 2 -- 0 2 0 0 0 0 1 n 0 0 68 11 . 2 -- 3 3 3 3 3 0 0 0 3 3 69 11 . 2 -- 3 0 3 3 2 0 0 0 1 3 70 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 71 11 . 2 0 1 3 3 3 3 0 1 1 2 3 72 11 . 2 1 0 3 3 3 3 0 3 0 3 3 73 11 . 2 0 3 0 3 1 1 0 3 3 3 3 74 11 . 2 0 3 0 3 3 3 0 3 0 3 3 75 11 . 2 0 3 1 3 3 3 0 1 0 3 3 76 11 . 2 -- 0 2 3 3 3 0 3 3 3 3 77 11 . 2 -- 0 2 3 3 3 0 3 0 3 3 78 11 . 2 -- 1 2 3 3 3 0 3 0 3 3 79 11 . 2 -- 0 1 3 3 3 0 3 1 3 3 80 11 . 2 -- 0 1 3 3 3 0 3 0 3 3 81 11 . 2 -- 0 3 3 3 3 1 3 0 3 3 82 11 . 2 -- 1 0 3 2 1 0 3 3 3 3 83 11 . 2 -- 0 1 3 3 3 0 3 0 3 3 84 11 . 2 -- 1 2 3 3 3 0 3 1 3 3 85 11 . 2 -- 1 3 3 3 3 2 3 3 3 3 86 11 . 2 -- 0 3 3 3 3 0 3 2 3 3 87 11 . 2 -- 0 1 1 1 1 0 0 n 1 3 88 11 . 2 -- 0 2 2 3 3 0 2 n 3 3 89 11 . 2 -- 0 3 3 3 3 0 2 2 3 3 90 11 . 2 -- 0 3 3 3 3 0 0 0 2 3 91 11 . 2 -- 0 2 3 3 1 0 0 n 2 3 92 11 . 2 -- 0 2 3 3 2 0 1 0 2 3 93 11 . 2 -- 0 0 1 3 3 0 0 0 3 3 94 11 . 2 -- 1 0 0 1 0 0 0 0 3 3 95 11 . 2 -- 1 2 3 3 3 0 3 2 3 3 96 11 . 2 -- 0 3 3 3 3 0 3 0 3 3 97 11 . 2 -- 0 2 3 3 3 0 3 3 3 3 98 11 . 2 3 1 3 3 3 3 1 3 2 3 3 99 11 . 2 -- 1 3 3 3 3 0 3 0 3 3 100 11 . 2 -- 2 3 3 3 3 2 3 3 3 3 101 11 . 2 3 0 3 3 3 3 0 3 0 3 3 102 11 . 2 0 1 3 3 3 3 1 3 0 3 3 103 11 . 2 1 1 3 2 3 3 0 1 0 3 3 104 11 . 2 0 0 1 2 3 3 0 0 0 1 3 105 11 . 2 0 1 2 3 3 3 0 3 3 3 3 106 11 . 2 2 2 3 3 3 3 0 3 0 3 3 107 11 . 2 2 0 1 1 3 1 0 0 0 0 1 108 11 . 2 1 1 0 2 3 2 0 0 0 0 0 109 11 . 2 0 1 0 3 3 3 1 0 0 0 3 110 11 . 2 1 0 1 1 2 1 0 0 0 3 3 111 11 . 2 1 0 0 0 2 1 0 0 2 1 3 112 11 . 2 3 0 3 3 3 3 0 0 0 3 3 113 11 . 2 0 0 3 3 3 3 0 0 3 3 3 114 11 . 2 3 3 3 3 3 3 3 3 3 3 3 115 11 . 2 0 1 3 3 3 3 0 0 3 3 3 116 11 . 2 1 3 3 3 3 3 1 3 1 3 3 117 11 . 2 3 1 3 3 3 3 1 3 3 3 3 118 11 . 2 3 3 3 3 3 3 3 3 3 3 3 119 11 . 2 0 0 2 3 3 3 3 3 0 3 3 120 11 . 2 0 0 1 2 2 3 0 3 0 3 3 121 11 . 2 3 0 3 3 3 3 1 3 3 3 3 122 11 . 2 1 0 3 3 3 3 2 3 0 3 3 123 11 . 2 1 1 3 2 3 3 0 0 0 3 3 124 11 . 2 3 2 3 3 3 3 3 3 3 3 3 125 11 . 2 3 3 3 3 3 3 3 3 3 3 3 126 11 . 2 1 1 3 3 3 3 0 3 2 3 3 127 11 . 2 3 3 3 3 3 3 3 3 3 3 3 128 11 . 2 3 2 3 3 3 3 3 3 3 3 3 129 11 . 2 3 1 3 3 3 3 3 3 3 3 3 130 11 . 2 2 1 3 3 3 3 0 3 0 2 3 131 11 . 2 0 1 3 3 3 3 0 3 3 3 3 132 11 . 2 0 0 1 0 0 0 0 2 1 3 3 133 11 . 2 0 0 3 3 3 3 0 2 0 3 3 134 11 . 2 0 0 3 3 3 3 0 2 0 3 3 135 11 . 2 0 1 2 2 3 3 0 n 0 0 0 135 * 11 . 2 0 0 1 2 3 2 0 n 0 0 0 136 11 . 2 3 2 3 3 3 3 1 3 3 -- 3 137 11 . 2 3 1 0 1 2 2 0 3 -- 3 3 138 11 . 2 0 0 1 2 3 3 0 2 3 -- 3 139 11 . 2 0 0 0 1 0 0 0 0 0 0 3 140 11 . 2 3 0 0 2 0 0 0 0 n 0 0 141 11 . 2 0 0 0 2 3 3 0 0 n 3 3 142 11 . 2 3 3 3 3 3 3 2 3 3 -- 3 143 11 . 2 3 2 3 3 3 3 2 3 3 -- 3 144 11 . 2 3 0 3 3 3 3 1 3 3 -- 3 145 11 . 2 1 0 2 2 3 3 1 3 0 -- 3 146 11 . 2 3 1 3 3 3 3 2 3 3 -- 3 147 11 . 2 1 0 1 3 3 3 0 3 1 3 3 148 11 . 2 0 0 2 0 3 2 1 0 0 1 3 149 11 . 2 3 1 3 3 3 3 0 3 3 3 3 150 11 . 2 3 0 0 2 3 0 0 3 3 1 3 151 11 . 2 3 0 3 3 3 3 1 0 0 2 3 152 11 . 2 3 0 3 3 3 3 0 3 0 -- 3 153 11 . 2 2 0 3 3 3 3 0 0 0 2 3 154 11 . 2 3 2 3 3 3 3 3 3 3 3 3 155 11 . 2 3 0 1 3 3 2 0 0 0 0 3 156 11 . 2 3 3 3 3 3 3 2 3 3 3 3 157 11 . 2 3 0 3 3 3 3 1 3 1 3 3 158 11 . 2 0 0 3 3 3 3 0 3 0 3 3 159 11 . 2 0 0 0 0 3 1 0 3 1 3 3 160 11 . 2 0 0 0 0 0 0 0 1 0 0 3 161 11 . 2 3 0 3 3 3 3 0 0 0 -- 3 162 11 . 2 0 0 1 2 3 3 0 0 0 3 3 163 11 . 2 1 0 1 1 3 3 0 0 0 3 3 164 11 . 2 3 0 3 3 3 3 0 3 0 3 3 165 11 . 2 1 0 3 3 3 3 1 3 0 3 3 166 11 . 2 3 0 1 1 3 3 0 3 0 3 3 167 11 . 2 3 0 2 3 3 3 1 3 0 1 3 168 11 . 2 3 1 3 3 3 3 2 3 1 3 3 169 11 . 2 1 0 3 3 3 3 0 0 0 1 3 170 11 . 2 3 3 3 3 3 3 3 3 3 3 3 171 11 . 2 3 2 3 3 3 3 2 3 3 3 3 172 11 . 2 3 2 3 3 3 3 1 3 1 3 3 173 11 . 2 3 2 3 3 3 3 3 3 2 3 3 174 11 . 2 0 0 1 0 2 0 0 0 0 0 3 175 11 . 2 1 0 3 3 3 3 0 1 0 3 3 176 11 . 2 0 0 3 3 3 3 0 3 0 3 3 177 11 . 2 0 0 0 0 3 1 0 2 0 0 3 178 11 . 2 3 2 3 3 3 3 3 3 3 3 3 179 11 . 2 1 0 0 0 3 1 0 0 0 0 3 180 11 . 2 3 1 3 3 3 3 0 3 3 3 3 181 11 . 2 0 0 0 2 2 1 0 1 3 0 3 182 11 . 2 0 0 0 0 3 3 0 0 0 1 3 183 11 . 2 1 0 3 3 3 3 0 3 0 3 3 184 11 . 2 0 0 2 1 3 3 0 1 0 3 3 185 11 . 2 0 0 2 1 3 3 0 0 0 3 3 186 11 . 2 0 0 0 0 0 0 0 0 0 0 3 187 11 . 2 1 0 2 3 3 3 0 3 0 3 3 188 11 . 2 2 1 3 3 3 3 1 3 0 3 3 189 11 . 2 0 0 0 0 0 0 0 0 0 0 0 190 11 . 2 3 1 3 3 3 3 1 3 3 3 3 191 11 . 2 3 3 3 3 3 3 3 3 3 n 3 192 11 . 2 0 0 2 3 3 1 0 1 0 n 3 193 11 . 2 0 0 1 0 0 0 0 0 0 n 3 194 11 . 2 3 1 3 3 3 3 2 3 3 3 3 195 11 . 2 0 0 0 1 2 0 0 0 3 1 3 196 11 . 2 3 3 3 3 3 3 3 3 3 3 3 197 11 . 2 0 0 0 0 2 0 0 0 n 0 3 198 11 . 2 1 1 2 3 3 3 0 0 0 3 3 199 11 . 2 3 2 3 3 3 3 3 3 2 3 3 200 11 . 2 3 0 3 3 3 3 2 3 3 3 3 201 11 . 2 0 0 3 3 3 3 1 3 3 3 3 202 11 . 2 3 0 3 3 3 3 1 3 3 3 3 203 11 . 2 0 0 3 3 3 3 0 0 3 1 3 204 11 . 2 3 0 3 3 3 3 1 3 3 3 3 205 11 . 2 3 3 3 3 3 3 1 3 3 3 3 206 11 . 2 3 2 3 3 3 3 1 3 3 3 3 207 11 . 2 3 0 3 3 3 3 0 3 3 3 3 208 11 . 2 3 0 3 3 3 3 1 3 3 3 3______________________________________ the compounds were further tested by utilizing the above procedure on the following plant species , i . e ., on weeds in the presence of crop plants . ______________________________________l - soybean r - hemp sesbaniam - sugarbeet e - common lambsquartersn - wheat f - pennsylvania smartweedo - rice c - velvetleafp - grain sorghum j - downy bromeb - cocklebur s - panicum spp . q - wild buckwheat k - barnyardgrassd - morningglory t - large crabgrass______________________________________ table 3__________________________________________________________________________pre - emergent activity for weeds in crop plantsexample no . kg / ha l m n o p b q d r e f c j s k t__________________________________________________________________________ 1 5 . 6 0 3 0 0 2 0 0 1 1 3 3 1 1 2 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 5 . 6 0 3 2 2 3 0 3 3 2 3 3 2 3 3 3 3 1 . 12 0 1 0 0 0 0 0 0 0 0 0 0 0 1 1 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 5 . 6 2 3 0 3 3 0 3 3 3 3 2 3 3 3 3 3 1 . 12 0 2 0 0 2 0 2 0 0 1 1 1 1 3 3 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 4 5 . 6 0 1 0 0 2 0 0 0 1 0 0 0 2 2 2 2 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 5 . 6 1 3 1 3 3 0 2 2 2 3 2 2 3 3 3 3 1 . 12 0 1 0 0 0 0 0 2 2 2 1 1 1 2 3 3 0 . 28 0 0 0 0 0 n 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 n 0 0 0 0 0 0 0 0 0 0 6 5 . 6 0 3 1 1 3 n 3 3 3 3 3 2 3 3 3 3 1 . 12 0 0 0 0 0 n 0 0 0 2 1 1 1 0 0 3 0 . 28 0 0 0 0 0 n 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 n 0 0 0 0 0 0 0 0 0 0 7 5 . 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 8 5 . 6 0 0 1 1 3 0 0 0 0 0 0 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 9 5 . 6 1 3 3 2 3 0 3 3 3 3 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3 3 3 1 . 12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 0 . 28 2 3 3 3 3 0 3 3 2 3 3 2 3 3 3 3 0 . 056 2 0 1 2 3 0 3 0 1 2 1 1 2 3 3 3 0 . 0112 0 0 0 1 1 0 0 0 0 1 0 0 0 1 1 3128 5 . 6 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 3 2 3 3 3 3 3 3 3 0 . 28 1 2 1 1 2 0 3 2 2 3 3 1 3 3 3 3 0 . 056 0 0 0 0 1 0 0 0 1 0 0 0 2 3 3 3 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0129 5 . 6 2 2 3 3 3 0 2 3 3 3 3 1 3 3 3 3 1 . 12 0 0 1 0 1 0 1 1 0 0 1 0 3 1 2 1 0 . 28 0 0 0 0 0 0 1 0 0 1 0 0 0 0 0 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0130 5 . 6 0 3 0 0 2 0 0 2 0 3 3 0 2 1 2 2 1 . 12 0 3 0 0 0 0 n2 0 2 1 0 2 0 0 0 0 . 28 0 1 0 0 0 0 1 0 0 0 0 0 2 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0131 5 . 6 0 0 3 2 3 0 0 0 0 0 0 0 3 3 3 3 1 . 12 0 0 1 0 2 0 0 0 0 0 0 0 3 1 2 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 0 n 0 0 0 0 0 0 0 0 0132 5 . 6 0 1 3 1 0 0 0 0 1 2 1 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 2 1 0 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0133 5 . 6 1 2 2 2 3 0 3 2 2 3 3 2 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 1 0 0 2 2 3 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1134 5 . 6 1 2 2 3 3 0 3 2 2 3 3 2 3 3 3 3 1 . 12 0 2 0 0 0 0 0 0 0 3 0 0 1 2 2 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0135 5 . 6 0 3 0 0 0 0 2 2 2 3 3 0 1 1 0 0 1 . 12 0 3 0 0 0 0 2 2 1 2 1 0 0 0 0 0 0 . 28 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0137 5 . 6 0 3 1 1 3 0 0 0 1 2 1 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 3 2 0 0 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0139 5 . 6 0 3 0 0 0 0 0 0 0 2 1 1 1 1 2 3 1 . 12 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0141 5 . 6 0 2 0 0 0 0 0 0 0 0 0 0 0 1 1 2 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0147 5 . 6 1 0 3 2 3 0 2 2 1 3 3 0 3 3 3 3 1 . 12 0 0 0 1 0 0 1 0 0 1 0 0 3 2 3 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0148 5 . 6 0 0 0 0 0 0 3 0 0 3 1 0 3 0 3 3 1 . 12 0 1 0 0 0 0 3 1 0 2 1 0 3 1 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0149 5 . 6 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 1 . 12 0 1 2 2 3 0 3 2 2 3 3 2 3 3 3 3 0 . 28 0 0 0 0 1 0 3 0 1 3 0 0 0 1 3 3 0 . 056 0 0 0 0 0 0 2 0 0 1 0 0 1 0 0 1 0 . 0112 0 0 0 0 0 0 2 0 0 1 0 0 1 1 0 1150 5 . 6 2 0 3 2 1 0 1 1 1 3 3 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0151 5 . 6 0 1 0 1 3 0 1 2 1 3 2 0 3 3 3 3 1 . 12 0 0 0 1 1 0 0 0 0 1 0 0 1 0 0 1 0 . 28 0 0 0 0 0 0 0 0 0 1 0 0 0 1 0 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0153 5 . 6 n 2 0 2 2 0 2 2 2 3 3 1 3 3 3 3 1 . 12 0 1 0 1 1 0 0 0 0 1 1 0 1 0 2 2 0 . 28 0 1 0 0 1 0 0 0 0 1 0 0 0 1 0 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1155 5 . 6 0 3 0 0 1 0 2 3 0 2 2 0 3 0 0 1 1 . 12 0 2 0 0 0 0 1 2 0 2 1 0 1 0 1 0 0 . 28 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0156 5 . 6 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 2 2 3 3 3 3 3 3 3 0 . 28 1 1 2 2 3 0 2 1 2 3 3 2 2 3 3 3 0 . 056 0 0 0 0 1 0 1 0 1 2 1 0 0 1 2 3 0 . 0112 0 0 0 0 0 0 0 0 0 1 0 0 0 0 1 1157 5 . 6 3 3 3 3 1 0 3 3 3 3 3 2 3 3 3 3 1 . 12 3 2 1 2 0 0 0 2 2 3 3 2 2 3 3 3 0 . 28 1 1 0 0 0 0 0 1 0 0 0 0 0 2 2 3 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0158 5 . 6 0 1 2 1 3 0 1 3 2 2 2 0 3 3 3 3 1 . 12 0 0 1 1 0 0 3 0 0 0 1 0 0 2 3 2 0 . 28 0 0 0 0 0 0 3 1 0 0 0 0 2 0 0 0 0 . 056 0 0 0 0 0 0 3 1 0 0 0 0 0 0 0 0 0 . 0112 0 0 0 0 0 0 2 0 0 0 0 0 1 0 0 0159 5 . 6 0 0 1 1 2 0 1 2 1 1 2 0 2 3 3 3 1 . 12 0 0 0 0 0 0 1 1 0 1 0 0 0 0 0 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0160 5 . 6 0 1 1 0 0 0 0 0 0 0 0 0 1 0 2 0 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0162 5 . 6 0 1 0 0 3 0 0 1 1 3 2 1 3 3 3 3 1 . 12 0 0 0 0 0 0 0 n 0 0 1 0 0 0 2 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0163 5 . 6 0 0 0 0 1 0 1 n 1 3 2 0 2 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0164 5 . 6 2 3 1 0 3 0 3 3 3 3 3 2 3 3 3 3 1 . 12 0 1 0 0 2 0 0 n 0 3 1 1 3 3 3 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0165 5 . 6 0 3 3 3 3 0 1 2 2 3 3 2 3 3 3 3 1 . 12 0 1 0 1 2 0 0 1 0 0 1 0 2 3 3 3 0 . 28 0 0 0 0 1 0 0 0 0 0 0 0 0 0 1 1 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0166 5 . 6 3 2 3 0 2 0 3 1 0 3 3 1 3 3 3 3 1 . 12 0 0 0 0 0 0 0 n 0 2 1 0 0 0 0 2 0 . 56 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 014 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0167 5 . 6 1 3 1 2 0 0 2 2 0 3 2 1 3 0 1 2 1 . 12 0 1 0 0 0 0 1 0 0 2 0 0 1 0 0 0 0 . 28 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0168 5 . 6 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 1 . 12 0 3 2 2 3 0 3 3 2 3 3 2 3 3 3 3 0 . 28 0 0 1 1 0 0 0 1 0 3 1 0 2 2 3 3 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0169 5 . 6 0 3 0 1 0 0 1 0 0 3 1 0 1 1 0 3 1 . 12 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 2 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0170 5 . 6 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 0 . 28 1 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 0 . 056 0 3 2 3 3 0 3 0 3 3 3 3 3 3 3 3 0 . 0112 0 2 0 0 1 0 1 0 0 3 2 1 0 1 3 3171 5 . 6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 0 . 28 0 2 3 3 3 0 2 2 2 3 3 2 3 3 3 3 0 . 056 0 0 1 1 3 0 0 0 0 2 2 0 2 3 3 3 0 . 0112 0 0 0 0 0 0 0 0 0 1 0 0 0 0 2 3172 5 . 6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 0 . 28 0 2 2 2 3 0 2 0 1 3 3 1 3 3 3 3 0 . 056 0 0 0 1 0 0 1 0 0 0 0 0 2 2 2 3 0 . 0112 0 0 0 0 0 0 0 0 1 1 1 1 1 0 0 0173 5 . 6 3 3 3 3 3 1 3 3 3 3 3 2 3 3 3 3 1 . 12 0 3 1 1 3 0 3 3 3 3 3 1 3 3 3 3 0 . 28 0 2 0 0 3 0 0 1 2 2 3 0 3 3 3 3 0 . 056 0 1 0 0 0 0 0 0 1 0 1 0 1 2 3 2 0 . 0112 0 0 0 0 0 0 0 n 0 0 1 0 0 0 0 0174 5 . 6 0 2 0 1 0 0 0 0 0 3 1 0 3 0 0 2 1 . 12 0 0 0 0 0 0 0 0 0 1 0 0 2 0 0 1175 5 . 6 0 3 1 1 3 0 0 1 1 2 3 1 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 1 0 2 1 3 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0176 5 . 6 1 3 3 3 3 0 3 2 3 3 3 2 3 3 3 3 1 . 12 0 3 2 1 3 0 2 0 1 3 2 0 3 3 3 3 0 . 28 0 1 0 0 0 0 0 0 0 0 0 0 3 0 2 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0177 5 . 6 2 3 1 1 0 0 2 0 1 3 2 1 3 1 3 3 1 . 12 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1178 5 . 6 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1 . 12 3 3 3 3 3 0 3 3 3 3 3 2 3 3 3 3 0 . 28 0 3 1 1 3 0 3 2 2 3 3 0 3 3 3 3 0 . 056 0 0 0 0 0 0 3 0 0 0 0 0 3 3 3 3 0 . 0112 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 2179 5 . 6 0 3 0 0 0 0 0 0 0 2 1 0 2 1 2 2 1 . 12 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0180 5 . 6 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 1 . 12 0 2 2 2 2 0 2 2 2 3 3 2 2 3 3 3 0 . 56 0 0 2 0 1 0 1 1 0 2 3 0 2 3 3 3 0 . 28 0 0 1 0 1 0 0 0 0 0 2 0 2 3 3 3 0 . 14 0 0 0 0 0 0 0 0 0 0 1 0 1 1 3 3 0 . 07 0 1 1 0 0 0 0 0 0 1 0 0 1 0 1 1 0 . 035 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0182 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0818 5 . 6 0 3 0 0 0 0 2 0 0 2 2 0 1 1 3 2 1 . 12 0 2 0 0 0 0 0 0 0 2 2 0 0 0 0 0 0 . 56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0182 5 . 6 0 1 0 1 3 0 1 1 1 2 2 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 1 0 0 0 2 3 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1183 5 . 6 1 3 3 3 3 0 3 2 3 3 3 1 3 3 3 3 1 . 12 0 0 2 1 3 0 0 1 1 2 1 n 1 3 3 3 0 . 28 1 0 0 0 1 0 0 0 0 0 1 0 0 0 3 2 0 . 056 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1184 5 . 6 1 0 1 0 2 0 0 0 0 0 2 0 2 3 3 3 1 . 12 0 0 1 0 0 0 0 0 0 0 1 0 0 0 1 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1185 5 . 6 0 1 0 1 3 0 1 1 1 0 2 0 3 3 3 3 1 . 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1186 5 . 6 0 3 0 1 0 1 0 2 2 2 2 1 1 0 1 3 1 . 12 0 2 0 0 0 0 0 0 1 2 2 1 0 0 0 1188 5 . 6 3 3 3 3 3 0 3 3 3 3 3 3 3 3 3 3 1 . 12 0 3 2 2 2 0 2 2 3 2 3 3 2 3 3 3 0 . 56 0 3 1 1 2 0 2 2 2 2 3 2 2 3 3 3 0 . 28 0 2 0 1 1 0 1 1 2 1 3 0 1 3 3 3 0 . 14 0 1 0 0 1 0 0 0 0 0 2 0 0 2 3 3 0 . 07 0 1 0 0 0 0 0 0 0 0 1 0 0 0 1 2190 5 . 6 1 3 1 2 2 1 3 2 2 3 3 2 3 3 3 3 1 . 12 1 3 1 1 1 1 2 1 0 3 2 1 3 2 3 3 0 . 56 0 0 1 0 1 0 2 0 0 1 1 0 2 1 1 2 0 . 28 0 1 1 1 0 0 2 0 0 0 0 0 0 0 0 0 0 . 14 0 1 0 0 0 0 2 0 0 0 0 0 0 0 0 1 0 . 07 0 1 0 0 0 0 2 0 0 1 0 0 2 0 0 1 0 . 035 0 1 2 1 0 0 1 0 0 1 1 0 1 0 0 0191 5 . 6 3 3 3 3 3 1 3 3 3 3 3 3 3 3 3 3 1 . 12 1 3 3 3 3 0 3 2 2 3 3 3 3 3 3 3 0 . 56 0 3 3 3 3 0 2 1 2 3 3 2 3 3 3 3 0 . 28 0 1 2 2 3 0 1 0 1 2 2 0 3 3 3 3 0 . 14 0 1 1 1 3 0 1 0 0 0 2 0 2 2 3 2 0 . 07 0 0 0 1 1 0 0 0 0 0 1 0 3 3 3 1 0 . 035 0 0 0 0 0 0 0 0 0 0 1 0 1 0 1 0 0 . 0182 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 009 0 0 0 0 0 0 0 0 0 0 0 n 0 0 0 0192 5 . 6 0 2 1 0 3 0 2 2 1 3 3 3 3 3 3 3 1 . 12 0 1 0 0 0 0 0 0 1 3 1 0 0 1 3 3 0 . 56 0 1 0 0 0 0 0 0 0 1 2 1 1 0 0 1 0 . 28 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 . 14 0 0 0 0 0 0 1 0 0 2 0 0 1 0 0 0193 5 . 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 . 12 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 56 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 28 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0__________________________________________________________________________ the post - emergence herbioidal activity of some of the various compounds of this invention was demonstrated by greenhouse testing in the following manner . top soil is placed in aluminum pans having holes in the bottom and compacted to a depth of 0 . 95 to 1 . 27 cm . from the top of the pan . a predetermined number of seeds of each of several dicotyledonous and monocotyledonous annual plant species and / or vegetative propagules for the perennial plant species were placed on the soil and pressed into the soil surface . the seeds and / or vegetative propagules are covered with soil and leveled . the pans are then placed on a bench in the greenhouse and watered from below as needed . after the plants reach the desired age ( two to three weeks ), each pan , is removed individually to a spraying chamber and sprayed by means of an atomizer , operating at a spray pressure of 170 . 3 kpa ( 10 psig ) at the application rates noted . in the spray solution is an amount of an emulsifying agent mixture to give a spray solution or suspension which contains about 0 . 4 % by volume of the emulsifier . the spray solution or suspension contains a sufficient amount of the candidate chemical in order to give application rates of the active ingredient corresponding to those shown in the tables while applying a total amount of solution or suspension equivalent to 1870 l / ha ( 200 gallons / acre ). the pans were returned to the greenhouse and watered as before and the injury to the plants as compared to the control is observed at approximately 10 - 14 days ( usually 11 days ) and in some instances observed again at 24 - 28 days ( usually 25 days ) after spraying . these latter observations are designated by an asterisk (*) following the column of example numbers in the table . the post - emergent herbicidal activity index used in table 4 is as follows : ______________________________________plant response index______________________________________0 - 24 % inhibition 025 - 49 % inhibition 150 - 74 % inhibition 275 - 99 % inhibition 3100 % inhibition 4species not planted -- species planted , no data n______________________________________ table 4______________________________________post - emergent activity for weedsexample no . kg / ha a b c d e f g h i j k______________________________________ 1 11 . 2 0 0 0 0 0 0 0 0 0 0 0 2 11 . 2 0 0 0 0 0 0 0 0 0 0 0 3 11 . 2 0 0 0 0 0 0 0 0 -- 0 0 4 11 . 2 0 0 0 0 0 0 1 0 -- 0 1 5 11 . 2 0 n 0 1 0 0 0 0 0 0 0 6 11 . 2 0 0 0 0 0 0 0 0 -- 0 0 7 11 . 2 n 3 1 3 4 1 0 0 0 0 2 7 * 11 . 2 n 4 1 3 4 1 0 0 0 0 1 7 * 11 . 2 n 3 1 3 3 0 0 0 0 0 1 8 11 . 2 0 0 0 0 0 0 0 0 0 0 0 9 11 . 2 0 0 0 0 0 0 0 0 0 0 0 10 11 . 2 n 0 1 0 0 0 0 0 0 0 0 11 11 . 2 0 n 0 0 0 0 0 0 0 0 0 12 11 . 2 0 0 0 0 0 0 0 0 -- 0 0 13 11 . 2 0 n 0 0 0 0 0 0 0 0 0 14 11 . 2 0 0 0 0 0 0 0 0 n 0 0 15 11 . 2 0 n 0 0 0 0 0 0 0 0 0 16 11 . 2 0 0 0 0 0 0 0 0 n 0 0 17 11 . 2 -- 0 1 1 n 0 0 0 0 0 1 18 11 . 2 -- 0 0 0 0 0 0 1 0 0 1 19 11 . 2 -- 0 0 0 0 0 0 0 1 0 0 20 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 21 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 22 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 23 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 24 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 25 11 . 2 n 0 0 1 1 0 1 1 0 0 1 26 11 . 2 -- 0 1 3 3 0 1 0 0 0 1 26 * 11 . 2 -- 1 0 3 3 0 0 0 0 0 1 27 11 . 2 -- 1 1 1 1 0 1 0 0 0 1 28 11 . 2 -- 1 0 1 3 0 0 0 0 0 0 29 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 30 11 . 2 -- 0 0 1 n 0 0 0 0 0 0 31 11 . 2 -- 0 0 1 0 0 0 0 0 0 1 32 11 . 2 -- 0 0 0 0 0 0 0 2 0 1 33 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 34 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 35 11 . 2 -- 1 0 0 0 0 0 0 0 0 0 36 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 37 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 38 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 39 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 40 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 41 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 42 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 43 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 44 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 45 11 . 2 -- 0 0 1 1 0 0 0 0 0 0 46 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 47 11 . 2 -- 0 0 0 2 0 0 0 0 0 1 48 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 49 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 50 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 51 11 . 2 -- 1 0 0 0 0 0 0 0 0 0 52 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 53 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 54 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 55 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 56 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 57 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 58 11 . 2 -- 0 0 0 1 0 0 0 0 0 1 59 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 60 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 61 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 62 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 63 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 64 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 65 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 66 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 67 11 . 2 -- 1 0 0 0 0 0 0 0 0 0 68 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 69 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 70 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 71 11 . 2 0 1 1 1 1 0 0 0 0 0 0 72 11 . 2 0 0 0 0 0 0 0 0 n 0 0 73 11 . 2 n 0 0 0 0 0 0 0 0 0 0 74 11 . 2 n 0 0 0 0 0 0 0 0 0 0 75 11 . 2 0 0 0 0 0 0 0 0 0 0 0 76 11 . 2 0 0 0 0 0 0 0 0 0 0 0 77 11 . 2 0 0 0 0 0 0 0 0 0 0 0 78 11 . 2 0 0 0 0 0 0 0 0 0 0 0 79 11 . 2 0 0 0 0 0 0 0 0 0 0 0 80 11 . 2 0 0 0 0 0 0 0 0 0 0 0 81 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 82 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 83 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 84 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 85 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 86 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 87 11 . 2 -- 0 0 0 0 0 0 0 0 0 0 88 11 . 2 -- 0 1 0 0 0 0 0 n 0 0 89 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 90 11 . 2 -- 0 1 0 0 0 0 0 n 0 0 91 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 92 11 . 2 -- 0 0 0 0 0 0 0 n 0 0 93 11 . 2 -- 0 0 0 0 0 0 0 0 0 1 94 11 . 2 -- 0 1 0 0 0 0 0 n 0 0 95 11 . 2 -- 0 1 0 0 0 0 1 0 0 0 96 11 . 2 -- 0 1 1 0 0 0 0 0 0 0 97 11 . 2 -- 0 0 0 1 0 0 0 0 0 0 98 11 . 2 -- 0 0 1 0 0 0 0 0 0 0 99 11 . 2 -- 0 1 1 0 0 0 1 0 0 0 100 11 . 2 -- 0 1 1 0 0 0 0 0 0 0 101 11 . 2 -- 0 0 n 0 0 0 0 0 0 1 102 11 . 2 -- 1 0 0 0 0 0 0 0 0 1 103 11 . 2 0 0 0 1 0 0 0 0 0 0 0 104 11 . 2 0 0 0 0 0 0 0 0 0 0 0 105 11 . 2 0 0 1 1 0 0 0 0 0 0 0 106 11 . 2 0 1 1 1 0 0 0 0 0 0 1 107 11 . 2 1 1 0 1 4 0 1 0 0 0 1 107 * 11 . 2 2 1 1 2 4 0 1 0 0 0 1 108 11 . 2 0 1 1 1 3 0 0 0 0 0 1 109 11 . 2 0 0 0 0 1 0 0 1 0 0 1 110 11 . 2 0 0 0 0 0 0 0 0 0 0 0 111 11 . 2 0 0 0 0 1 0 0 0 0 0 0 112 11 . 2 0 1 1 0 1 0 0 0 0 0 1 113 11 . 2 1 1 1 1 0 0 0 0 0 0 0 114 11 . 2 1 1 0 1 0 0 0 0 0 0 0 115 11 . 2 0 0 0 0 0 0 0 0 0 0 0 116 11 . 2 0 0 0 0 0 0 0 0 0 0 0 117 11 . 2 0 0 0 0 0 0 0 0 0 0 0 118 11 . 2 0 n 1 2 1 1 1 0 0 0 2 119 11 . 2 0 0 0 0 0 0 0 0 0 0 0 120 11 . 2 0 0 0 0 0 0 0 0 0 0 0 121 11 . 2 0 0 0 0 1 0 0 0 0 0 0 122 11 . 2 0 0 0 0 0 0 0 0 0 0 0 123 11 . 2 0 0 0 n 0 0 0 0 0 0 0 124 11 . 2 0 0 2 1 1 0 0 0 0 0 1 125 11 . 2 0 0 1 n 1 0 0 0 1 0 2 126 11 . 2 0 1 0 n 0 0 0 0 0 0 0 127 11 . 2 n 2 1 1 0 1 1 0 0 0 2 128 11 . 2 0 1 0 0 1 0 0 0 0 0 1 129 11 . 2 0 0 0 0 0 0 0 0 0 0 0 130 11 . 2 0 1 1 1 0 0 0 0 0 0 1 131 11 . 2 0 0 0 0 0 0 0 0 0 0 0 132 11 . 2 0 0 0 0 0 0 0 0 0 0 0 133 11 . 2 0 0 0 0 0 0 0 0 0 0 0 134 11 . 2 0 0 0 0 0 0 0 0 0 0 0 135 11 . 2 n 3 2 3 3 1 1 3 1 0 2 135 * 11 . 2 n 3 2 3 3 2 0 3 1 0 1 136 11 . 2 4 0 0 2 3 0 0 0 0 -- 0 137 11 . 2 n 0 0 0 0 0 0 0 0 0 0 138 11 . 2 0 0 0 0 4 0 0 0 0 -- 0 139 11 . 2 0 0 0 0 0 0 0 0 0 0 0 140 11 . 2 0 0 0 0 0 0 0 0 n 0 0 141 11 . 2 n 0 0 0 0 0 0 0 n 0 0 142 11 . 2 0 0 0 1 0 0 0 0 0 0 0 143 11 . 2 0 1 1 1 0 0 0 0 n 0 0 144 11 . 2 0 0 0 0 0 0 0 0 0 0 0 145 11 . 2 0 0 0 0 2 0 0 0 0 0 0 146 11 . 2 0 0 0 0 0 0 0 0 n 0 1 147 11 . 2 0 0 0 0 0 0 0 0 0 0 0 148 11 . 2 0 0 1 0 1 0 0 0 0 0 0 149 11 . 2 0 0 0 0 1 0 0 0 0 0 0 150 11 . 2 0 0 0 0 0 0 0 0 0 0 0 151 11 . 2 0 0 0 1 0 0 0 0 0 0 0 152 11 . 2 0 0 1 1 0 0 0 0 n 0 0 153 11 . 2 0 0 0 0 0 0 0 0 0 0 0 154 11 . 2 0 0 0 0 0 0 0 n 0 0 0 155 11 . 2 0 0 1 1 0 0 0 0 0 0 0 155 11 . 2 n 0 1 0 0 0 0 0 0 0 1 157 11 . 2 1 0 1 0 0 0 0 0 0 0 0 158 11 . 2 0 0 0 0 0 0 0 0 0 0 0 159 11 . 2 0 0 0 0 0 0 0 0 0 0 0 160 11 . 2 0 0 0 0 0 0 0 0 0 0 1 161 11 . 2 0 0 0 0 0 0 0 0 n 0 0 162 11 . 2 0 0 0 0 0 0 0 0 0 0 0 163 11 . 2 0 0 0 0 0 0 0 0 0 0 0 164 11 . 2 n 0 0 0 0 0 0 0 1 0 0 165 11 . 2 0 0 1 0 0 0 0 0 0 1 0 166 11 . 2 0 0 0 0 0 0 0 0 0 0 0 167 11 . 2 1 1 1 1 2 0 0 0 0 0 1 168 11 . 2 0 0 1 1 0 0 0 0 0 0 0 169 11 . 2 n 0 1 0 0 0 0 0 0 0 0 170 11 . 2 1 1 1 1 0 0 0 0 0 0 1 171 11 . 2 n 0 0 0 0 0 0 0 0 0 1 172 11 . 2 n 0 0 0 0 0 0 0 0 0 0 173 11 . 2 0 0 1 0 0 0 0 0 0 0 0 174 11 . 2 0 0 0 0 0 0 0 0 0 0 0 175 11 . 2 0 0 0 0 0 0 0 0 0 0 0 176 11 . 2 0 0 1 0 n 0 0 0 0 0 0 177 11 . 2 0 0 0 0 0 0 0 0 0 0 0 178 11 . 2 0 0 0 0 0 0 0 0 0 0 0 179 11 . 2 0 0 0 0 0 0 0 0 0 0 0 180 11 . 2 0 0 1 0 0 0 0 0 0 0 1 181 11 . 2 0 0 0 0 0 0 0 0 0 0 0 182 11 . 2 0 0 0 0 n 0 0 0 0 0 0 183 11 . 2 0 0 0 0 0 0 0 0 0 0 0 184 11 . 2 0 0 1 0 n 0 0 0 0 0 0 185 11 . 2 0 0 0 0 n 0 0 0 0 0 0 186 11 . 2 0 0 0 0 0 0 0 0 0 0 0 187 11 . 2 0 0 0 0 0 0 0 0 0 0 0 188 11 . 2 1 2 1 1 1 0 0 0 0 0 1 189 11 . 2 0 0 0 0 0 0 0 0 0 0 0 190 11 . 2 0 0 0 0 0 0 0 0 0 0 0 191 11 . 2 0 0 0 0 0 0 0 0 0 0 0 192 11 . 2 0 0 0 0 0 0 0 0 0 0 0 193 11 . 2 0 0 0 0 0 0 0 0 0 0 0 194 11 . 2 0 0 0 0 0 0 0 0 n 0 1 195 11 . 2 0 0 0 0 0 0 0 0 n 0 0 196 11 . 2 0 0 0 0 0 0 0 0 n 0 0 197 11 . 2 0 0 0 0 0 0 0 0 0 0 0 198 11 . 2 0 0 0 0 0 0 0 0 0 0 0 199 11 . 2 0 0 0 0 0 0 0 0 0 0 0 200 11 . 2 0 0 0 0 0 0 0 0 0 0 0 201 11 . 2 0 0 0 0 0 0 0 0 0 0 0 202 11 . 2 0 0 0 0 0 0 0 0 0 0 0 203 11 . 2 0 0 0 0 0 0 0 0 0 0 0 204 11 . 2 0 0 0 0 0 0 0 0 0 0 0 205 11 . 2 0 0 0 0 0 0 0 0 0 0 0 206 11 . 2 0 0 0 0 0 0 0 0 0 0 0 207 11 . 2 0 0 0 0 1 0 0 0 0 0 0 208 11 . 2 0 0 0 0 0 0 0 0 n 0 0______________________________________ as can be seen from the data above , some of the compounds appear to be quite safe on certain crops and can thus be used for selective control of weeds in these crops . the herbicidal compositions of this invention , including concentrates which require dilution prior to application , may contain at least one active ingredient and an adjuvant in liquid or solid form . the compositions are prepared by admixing the active ingredient with an adjuvant including diluents , extenders , carriers , and conditioning agents to provide compositions in the form of finely - divided particulate solids , granules , pellets , solutions , dispersions or emulsions . thus , it is believed that the active ingredient could be used with an adjuvant such as a finely - divided solid , a liquid of organic origin , water , a wetting agent , a dispersing agent , an emulsifying agent or any suitable combination of these . suitable wetting agents are believed to include alkyl benzene and alkyl naphthalene sulfonates , sulfated fatty alcohols , amines or acid amides , long chain acid esters of sodium isothionate , esters of sodium sulfosuccinate , sulfated or sulfonated fatty acid esters , petroleum sulfonates , sulfonated vegetable oils , ditertiary acetylenic glycols , polyoxyethylene derivatives of alkylphenols ( particularly isooctylphenol and nonylphenol ) and polyoxyethylene derivatives of the mono - higher fatty acid esters of hexitol anhydrides ( e . g ., sorbitan ). preferred dispersants are methyl , cellulose , polyvinyl alcohol , sodium lignin sulfonates , polymeric alkyl naphthalene sulfonates , sodium naphthalene sulfonate , and polymethylene bisnaphthalene sulfonate . wettable powders are water - dispersible compositions containing one or more active ingredients , an inert solid extender and one or more wetting and dispersing agents . the inert solid extenders are usually of mineral origin such as the natural clays , diatomaceous earth and synthetic minerals derived from silica and the like . examples of such extenders include kaolinites , attapulgite clay and synthetic magnesium silicate . the wettable powders compositions of this invention usually contain from above 0 . 5 to 60 parts ( preferably from 5 - 20 parts ) of active ingredient , from about 0 . 25 to 25 parts ( preferably 1 - 15 parts ) of wetting agent , from about 0 . 25 to 25 parts ( preferably 1 . 0 - 15 parts of dispersant and from 5 to about 95 parts ( preferably 5 - 50 parts ) of inert solid extender , all parts being by weight of the total composition . where required , from about 0 . 1 to 2 . 0 parts of the solid inert extender can be replaced by a corrosion inhibitor or anti - foaming agent or both . other formulations include dust concentrates comprising from 0 . 1 to 60 % by weight of the active ingredient on a suitable extender ; these dusts may be diluted for application at concentrations within the range of from about 0 . 1 - 10 % by weight . aqueous suspensions or emulsions may be prepared by stirring a nonaqueous solution of a water - insoluble active ingredient and an emulsification agent with water until uniform and then homogenizing to give stable emulsion of very finely - divided particles . the resulting concentrated aqueous suspension is characterized by its extremely small particle size , so that when diluted and sprayed , coverage is very uniform . suitable concentrations of these formulations contain from about 0 . 1 - 60 % preferably 5 - 50 % by weight of active ingredient , the upper limit being determined by the solubility limit of active ingredient in the solvent . concentrates are usually solutions of active ingredient in water - immiscible or partially waterimmiscible solvents together with a surface active agent . suitable solvents for the active ingredient of this invention include dimethylformamide , dimethylsulfoxide , n - methyl - pyrrolidone , hydrocarbons , and water - immiscible ethers , esters , or ketones . however , other high strength liquid concentrates may be formulated by dissolving the active ingredient in a solvent then diluting , e . g ., with kerosene , to spray concentration . the concentrate compositions herein generally contain from about 0 . 1 to 95 parts ( preferably 5 - 60 parts ) active ingredient , about 0 . 25 to 50 parts ( preferably 1 - 25 parts ) surface active agent and where required about 4 to 94 parts solvent , all parts being by weight based on the total weight of emulsifiable oil . granules are physically stable particulate compositions comprising active ingredient adhering to or distributed through a basic matrix of an inert , finely - divided particulate extender . in order to aid leaching of the active ingredient from the particulate , a surface active agent such as those listed hereinbefore can be present in the composition . natural clays , pyrophyllites , illite , and vermiculite are examples of operable classes of particulate mineral extenders . the preferred extenders are the porous , absorptive , preformed particules such as preformed and screened particulate attapulgite or heat expanded , particulate vermiculite and the finely - divided clays such as kaolin clays , hydrated attapulgite or bentonitic clays . these extenders are sprayed or blended with the active ingredient to form the herbicidal granules . the granular compositions of this invention may contain from about 0 . 1 to about 30 parts by weight of active ingredient per 100 parts by weight of clay and 0 to about 5 parts by weight of surface active agent per 100 parts by weight of particulate clay . the compositions of this invention can also contain other additaments , for example , fertilizers , other herbicides , other pesticides , safeners and the like used as adjuvants or in combination with any of the above - described adjuvants . chemicals useful in combination with the active ingredients of this invention included , for example , triazines , ureas , carbamates , acetamides , acetanilides , uracils , acetic acid or phenol derivatives , thiolcarbamates , triazoles , benzoic acids , nitriles , biphenyl ethers and the like such as : fertilizer useful in combination with the active ingredients include , for example ammonium nitrate , urea , potash and superphosphate . other useful additaments include materials in which plant organisms take root and grow such as compost , manure , humus , sand and the like . herbicidal formulations of the types described above are exemplified in several illustrative embodiments below . ______________________________________ weight percent______________________________________i . emulsifiable concentratesa . compound of example no . 3 11 . 0free acid of complex organic 5 . 59phosphate or aromatic oraliphatic hydrophobe base ( e . g ., gafac re - 610 , registeredtrademark of gaf corp .) polyoxyethylene / polyoxypropylene 1 . 11block copolymer with butanol ( e . g ., tergitol xh , registeredtrademark of union carbide corp .) pheno1 5 . 34monochlorobenzene 76 . 96 100 . 00b . compound of example no . 14 25 . 00free acid of complex organic 5 . 00phosphate of aromatic oraliphatic hydrophobe base ( e . g ., gafac re - 610 ) polyoxyethylene / polyoxypropylene 1 . 60block copolymer with butanol ( e . g ., tergitol xh ) phenol 4 . 75monochlorobenzene 63 . 65 100 . 00ii . flowablesa . compound of example no . 24 25 . 00methyl cellulose 0 . 3silica aerogel 1 . 5sodium lignosulfonate 3 . 5sodium n - methyl - n - oleyl taurate 2 . 0water 67 . 7 100 . 00b . compound of example no . 18 45 . 0methyl cellulose . 3silica aerogel 1 . 5sodium lignosulfonate 3 . 5sodium n - methyl - n - oleyl taurate 2 . 0water 47 . 7 100 . 00iii . wettable powdersa . compound of example no . 5 25 . 0sodium lignosulfonate 3 . 0sodium n - methyl - n - oleyl - taurate 1 . 0amorphous silica ( synthetic ) 71 . 0 100 . 00b . compound of example 21 80 . 00sodium dioctyl sulfosuccinate 1 . 25calcium lignosulfonate 2 . 75amorphous silica ( synthetic ) 16 . 00 100 . 00c . compound of example no . 6 10 . 0sodium lignosulfonate 3 . 0sodium n - methyl - n - oleyl - taurate 1 . 0kaolinite clay 86 . 0 100 . 00iv . dustsa . compound of example no . 13 2 . 0attapulgite 98 . 0 100 . 00b . compound of example no . 10 60 . 0montmorillonite 40 . 0 100 . 00c . compound of example no . 54 30 . 0ethylene glycol 1 . 0bentonite 69 . 0 100 . 00d . compound of example no . 62 1 . 0diatomaceous earth 99 . 0 100 . 00v . granulesa . compound of example no . 52 15 . 0granular attapulgite ( 20 / 40 mesh ) 85 . 0 100 . 00b . compound of example no . 70 30 . 0diatomaceous earth ( 20 / 40 ) 70 . 0 100 . 00c . compound of example no . 58 1 . 0ethylene glyco1 5 . 0methylene blue 0 . 1pyrophyllite 93 . 9 100 . 00d . compound of example no . 46 5 . 0pyrophyllite ( 20 / 40 ) 95 . 0 100 . 00______________________________________ when operating in accordance with the present invention , effective amounts of the compounds of this invention are applied to the soil containing the seeds , or vegetative propagules or may be incorporated into the soil media in any convenient fashion . the application of liquid and particulate solid compositions to the soil can be carried out by conventional methods , e . g ., power dusters , boom and hand sprayers and spray dusters . the compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages . the exact amount of active ingredient to be employed is dependent upon various factors , including the plant species and stage of development thereof , the type and condition of soil , the amount of rainfall and the specific compounds employed . in selective preemergence application or to the soil , a dosage of from about 0 . 02 to about 11 . 2 kg / ha , preferably from about 0 . 1 to about 5 . 60 kg / ha , is usually employed . lower or higher rates may be required in some instances . one skilled in the art can readily determine from this specification , including the above examples , the optimum rate to be applied in any particular case . the term &# 34 ; soil &# 34 ; is employed in its broadest sense to be inclusive of all conventional &# 34 ; soils &# 34 ; as defined in webster &# 39 ; s new international dictionary , second edition , unabridged ( 1961 ). thus , the term refers to any substance or media in which vegetation may take root and grow , and includes not only earth but also compost , manure , muck , humus , sand , and the like , adapted to support plant growth . although the invention is described with respect to specific modifications , the details thereof are not to be construed as limitations . | 0 |
fig1 illustrates a digital video recorder (“ dvr ”) set - top box 100 having input video feeds 102 a - 102 c and tuners 104 . the tuners 104 are connected through digital transport multiplexers 106 to a cpu 108 , a main memory 110 , and a disk 112 . the digital transport multiplexers are further connected to audio / video decoders 114 , which in turn are connected to television monitors 116 . the tuners 104 are operable to select a video feed from a cable feed 102 a , a satellite feed 102 b , or a terrestrial feed 102 c . one of sufficient skill in the relevant arts will recognize that the feeds 102 a - 102 c could be any other medium of video transmission . the tuners 104 provide the selected video to digital transport multiplexers 106 . the digital transport multiplexers 106 are then operable to transmit the selected video feed to audio / video decoders 114 for display on one or more television monitors 116 . the digital transport multiplexers 106 can alternatively transmit the selected video feed to a cpu 108 and a main memory 110 for storage in a disk 112 . furthermore , the cpu 108 can transmit a video feed stored on disk 112 through the main memory 110 to the digital transport multiplexers 106 . the digital transport multiplexers 106 can be instructed to forward the video feed stored on disk 112 to the audio / video decoders 114 rather than the selected video feed coming from tuners 104 . in this scenario , the audio / video decoders 114 will decode and transmit the video feed stored on disk 112 to the television monitors 116 for display . one skilled in the relevant arts will appreciate that a number of different memory devices may be used instead of disk 112 , including but not limited to such memory devices not typically used in dvr applications where the disclosed invention may nevertheless be employed . a typical organizational structure for storing data in a disk such as disk 112 is shown in fig2 . a disk 202 can be divided into one or more partitions 204 . each partition has partition contents 206 which include inodes 208 and data blocks 210 . an individual inode 212 comprises meta data 214 , direct block pointers 216 , indirect block pointers 218 , doubly indirect block pointers 220 , and triply indirect block pointers 222 . one of sufficient skill in the relevant arts will appreciate that the quantity and availability of each kind of n - way indirect block pointers may vary based on the system , and may include greater or fewer levels of indirect block access . an inode 212 comprises meta data 214 , used for storing information about a file , and a series of block pointers . each of the block pointers in the inode 212 contain a pointer to a block location within the data blocks 210 . the direct block pointers 216 each contain a pointer to a block location comprising a block of data 224 within data blocks 210 . indirect block pointers 218 contain a pointer to a block location comprising a direct block list 226 . the direct block list 226 comprises pointers to block locations , each comprising a block of data 224 . similarly , the doubly - indirect block pointers 220 contain a pointer to a block location comprising an indirect block list 228 , which in turn comprises pointers to block locations comprising direct block lists 226 . the direct block lists 226 comprise pointers to block locations , each comprising a block of data 224 . triply - indirect block pointers 222 contain a pointer to a block location comprising a doubly - indirect block list 230 . the doubly - indirect block list 230 comprises pointers to block locations comprising indirect block lists 228 , which in turn operate as detailed above . in a typical storage system , a single file stored on a disk 202 is associated with a particular inode 212 . if the file size is less than the size of a single block , then a single direct block pointer 216 will be used to point to the single block 224 where the data is placed . if the file is larger , then indirect block pointers are used in order to reference a direct block list 226 containing pointers to multiple data blocks 224 . assuming a block size of 4 kb and a block list size of 1024 entries , a direct block list 226 contains pointers for 4 mb worth of data blocks 224 . accordingly , an indirect block list 228 with 1024 entries contains pointers for 1024 direct block lists 226 , each comprising pointers for 4 mb worth of data blocks 224 . therefore , indirect block lists 228 in a typical system comprises pointers for 4 gb worth of data blocks 224 . in a similar manner , doubly indirect block list 230 comprises 4 tb worth of data blocks 224 . as a consequence , the singly indirect pointer within the inode may point to up to 4 mb of data , the doubly indirect pointer 4 gb of data , and the triply indirect pointer 4 tb of data . each block pointer may reference any particular 4 kb block on the disk 202 without limitation . accordingly , it is possible for a first data block 224 referenced within a direct block list 226 to be located at a drastically different location on disk 202 than a second data block 224 referenced within the direct block list 226 , with both blocks being part of a common file . because an inode traditionally represents an entire single file , blocks located in drastically different locations on disk will cause slowdowns when attempting to access the file . therefore , it is desirable to have all of the blocks that form a file to be allocated contiguously . turning now to fig3 , a block bitmap 300 is also present in a typical filesystem alongside the inode tree structure . the block bitmap 300 contains an entry for each block in the entire filesystem , each entry indicating whether the block is free 302 or used 304 . a block is marked as used 304 whenever a direct pointer within an inode as depicted in fig2 points to the block . as one of sufficient skill in the relevant arts will acknowledge , multiple pointers can reference the same block . accordingly , the block bitmap 300 is sometimes marked with a count of how many direct pointers point to the block . when the last direct pointer within an inode is zeroed or pointed to a different block , the relevant block is marked as free 302 and may be allocated to a new file . fig4 is a flowchart 400 illustrating the steps by which a garbage collection inode (“ gci ”) may be employed in order to facilitate the deletion of a file , in accordance with an embodiment of the present invention . at step 402 , an instruction to delete a particular file is received . the instruction contains a unique identifier for the file , such as a file name , in accordance with an embodiment of the present invention . using the unique identifier , the file &# 39 ; s associated inode can be determined at step 404 . the inode &# 39 ; s data block pointers are copied in step 406 to a gci , and the pointers are zeroed and the entire inode freed in step 408 . with the data block pointers now located in the gci , it is possible to iterate through all of the data block pointers in the gci and mark the data blocks pointed to by each of the data block pointers as freed in step 410 . in accordance with an embodiment of the present invention , data block pointers from multiple inodes may be copied , as in step 406 , to the gci before previous data block pointers have been completely deleted . the operation by which the copying step 406 is performed takes significantly less time than a deletion operation , in accordance with an embodiment of the present invention . accordingly , several files and their associated inodes may be marked for deletion through this process by copying the data block pointers as in step 406 to the gci in less time than it would take to delete each file using the methods in the prior art . fig5 compares the operation of a gci 508 to an inode 502 in accordance with an embodiment of the present invention . the gci 508 is a specially - designated inode with the same structure as a regular inode 502 . however , the gci 508 will have its block pointers initially zeroed 510 , such that the gci 508 does not represent any area of memory . fig5 illustrates , on the left column of the dashed lines 514 , the state of an inode 502 to be deleted , and the state of the gci 508 on the right column of the dashed lines 514 . both the inode 502 and the gci 508 are shown prior to deletion 500 along the dashed lines 516 , and after deletion 512 below the dashed lines 516 . with continued reference to fig4 , if a user wishes to delete a recording represented by inode 502 , an instruction is provided as in step 402 indicating the recording or file to be deleted . as in step 404 , the inode 502 associated with the file is determined . this inode 502 contains a pointer to a location a 0 where , for example , a doubly indirect block list 506 is found . the doubly indirect block list 506 contains indirect pointers to other lists , and traversing these lists eventually leads to the specific data blocks that comprise the recording represented by the inode 502 . traditionally , the filesystem would have to traverse through each block list to reach each data block , free the pointer referring to the data block , and furthermore mark the pointed to block as free in the block bitmap 300 ( fig3 ). considering a situation prior to deletion 500 of the recording represented by the inode 502 , it is possible to realize a more efficient deletion operation through the use of the gci 508 . this is accomplished by transferring the address of a block list pointer 504 from the inode representing the recording to be deleted to the appropriate pointer in the gci 508 as in step 406 . as indicated in fig5 after deletion 512 , the gci 508 would subsequently contain pointers to the data blocks that form the to - be - deleted recording . as in step 408 , the original inode 502 has its pointer to the data blocks that form the to - be - deleted recording zeroed 510 . the inode 502 is now empty . by performing this transfer on a pointer to a list of lists of data blocks , the entire recording to be deleted can be easily transferred to the gci 508 in only two operations . the data remains on the disk until the block bitmap 300 ( fig3 ) has been updated such that the data blocks which compose the to - be - deleted recording are set to a free state 302 . this is accomplished as in step 410 by iterating through the pointers contained by the gci 508 and marking the data blocks pointed to by the pointers as free . with the blocks to be freed pointed to by the gci 508 , a separate process is operable to parse through the gci 508 to free each of the relevant blocks as in step 410 ( fig4 ), in accordance with an embodiment of the present invention . the separate process may be a low priority process in order to free the blocks in the background without interrupting the operation of the dvr 100 ( fig1 ). in accordance with an embodiment of the present invention , the separate process frees the data blocks pointed to by the gci 508 by traversing the gci 508 , zeroing the data block pointers , and marking the relevant block location in the block bitmap 300 as freed , as in step 410 ( fig4 ). one skilled in the relevant arts will appreciate that any method which can be used to delete an inode may similarly be applied to deletion of the recording pointed to by the gci 508 . by deferring the lengthy process of iterating through the data block pointers in the gci 508 and freeing the blocks to a separate , low priority process , filesystem functionality is not monopolized by the deletion requests , which otherwise block access to the disk resources until completed . accordingly , a dvr 100 implementing this method to delete a recording from a disk 112 will allow a user to perform further operations immediately after requesting the deletion of a recording , rather than having to wait for the deletion to actually complete . various aspects of the present invention can be implemented by software , firmware , hardware , or a combination thereof . fig6 illustrates an example computer system 600 in which the present invention , or portions thereof , can be implemented as computer - readable code . for example , the method illustrated by flowchart 400 of fig4 can be implemented in system 600 . various embodiments of the invention are described in terms of this example computer system 600 . after reading this description , it will become apparent to a person skilled in the relevant art how to implement the invention using other computer systems and / or computer architectures . computer system 600 includes one or more processors , such as processor 604 . processor 604 can be a special purpose or a general purpose processor . processor 604 is connected to a communication infrastructure 606 ( for example , a bus or network ). computer system 600 also includes a main memory 608 , preferably random access memory ( ram ), and may also include a secondary memory 610 . secondary memory 610 may include , for example , a hard disk drive 612 and / or a removable storage drive 614 . removable storage drive 614 may comprise a floppy disk drive , a magnetic tape drive , an optical disk drive , a flash memory , or the like . the removable storage drive 614 reads from and / or writes to a removable storage unit 618 in a well known manner . removable storage unit 618 may comprise a floppy disk , magnetic tape , optical disk , etc . which is read by and written to by removable storage drive 614 . as will be appreciated by persons skilled in the relevant art ( s ), removable storage unit 618 includes a computer usable storage medium having stored therein computer software and / or data . in alternative implementations , secondary memory 610 may include other similar means for allowing computer programs or other instructions to be loaded into computer system 600 . such means may include , for example , a removable storage unit 622 and an interface 620 . examples of such means may include a program cartridge and cartridge interface ( such as that found in video game devices ), a removable memory chip ( such as an eprom , or prom ) and associated socket , and other removable storage units 622 and interfaces 620 which allow software and data to be transferred from the removable storage unit 622 to computer system 600 . computer system 600 may also include a communications interface 624 . communications interface 624 allows software and data to be transferred between computer system 600 and external devices . communications interface 624 may include a modem , a network interface ( such as an ethernet card ), a communications port , a pcmcia slot and card , or the like . software and data transferred via communications interface 624 are in the form of signals which may be electronic , electromagnetic , optical , or other signals capable of being received by communications interface 624 . these signals are provided to communications interface 624 via a communications path 626 . communications path 626 carries signals and may be implemented using wire or cable , fiber optics , a phone line , a cellular phone link , an rf link or other communications channels . in this document , the terms “ computer program medium ” and “ computer usable medium ” are used to generally refer to media such as removable storage unit 618 , removable storage unit 622 , a hard disk installed in hard disk drive 612 , and signals carried over communications path 626 . computer program medium and computer usable medium can also refer to memories , such as main memory 608 and secondary memory 610 , which can be memory semiconductors ( e . g . drams , etc .). these computer program products are means for providing software to computer system 600 . computer programs ( also called computer control logic ) are stored in main memory 608 and / or secondary memory 610 . computer programs may also be received via communications interface 624 . such computer programs , when executed , enable computer system 600 to implement the present invention as discussed herein . in particular , the computer programs , when executed , enable processor 604 to implement the processes of the present invention , such as the steps in the method illustrated by flowchart 400 of fig4 discussed above . accordingly , such computer programs represent controllers of the computer system 600 . where the invention is implemented using software , the software may be stored in a computer program product and loaded into computer system 600 using removable storage drive 614 , interface 620 , hard drive 612 or communications interface 624 . the invention is also directed to computer products comprising software stored on any computer useable medium . such software , when executed in one or more data processing device , causes a data processing device ( s ) to operate as described herein . embodiments of the invention employ any computer useable or readable medium , known now or in the future . examples of computer useable mediums include , but are not limited to , primary storage devices ( e . g ., any type of random access memory ), secondary storage devices ( e . g ., hard drives , floppy disks , cd roms , zip disks , tapes , magnetic storage devices , optical storage devices , mems , nanotechnological storage device , etc . ), and communication mediums ( e . g ., wired and wireless communications networks , local area networks , wide area networks , intranets , etc .). example embodiments of the methods , systems , and components of the present invention have been described herein . as noted elsewhere , these example embodiments have been described for illustrative purposes only , and are not limiting . other embodiments are possible and are covered by the invention . such other embodiments will be apparent to persons skilled in the relevant art ( s ) based on the teachings contained herein . thus , the breadth and scope of the present invention should not be limited by any of the above - described exemplary embodiments , but should be defined only in accordance with the following claims and their equivalents . furthermore , the disclosed data storage techniques are not limited to any particular memory device or those commonly used in dvr applications . | 6 |
referring to fig1 and 2 , there is shown one illustrative embodiment of a mounting rail for mounting camper shells to beds of vehicles . the mounting rail is comprised of a base element 10 which is formed with an elongate strip 12 and a upwardly extending lip 14 . the base element 10 is formed of a material of sufficient strength to accomplish the structural requirements herein described . the base element 10 is formed of extruded aluminum or similar material . the elongate strip 12 of the base element 10 is fashioned to fit on the top of a truck bed sidewall 20 . the elongate strip 12 can be fastened to the top of a truck bed sidewall 20 in any way presently known or to be discovered . the upwardly extending lip 14 of the base element 10 rises in a substantially perpendicular direction from one side of the elongate strip 12 . the upwardly extending lip 14 is adjacent and lateral from the downwardly projecting lower rim 24 of a camper shell and is fashioned so as to retain the downwardly projecting lower rim 24 of a camper shell from movement due to outward lateral forces . the mounting rail for mounting camper shells to beds of vehicles is further comprised of a clamp 30 . the clamp 30 is placed on the base element 10 inward and adjacent to the lower rim 24 of a camper shell . the clamp 30 is fastened to the base element 10 in a position adjacent and inward from the lower rim 24 of a camper shell by means of a rivet 32 or other fastening means . the clamp 30 supports the lower rim 24 of a camper shell against movement due to inward lateral forces . space between the upwardly extending lip 14 and the outer side of the lower rim 24 of a camper shell , and also space between the clamp 30 and inner side of the lower rim 24 of a camper shell , is filled and bound with an adhesive 36 . when the rivet 32 or other fastening means is fastened to the clamp 30 , and the base element 10 , the upper head of the rivet 32 is hidden from view by the structure of the clamp 30 . referring to fig3 a , 3b , and 3c , there are shown other illustrative embodiments of the clamp 30 of fig1 and 2 . in fig3 a the clamp 30 is a parallelogram ( exaggerated ) in shape so that when the rivet 32 of fig1 and 2 fastens the clamp 30 to the base element 10 , edge 38 of clamp 30 is forced snugly against the inner edge of the lower rim 24 of a camper shell , tightly securing the lower rim 24 of a camper shell between the clamp 30 and the upwardly extending lip 14 of the base element 10 . in fig3 b the clamp 30 is roughly rectangular or square in shape and has a foot 40 extending downward from the inward lower corner . the foot 40 of the clamp 30 deflects the pressures created in fastening the clamp 30 to the base element 10 so that edge 42 of clamp 30 is forced snugly against the inner edge of the lower rim 24 of a camper shell , tightly securing the lower rim 24 between the clamp 30 and the upwardly extending lip 14 . in fig3 c the clamp 30 is roughly rectangular or square in shape . pressures , in this embodiment , are created between edge 44 of the clamp 30 , the lower rim 24 of a camper shell , and the upwardly extending lip 14 of the base element 10 , by ether matching right angles meeting against an adhesive 36 placed between the clamp 30 and the lower rim 24 of a camper shell ; or by forming the base element 10 with an acute angle between the upwardly extending lip 14 and the remainder of the base element 10 , and the lower rim 24 of a camper shell with a complementary acute angle of the upwardly extending lip 14 , thereby creating pressures due to the difference in the angles . referring to fig4 there is shown another illustrative embodiment of a mounting rail for mounting camper shells to beds of vehicles . in this embodiment a recess 50 is formed in the underside of the base element 52 . the recess 50 receives in it the head 54 of a fastener 56 , thereby maintaining a flush lower surface on the base element 52 for mounting on a pickup bed . referring to fig5 there is shown yet another illustrative embodiment of a mounting rail for mounting camper shells to beds of vehicles . in this embodiment a mounting rail is formed from an elongate holder 60 and a bracket 62 . the elongate holder 60 and the bracket 62 are formed of the same materials as the mounting rail described hereinabove . the elongate holder 60 has a rectangular lip 64 formed on its outboard edge , and a well 66 formed in an area below the rectangular lip 64 . the bracket 62 is formed with a horizontal strip 68 and a vertical strip 70 . the inboard edge 76 of the horizontal strip 68 is received into the well 66 of the elongate holder 60 to secure the two pieces together against vertical pressures . the bracket 62 is further secured to the elongate holder 60 with a rivet 72 or other fastener as herein above described . the rivet 72 or other fastener extends from a point below the bracket 62 , through the elongate holder 60 , and terminates inside the rectangular lip 64 of the elongate holder 60 . the downwardly projecting lower rim 74 of a camper shell is received between the vertical strip 70 of the bracket 60 , and the outboard edge of the rectangular lip 64 . the lower rim 24 of a camper shell is retained between the vertical strip 70 of the bracket 62 , and the outboard edge of the rectangular lip 64 of the elongate holder 60 by means of adhesive 78 therebetween . it is to be understood that the above - described arrangements are only illustrative of an application of the present invention . numerous modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the present invention and the appended claims are intended to cover such modifications and arrangements . | 1 |
turning now to the figures and particularly fig1 through 4 , the present invention comprises broadly a temporary connector means here shown as a resilient ring 20 of foam rubber or the like carrying a pressure - sensitive adhesive layer 22 on its lower surface which in turn is protected by a removable film 24 . the opposite or upper surface of the ring 20 is permanently attached by any suitable means such as adhesive 26 to a support member 28 . the support member 28 can take various forms but one of the simplest is that of a convex sheet of resilient metal or spring plate of substantially the same size and shape as the included area of the resilient ring 20 so that in the device shown , the circular resilient ring 20 is attached to the circular support member 28 . centrally located with respect to the ring 20 and spaced radially inwardly therefrom is a resilient pad 30 that is secured by the adhesive 26 to the same surface of the support member 28 as the resilient ring 20 . for convenience , this surface and direction will hereinafter be referred to as the lower surface or downward direction as indicated in fig4 . however , it is to be clearly understood that this direction is solely for convenience and it is the position of the various elements relative to each other that is important , rather than whether the surfaces and forces are upward or downward . the lower surface of the central pad 30 is coated with a temporary pressure - sensitive adhesive 32 to which is adhered an attachment or patch 34 that is to be bonded to a supporting substrate 36 . assuming that the patch 34 is to be applied to the supporting substrate 36 , the method of using the device just disclosed is illustrated in fig5 through 8 . after appropriately cleaning the upper surface of the supporting substrate 36 and the lower or free surface of the patch 34 , a permanent setting or curable adhesive 40 is applied to the lower surface of the patch 34 as indicated in fig5 . the protective film 24 is removed from the adhesive layer 22 on the lower surface of the resilient ring 20 to uncover the pressure - sensitive adhesive layer 22 . the patch 34 is then properly located over the appropriate section of the supporting substrate 36 and pressure is then applied to the peripheral edges of the support member 28 as indicated in fig6 . this compresses the resilient ring 20 and causes the pressure - sensitive adhesive layer 22 to hold the resilient ring 20 temporarily to the supporting substrate 36 . at this time there is preferrably no or little contact between the patch 34 or the adhesive 40 thereon with the adjacent supporting substrate 36 . to adhere the patch 34 to the supporting substrate 36 , the center portion of the support member 28 is then pressed downwardly toward the supporting substrate 36 as indicated in fig7 . as previously mentioned , the support member 28 is formed of a resilient or springable material that has been warped to have a generally convex shape presented away from the supporting substrate 36 . when sufficient pressure is applied centrally to the upper surface of the support member 28 , as indicated in fig7 the support member 28 snaps over center from a convex to a concave shape . consequently , the upper surface of the resilient central pad 30 is moved toward the supporting substrate 36 and as a result , the pad 30 is compressed to force the patch 34 against the supporting substrate 36 . excess adhesive 40 is forced outwardly into an annular space between the pad 30 and the resilient ring 20 to form a ring 42 around the patch 34 . this flow of adhesive 40 can continue during setting of the adhesive whereby the force applied to the patch 34 tends to urge the patch continuously toward the supporting substrate 36 . at this point the pressure - sensitive adhesive layer 22 holds the resilient ring 20 to the supporting substrate 36 and the adhesive 26 holds the resilient ring 20 under tension to the support member 28 . the pressure - sensitive adhesive layer 22 applied to the lower surface of the resilient ring 20 must have sufficient strength to hold the resilient ring 20 firmly to the supporting substrate 36 while the adhesive 40 is curing . thus , the resilient ring 20 under tension applies a force to the support member 28 to urge the support member toward the supporting substrate , and thereby also apply a similarly directed force to the patch 34 . a study of the forces involved shows that the total force tending to separate the resilient ring 20 and the adhesive layer 22 from the supporting substrate 36 equals the total force pressing the patch 34 against the substrate . after the adhesive 40 has sufficiently cured , additional force is applied to lift the resilient ring 20 from the supporting substrate 36 , the pressure - sensitive adhesive layer 22 having less adhesive power than the curable adhesive 40 . the pressure - sensitve adhesive 32 releases the patch 34 from the resilient central pad 30 , as indicated in fig8 leaving the patch 34 in place as shown in fig3 . it will be recognized that the pressure - sensitive adhesive 32 connecting the patch 34 to the resilient central pad 30 need only have enough holding power to hold the patch 34 and the pad 30 together so that the two are conveniently united . on the other hand , the pressure - sensitive adhesive layer 22 that holds the resilient ring 20 to the supporting surface 36 must have greater holding power since , as indicated in fig7 the pressure applied to the ring 20 by the springable support member 28 places the ring 20 in tension , tending to pull the ring 20 from the supporting substrate 36 . it will also be recognized that it is important that the pressure - sensitive adhesive 32 that holds the patch 34 to the resilient central pad 30 must have less holding power than the curable adhesive 40 holding the patch 34 to the supporting substrate 36 . were this not so , when the resilient ring 20 and springable support member 28 are removed from the supporting substrate 36 , the bond between the central pad 30 and the batch 34 would be greater than the bond between the patch 34 and the supporting substrate 36 , and consequently the patch would be removed without having performed its intended function . in fig9 through 12 , there is illustrated another form of the attachment assembly in which the unit or attachment to be applied is what might be termed a hat - shaped attachment rather than the flat patch 34 shown in fig1 - 8 . the hat - shaped attachment finds a variety of uses as for example where a protuberance such as a nut is located on a flat substrate and a threaded rod extends through that flat substrate and into the nut . if a seal is to be provided over the nut and the threaded rod , the hat - shaped attachment 134 , best seen in fig1 , is useful . in this form of device the basic construction is similar to that previously described , with a resilient drag 120 having a pressure - sensitive adhesive layer 122 on its lower surface protected by a protective film 124 . the opposite surface of the resilient ring 120 is held by an adhesive layer 126 to a springable support member 128 of the type disclosed in fig1 - 8 . in the center of the support member 128 is a generally dome - shaped section 150 that extends through the support member and is held thereto by any suitable means . this construction is best seen in fig1 . centrally located with respect to the resilient ring 120 is a compressible or resilient central annular pad 130 that is held to the support member 128 by the suitable adhesive layer 126 . a layer of pressure - sensitive adhesive 132 on the opposite side of the pad 130 holds the hat - shaped attachment 134 with respect to the support member 128 . as with the previously described flat patch 34 , the surface of the hat - shaped attachment 134 that is be to bonded to a supporting substrate 136 is coated with an adhesive such as the curable or settable adhesive 40 previously described . the hat - shaped attachment 134 is installed by properly positioning the assembly and then pressing downwardly on the periphery of the support member 128 to attach the resilient ring 120 to the substrate 136 temporarily by means of the pressure - sensitive adhesive layer 122 . the dome - shaped section 150 is then pressed downwardly so that the support member 128 is forced over center in the same manner that the support member 28 is forced over center as illustrated in fig7 . after the adhesive 40 is properly cured and bonded , the support member 128 and the ring 120 and pad 130 are removed in the manner previously described , leaving the hat - shaped attachment 134 on the supporting substrate 136 as illustrated in fig1 . in fig1 and 14 , an attachment 234 and supporting substrate 236 are shown , comparable to the hat - shaped attachment 134 and the supporting substrate 136 of fig9 - 12 , the attachment 234 having a screw 252 projecting upwardly from the supporting substrate 236 as best seen in fig1 . the construction of this assembly is quite similar to that shown in fig1 with a springable over center type support member 228 carrying a resilient ring 220 cemented to the support member 228 by an adhesive layer 226 , with the resilient ring 220 having a pressure - sensitive adhesive layer 222 protected by a removable film 224 . a dome - shaped section 250 in the central portion of the support member 228 carries a compressible central annular pad 230 having a pressure - sensitive adhesive 232 that carries the attachment 234 having the upwardly projecting screw 252 . the construction is indicated in cross - section in fig1 , and the method of application is similar to that of the hat - shaped attachment 134 previously described . in fig1 and 16 there is shown another attachment generally similar to those previously described but carrying a threaded nut 356 . as illustrated in these figures , a deformable and springable over center type support member 328 , similar to the support members 128 and 228 , carries a dome - shaped center section 350 and an annular resilient ring 320 attached by means of an adhesive layer 326 . a layer of pressure - sensitive adhesive 322 on the ring 320 carries a protective film 324 all as previously described . a compressible central annular pad 330 centered with respect to the resilient ring 320 carries an attachment 334 held to the compressible pad 330 by a pressure - sensitive adhesive layer 332 . centrally located with respect to the attachment 334 is the nut 356 that may be held to the attachment member by any suitable means . the method and means for attachment to a supporting substrate 336 is comparable to that previously described with respect to the foregoing embodiments . it is to be understood , of course , that the attachment need not take the particular forms herein shown . thus , if a rectangular patch were to be applied to a supporting substrate , this can very conveniently be done . likewise , it is not important that the supporting substrate be planar since it frequently happens that a patch must be applied to a curved surface which may be curved in one or two meridians . the resilient ring 30 and the central pad 30 apply sufficient positive pressure to the patch 34 to cause the patch to conform to the surface configuration of the supporting substrate 36 . additionally , the nature of the adhesive materials is not restricted . the adhesive 40 , for example , may be one that gains its strength by evaporation of a solvent ; one that gains its strength by chemical reaction , as is the case in some of the epoxy adhesives ; or an adhesive that gains its strength and produces a bond by melting as some glue - like materials or even solder . in each case , it is important that the bond formed between the patch 34 and the supporting substrate 36 be the strongest of the various bonds to be established . the temporary bond formed between the resilient ring 20 and the supporting substrate 36 will be the next strongest bond since in pressing the patch 34 against the supporting substrate 36 , the support member 28 is moved to place the resilient ring 20 in tension , tending to pull it away from the supporting substrate . it is important that the resilient ring 20 not be pulled away from the supporting substrate 36 by the action of the springable support member 28 , but it is also important that it be possible to remove the resilient ring 20 without a great deal of difficulty after the bond between the patch 34 and supporting substrate has been completed . the bond created by the pressure - sensitive adhesive 32 holding the patch 34 to the compressible central pad 30 should be a relatively weak bond since it is important that the pad 30 be removed from the patch 34 without any undue strain tending to remove the patch from the supporting substrate 36 . it is also to be understood that it is not essential that the springable support member 28 take the form of a convex disk that can be pressed by the thumb to assume an over center concave shape . depending upon the size of the patch and its nature , it may be necessary to strike the support member , as with a hammer , to move it over center to the concave shape . while other forms for the support member may be used , the over center disc - shaped metal spring embodiment illustrated is one of the simplest forms available . a further embodiment of the invention is illustrated in fig1 - 19 and comprises an adhesive assembly with an attachment 50 similar to the attachment 234 of fig1 , wherein the attachment 50 supports an outwardly projecting threaded stud 51 . the attachment 50 is movably supported upon a support member 52 for securing the attachment 50 to a supporting surface or substrate 53 . more specifically , the support member includes a central hollow cylinder 54 with a radially inwardly projecting lip 55 at one end for threaded engagement with the stud 51 . a pair of vertically spaced annular grooves 56 and 57 are formed about the external diameter of the cylinder 54 , and these grooves 56 and 57 are positioned for selective reception of locking tabs 58 on a support member housing 59 . the support member housing 59 is also generally cylindrical in shape , and thus includes a central bore 60 for relatively free sliding reception of the cylinder 54 . the housing 59 has a plurality of the locking tabs 58 projecting radially inwardly from its upper end as viewed in fig1 and 19 , and these tabs 58 are sized for snap - fit reception either into either the lower groove 56 or the upper groove 57 . thus , the cylinder 54 carrying the attachment 50 is movable between a pair of positions and is lockable in the related position by means of the tabs 58 within one of the grooves 56 and 57 . importantly , the housing 59 is formed from a suitable metal or plastic material to accommodate the required movement of the tabs 58 between the grooves . the support member housing 59 also includes at its opposite or lower end , as viewed in fig1 - 19 , a radially outwardly projecting flange 61 to which is secured an annular , resilient ring 62 . this resilient ring 62 is conveniently secured to the flange 61 as by a layer 63 of suitable adhesive , and is formed from a compliant material such as a resilient foam or the like generally identical with the resilient ring 20 described above with respect to fig1 . this resilient ring 62 further includes on its face opposite the flange 61 a layer 64 of a temporary adhesive material such as a pressure - sensitive adhesive of the type referred to in fig1 as the adhesive layer 22 . in use , the adhesive assembly is temporarily secured to the supporting surface or substrate 53 by pressing upon the flange 61 of the support member housing 59 to secure the pressure - sensitive adhesive layer 64 to the substrate . at this point , the central cylinder 54 of the support member 52 is positioned within the housing 59 with the housing tabs 58 secured within the lower cylinder groove 56 . this retains the attachment 50 with its free or downwardly presented face 65 presented toward but spaced from the substrate 53 . as in the previous embodiments , a settable or curable permanent bond adhesive 66 has been applied to this face 65 of the attachment . when a satisfactory temporary bond is achieved between the resilient ring 62 and the substrate 53 by virtue of the layer 64 of pressure - sensitive adhesive , the central cylinder 54 of the support member 52 is pushed within the housing 59 toward the substrate 53 . as illustrated in fig1 , this translates the cylinder 54 within the housing 59 to lockingly reposition the locking tabs 58 within the upper groove 57 in the cylinder . conveniently , both the cylinder 54 and the housing 59 include at their upper ends , as viewed in fig1 - 19 , radially outwardly projecting flanges 67 and 68 , respectively , to facilitate manual grapsing of the cylinder 54 for movement thereof toward the substrate without disturbing the temporary bond between the resilient ring 62 and the substrate 53 . when the tabs 58 are locked within the upper groove 57 in the cylinder 54 , the attachment 50 is positioned with its free bonding face 65 in pressure - engagement with the substrate 53 . this forces the permanent adhesive 66 into intimate pressure - contact with the substrate 53 to fill microscopically sized pores and the like in both the attachment 50 and the substrate 53 to yield a rigid bond therebetween upon curing or setting . importantly , the position of the upper cylinder groove 57 is chosen so that the resilient ring 62 is placed in tension without releasing its temporary attachment to the substrate 53 whereby the ring 62 functions to urge the entire support member 52 towards the substrate . this correspondingly applies a positive force to the attachment 50 at all times to urge the attachment towards the substrate . to the extent that the permanent adhesive is capable of or desirous of flowing during setting or curing , this positive force applied to the attachment 50 accommodates such flowing by urging the attachment 50 to move closer to the substrate and thereby maximizes the adhesive bond between the attachment and the substrate . as soon as the permanent adhesive 66 has cured , the temporary bond between the resilient ring 62 and the substrate 53 can be broken as described in the previous embodiments ; then , the entire support member 52 can be removed from the stud 51 and the attachment 50 by rotating the support member to release the lip 55 of the cylinder 54 from threaded engagement with the stud 51 . this leaves the attachment 50 and the stud 51 secured firmly by the cured adhesive 66 to the substrate 53 , generally as shown in the previous embodiment in fig1 . still another embodiment of the invention is illustrated in fig2 - 22 , wherein an adhesive attachment assembly is shown including an attachment 71 carrying a threaded stud 72 generally identical to the attachment 50 and stud 51 of fig1 - 21 . this attachment 71 is secured temporarily by an adhesive layer 70 to a relatively small annular resilient ring 73 , which in turn is secured by another adhesive layer 74 to one end of a hollow , externally threaded carrier cylinder 75 . the stud 72 is received into the hollow interior of the cylinder 75 , and the opposite end of the cylinder 75 is closed by an enlarged cap 76 for easy manual grasping thereof , as will be described . the carrier cylinder 75 is threadably received within a threaded bore 77 of a generally cylindrical support member housing 78 , and thus is axially translatable within the housing 78 upon rotation of the cylinder 75 therein . as shown , this housing 78 includes , at its end opposite the cap 76 on the cylinder 75 , a radially outwardly projecting flange 79 to which is secured a relatively large annular resilient ring 80 by an adhesive layer 81 . this ring 80 generally corresponds with the resilient ring 20 shown and described with respect to fig1 and includes on its face opposite the flange 78 a layer 82 of a temporary adhesive such as a pressure - sensitive adhesive . in use , a permanent curable adhesive 86 such as an epoxy resin is applied to the free or bonding face 83 of the attachment 71 , with the cylinder 75 threadably positioned within the housing 78 to retract the attachment 71 from a substrate 84 ; then , the relatively large resilient ring 80 is secured temporarily to the substrate 84 by pressing the housing flange 79 toward the substrate , as illustrated by the arrows 85 in fig2 . once a satisfactory temporary bond is achieved between the resilient ring 80 and the substrate 84 , the threaded cylinder 75 is rotated to translate the attachment 71 into intimate engagement with the substrate 84 . importantly , the cylinder 75 is moved to a position to place the relatively large resilient ring 80 in tension and the smaller resilient ring 73 in compression , whereby the two rings 80 and 73 together react with the support member housing 78 and the cylinder 75 to apply a positive force to the attachment 71 for urging the attachment toward the substrate at all times . as described with respect to previous embodiments , this application of the positive force to the attachment assures maximum bonding strength between the attachment and the substrate . upon curing of the permanent adhesive 86 , the temporary bond between the larger resilient ring 80 and the substrate 84 is readily broken , whereupon the support member housing 78 , the resilient ring 80 , and the cylinder 75 are quickly and easily removed from the attachment 71 by breaking the relatively weak adhesive bond between the smaller resilient ring 73 and the attachment . this leaves the attachment 71 and the stud 72 securely bonded to the substrate 84 with an appearance generally corresponding to that shown in fig1 with respect to a previous embodiment . a further embodiment of the invention is illustrated in fig2 - 25 and comprises an attachment assembly including an attachment 91 carrying a threaded stud 92 . in this embodiment , the attachment 91 and the stud 92 are supported by a support member 93 including a central cylinder 94 having a radially inwardly projecting lip 95 at its lower end for threaded reception over the stud 92 . from the lip 95 , the cylinder 94 extends axially and concentrically about the stud 92 and has an annular ridge 96 projecting outwardly therefrom and positioned generally intermediate its length . the central cylinder 94 is received within a generally cylindrical support member housing 97 . this housing 97 includes , at its end opposite the attachment 91 , a radially inwardly projecting rim 98 in generally opposed relation with a corresponding radially outwardly projecting rim 99 at the opposite end of the central cylinder 94 . a compression spring 100 is positioned within the housing 97 and about the cylinder 94 to react between these two rims 98 and 99 and thereby function to apply an axial force to the cylinder 94 and the attachment 91 . the support member housing 97 also includes a radially outwardly projecting flange 101 at its end opposite the rim 98 , and this flange is secured by an adhesive layer 102 to an annular resilient ring 103 generally corresponding with the ring 20 of fig1 . this ring 103 in turn carries a layer 104 of a pressure - sensitive adhesive for temporary bonding to a substrate 106 , as described above with respect to the previous embodiments . in use , the central cylinder 94 is positioned as illustrated in fig2 with the annular ridge 96 in abutting engagement with the rim 98 on the support member housing 97 . the ridge 96 engages the rim 98 on its side opposite the attachment 91 to retain the spring 100 in a compact , compressed condition . in this position , a layer of permanent adhesive 107 is applied to the free or bonding face 108 of the attachment , and the resilient ring 103 is temporarily secured by the pressure - sensitive adhesive to the substrate 106 by pressing the housing flange 101 toward the substrate as shown by arrows 109 in fig2 . upon achieving a satisfactory bond between the resilient ring 103 and the substrate 106 , the central cylinder 94 is pushed toward the substrate 106 as shown by arrows 110 in fig2 . this snaps the ridge 96 on the cylinder 94 past the housing rim 98 to allow the compression spring 100 to thrust the attachment 91 into intimate contact with the substrate 106 . the spring 100 maintains a positive force upon the attachment to urge the attachment toward the substrate at all times . as described above with respect to previous embodiments , this application of positive force assures maximum bonding strength between the attachment and the substrate . importantly , the temporary bond between the resilient ring 103 and the housing flange 101 is sufficient to withstand the force applied to the attachment by the spring 100 . when the permanent adhesive 107 is cured , the temporary bond between the resilient ring 103 and the support member housing 97 is readily broken . this allows the entire support member 93 to be rotatably unthreaded from the stud 92 leaving the attachment 91 and the stud securely bonded to the substrate with an appearance generally corresponding to that shown in fig1 with regard to a previous embodiment of the invention . the adhesive attachment of this invention thus provides a movable support member carrying an attachment and adapted for temporary bonding to a substrate . the support member is movable to position the attachment in intimate contact with the substrate after temporary bonding of the support member to the substrate . appropriate apparatus is included for application of a positive force to the attachment to maintain the attachment firmly seated against the substrate throughout the curing time for a permanent adhesive , and to urge the attachment for further movement toward the substrate . in this manner , the attachment assembly accommodates any flowing of the permanent adhesive to result in maximum bonding strength between the attachment and the substrate . a variety of further modifications and improvements to the adhesive attachments described herein are believed to be apparent to one skilled in the art . for example , it should be understood that various studs , nuts , and the like can be utilized with each one of the embodiments shown and described . accordingly , no limitations upon the scope of the invention are intended , except as set forth in the appended claims . | 1 |
fig1 shows an embodiment of the invention applied to a scenario where a telephone conference is invoked and controlled via a web terminal device pc ( cc ), such as a personal computer connected to the internet ipnet . the controlling of the phone conference includes the steps of preparing and initiating a conference , adding a conferee to an already established conference , and closing the conference by on - hook . in this context the term “ conferee ” relates to all users who participate in the telephone conference except for the conference controller cc . in addition to the telephone conference a synchronised web surfing session may be provided for those conferees who have access to the internet ipnet . to initiate the telephone conference the conference controller cc sets up an http connection to the conference server ctc via the internet ipnet . authentication information such as details of the initiator , i . e . the conference controller cc , and the conferees tln1 , tln2 and tln3 as well as an access pin ( personal identification number ) may be provided . optionally , the controller cc may specify the use of a voip ( voice over ip ) connection mediated through the h . 323 or the sip ( session initiation protocol ) protocol in place of a pstn connection . for retrieval and storage of authentication information and authorisation information a ldap server ldap is placed in the vicinity of the web conference server ctc . the web conference server ctc is linked to an open service platform osp by means of corba ( common object request broker architecture ), which provides an environment for distributed applications on top of the tcp / ip ( transmission control protocol over internet protocol ) protocol stack . apis ( application programming interfaces ) of the open service platform osp allow for the provision of additional services and the implementation of additional service features . in addition , the open service platform ops receives signalling messages for call control of the telephone conference from a telephone switch ts , which are relayed to the web conference server ctc . messages between the open service platform osp and the telephone switch ts are exchanged via the protocols inap ( intelligent network user part ) and tcap ( transaction capability application part ). these two protocols are commonly used for communication between an ssp ( service switching point ) and an scp ( service control point ) in an in ( intelligent network ) network architecture with ss7 ( signalling system 7 ) signalling . the telephone switch ts , e . g . an isdn switch , assumes switching functions for the pstn connections of the telephone conference . possibly , a pstn connection is relayed to a media gateway mgw to allow for participation of conferees or the conference controller cc via voip ( voice over ip ). conferees may have internet access in addition to access to the pstn network . fig1 shows a conferee tln1 who disposes of a personal computer pc with internet access as well as a pstn telephone tel . the other conferees tln2 and tln3 are only connected to a pstn network pstnnet and participate through pstn connections . the conference controller cc may connect to the switching system or telephone switch ts , either by means of a pstn call ( telephone tel ( cc )) or through a voip call ( personal computer pc ( cc )). in the latter case a media gateway mgw is necessary to account for the change of bearer ( ip network with h . 323 versus pstn network with ss7 ). call - related signalling messages from the telephone switch ts , such as no - answer , could - not - be - reached , connected , release etc . are displayed in real time on the conference controller &# 39 ; s personal computer pc ( cc ) and optionally to conferees tln1 with internet access . the real - time notification of the conference controller cc and possibly of conferees tln1 with internet access is realised by means of a combination of server - side java servlets and dynamic http . the deployment of java applets has the advantage that a cc - side proxy ( interface ) can be serialised , i . e . admitted as parameter information to be exchanged between client , i . e . in this embodiment the conference controller &# 39 ; s personal computer pc ( cc ), and server ctc in the process of binding . thus , the cc - side proxy and other proxies involved in the application can be passed on to other clients . for example , an information handle including the cc - proxy can be put at the disposal of conferees tln1 with internet access so that new conferee - side proxies need not be generated . in the preferred embodiment the notification mechanism is based on server - side java servlets in combination with dynamic html . to start the notification mechanism a server - side servlet is invoked through an html request by the client pc ( cc ). by invoking the java servlet the client pc ( cc ) subscribes to receive notification messages transmitted from the telephone switch ts . an http connection is set up for streaming in messages from the server ctc to the client pc ( cc ). in contrast to the original client - server communication , where the http connection is closed after fetching an http page , the connection remains open while fresh notification messages are pushed to the client pc ( cc ). through the subscription by the client a format is specified for notification messages to be sent by the server ctc to the client pc ( cc ). this format is chosen to be a computer code that can be executed by the client &# 39 ; s browser , such as javascript , xml , html or java - serialised objects . the latter format can be used for browsers that make use of client - side java classes . via the subscription request by the client the transmission protocol for the streaming is specified , too . preferably , this protocol is chosen to be http , but other choices such as tcp ( transmission control protocol ), udp ( user datagram protocol ), rmi ( remote message invocation ) etc . are possible , too . the notification messages from the telephone switch ts that are received by the server ctc are formatted or adjusted for transmission to the client pc ( cc ). these messages are dispatched by means of a java servlet , which is sometimes called pushlet , that pushes or sends the notification messages to the client &# 39 ; s browser . the pushing or sending of computer code that is executed by the client &# 39 ; s browser is a mechanism originally applied in the framework of dynamic html ( dhtml ). traditionally , a page could be altered only by reloading a new page from the server . dhtml allows full control of an html document within a browser after the page has been loaded . from a programmer &# 39 ; s point of view the entire document in the web browser — frames , images , paragraphs , tables etc .— is represented as a hierarchical object model , the dom ( document object model ). through javascript or any other computer code executable by the browser one can dynamically manipulate the elements of the dom and thereby change the content or appearance of the document . the official standards body for dhtml - related specifications is the world wide web consortium ( w3c ). the client &# 39 ; s gui ( graphical user interface ) is dynamically updated with new notification messages streamed in from the server . fig2 shows a diagram with a sequence of exchanged messages for adding conferee tln2 to the telephone conference . the sequence of exchanged messages is : regc1 : a request regc1 to call conferee tln2 is transmitted from the client pc ( cc ) to the conference server ctc . mc1 : a message mc1 referring to the request to call conferee tln2 is transmitted from the server ctc to the telephone switch ts . c1 : upon reception of message mc1 a pstn call of conferee tln2 is issued by the telephone switch ts . rg : the pstn call is acknowledged from the telephone of conferee tln2 by generating a signal for the calling terminal device ( ringing ). mgrg : the acknowledgement by the telephone of conferee tln2 is signalled by the telephone switch ts to the server ctc via the notification message mgrg . resrg : the notification message mgrg is adapted and transmitted as a dhttp response resrg from the server ctc to the client pc ( cc ). reska : after every time period t an http response is sent from the server ctc to the client pc ( cc ) to inform the client that the http connection should be kept open ( ka : keep alive ). effectively , streaming is a call back by the server to the client during a client - server connection . ct : the connection between the telephone switch ts and the conferee &# 39 ; s telephone is established . mgct : the set - up of the connection between the telephone switch ts and conferee tln2 is signalled by the telephone switch ts to the server ctc via the notification message mgct . resct : the notification message mgct is adapted and transmitted as a dhttp response resct from the server ctc to the client pc ( cc ). although the above preferred embodiment describes a scenario where notification messages are transmitted from an isdn switch - to an internet terminal device pc ( cc ) via the internet , the present method could also be used in a constellation where notification messages are transmitted from a pbx ( private branch exchange ) via a private ip network ( intranet ). | 7 |
as illustrated by fig1 to 9 of the drawings , the mechanism is identical to that described in our aforesaid patent application and its mode of operation is the same . however , for the sake of complete disclosure the detailed description of the mechanism is repeated herein . the mechanism is indicated generally as 11 and is designed for installation in a door frame 12 to cooperate with a conventional dead - lock 13 fitted to a door 14 mounted within the frame . more particularly , mechanism 11 includes a catch member 16 which can cooperate with the spring loaded bolt 17 of the lock 13 to provide a locking function . however , this catch member 16 can be pivoted to an inoperative position so as to release bolt 17 and permit the door to open . the condition of catch member 16 is controlled by an electric solenoid included in the mechanism . mechanism 11 has a body 15 comprised of a hollow casing 18 and a front plate 22 . casing 18 includes a removable side plate 19 held in position by screws 23 and it is fastened to front plate 22 by means of screws 21 . body 15 has a lower relatively deep slot 25 to register with the bolt 17 of lock 13 and door 14 swings to its closed position and an upper relatively short slot 26 to register with the dead lock actuator bar 27 of the lock 13 as will be more fully explained below . catch member 16 is mounted across slot 25 . more particularly , it is pivotally mounted on a pivot pin 28 which traverses slot 25 and extends into holes in casing wall portions 30 , 35 which define upper and lower walls of the slot . it is shaped generally as a long bar of l - shaped transverse cross - section , one limb 31 of which is mounted on the pivot pin 28 and the other limb 32 of which serves as the catch for lock bolt 17 . limb 31 has a bore 33 extending through it to receive pivot pin 28 and is counter - bored at each end to provide end recesses 34 to house a pair of torsion springs 36 disposed about pin 28 . springs 36 have short end arms 37 which project into slots 38 formed in the walls of recesses 34 of catch member 16 and rather longer arms 38 which react against the side wall 40 of casing 18 . they bias catch member 16 toward the position shown in fig1 and 4 in which position the flat end surface 45 of its limb 31 abuts the casing side wall 40 to limit pivoting movement and its limb 32 is generally parallel with wall 40 and can serve as a catch for the spring loaded lock bolt 17 . this is most clearly illustrated in fig4 in which the phantom lines indicate the position of the door and the lock bolt as the door approaches the fully closed position and the full lines show the position of these components when the door is fully closed . the outer end of limb 32 of the catch member is chamfered to provide a sloping striker face 41 which is struck by the lock bolt as the door is closed to force the lock bolt back against its spring loading . as the door reaches its fully closed position the lock bolt is forced outwardly by its spring loading to locate behind the side face 42 of catch limb 32 . at the same time the dead lock actuator bar 27 of the lock enters slot 26 and strikes a ramp surface 55 formed in front plate 22 at the end of the slot so as to be actuated to move the dead lock pin within the lock in the usual manner . as will be described below catch member 16 can be locked in position so that face 42 of its limb 32 acts as a locking face to prevent opening of the door . however , catch member can be released so that it can be pivoted about pivot pin 28 to allow release of the door in the manner shown in fig5 . the locking and release of catch member 16 is achieved through a detent mechanism comprised of a lever 43 and a keeper member 44 which is controlled by means of a solenoid 46 . lever 43 is in the form of a long bar provided at one end with a bore 48 to receive a pivot pin 47 by which it is pivotally mounted on casing 18 . it is disposed within casing 18 immediately behind catch member 16 and it extends longitudinally of the catch member . more specifically , it is arranged to engage the outer corner part 49 of the catch member at the junction between the two limbs 31 , 32 . this outer corner part of the catch member serves as a cam to engage lever 43 and pivot it about its pivot pin 47 when catch member 16 is pivoted between its operative and inoperative positions . it has a cam surface 51 which is cylindrically curved about the pivot axis of catch member 16 and a leading cam edge 52 which subtends an angle of rather more than 90 ° to surface 51 . lever 43 is biased into firm engagement with catch member 16 by two helical compression springs 53 acting directly between the lever and a rear wall portion 54 of casing 18 . it is formed from rectangular bar stock so as to have flat front and side faces 56 , 57 but one corner edge 58 is relieved by a saw - tooth notch 59 to form a flat triangular cam face 61 which engages the leading cam edge 52 of catch member 16 when the catch member is in its operative position . this condition of the catch member 16 and lever 43 is illustrated by fig2 and 4 . it will be seen that lever 43 , although extending generally longitudinally of catch member 16 , subtends a slight acute angle to it and its triangular cam face 61 lies flat against an end part of cam edge 52 . keeper member 44 acts to enable lever 43 to be locked in this condition or released according to the supply of electrical signals to solenoid 46 . keeper member 44 is shaped generally as a bell crank . it has two mutually perpendicular arms 62 , 63 and is pivotally mounted on body 18 by a pivot pin 64 . its arm 62 is transverse to lever 43 and has a notch 66 to engage the outer end of the lever so as to provide a detent action holding the lever in the position shown in fig2 . notch 66 is generally of saw - tooth shape to define a sloping catch face 67 and the outer end of lever 43 is notched at 68 so as to be shaped as a tooth having a tooth face 69 to engage the catch face 67 of the keeper arm . keeper member 44 may be held in its keeping position shown in fig2 by the action of solenoid 46 . this solenoid has a coil 71 wound on a body 72 about a central core 73 . it is mounted in casing 18 so that when energized its magnetized core will attract the outer end of actuator arm 63 of keeper member 44 to hold the keeper member in its keeping position . its core is connected to a mild steel backing plate 50 which extends close to the outer end of arm 63 so as to direct magnetic flux through the keeper member and thus increase the attractive force of the solenoid . as shown in fig2 a slight clearance is maintained between the solenoid core and arm 63 to prevent sticking when the solenoid is de - energized . keeper member 44 is biased away from its keeping position by a biasing spring 74 . this spring has a coiled portion 76 looped around the keeper member pivot pin 64 and two end arms 77 , 78 which are engaged respectively with the casing 18 and a hole in keeper arm 62 . when solenoid 46 is energized it holds the keeper member in its keeping position against the action of biasing spring 74 . however , when solenoid 46 is de - energized spring 74 acts to pivot keeper member 44 to the position shown in fig3 in which its actuator arm 63 is held against an adjustable stop screw 74 and its keeper arm 62 is drawn away from keeping engagement with the outer end of lever 43 . the only action then holding catch member 16 in its catch position is that provided by springs 53 acting on lever 43 . however , because of the cam action between lever 43 and cam portion 49 of the catch member only a light force is needed on catch member 16 to pivot it away from its operative position to force lever 43 back against its biasing springs to the inoperative position shown in fig3 and 5 . at the start of such movement of the catch member its cam edge 52 acts on the triangular cam face 61 of lever 43 to force the lever backwardly against its biasing springs until the cylindrical curved cam surface 51 can engage the flat front face 56 of the lever as shown in fig5 . the rear part of casing 18 has a compartment 81 which houses a micro - switch 82 the actuator 83 of which is engaged by a bracket 84 on lever 43 when the lever is moved consequent to pivoting of catch member 16 to its inoperative position . electrical leads from solenoid 46 and micro - switch 82 are connected within casing 18 to a terminal block 86 which is located partly within compartment 82 but extends rearwardly through an opening in the back wall 87 of the casing and is fitted outside the casing with a series of terminals 88 for connection to external wiring . the catch mechanism illustrated in fig1 to 8 will operate to hold the door locked for so long as solenoid 46 is energized . by de - energizing the solenoid , catch member 16 is freed and the door can be opened . the mechanism has a wide range of applications . for example it may be used in a fire door installation in order to maintain a fire door in a normally locked condition but to release the door in response to a signal created by a smoke or heat detector acting through any suitable relay to interrupt the supply of power to solenoid 46 . in other applications the supply of power to solenoid 46 may be interrupted by operation of a push button located inside a building or by a signal derived from a reader device in response to a magnetically coded key or card . micro - switch 82 may be used to derive a warning or alarm signal each time that the door is opened . fig9 illustrates a modification by which the mechanism is adapted to keep a door locked when the solenoid is de - energized and releases the door when the solenoid receives an electrical signal . the components of the mechanism are not altered but the setting of spring 74 is altered to bias keeper member 44 toward its keeping position and solenoid 46 is displaced through 90 ° from its previous position so as to act directly on keeper arm 62 rather than on arm 63 of the keeper member . the re - setting of biasing spring 74 involves insertion of its arm 77 in a hole drilled in arm 63 instead of in the hole in arm 62 and the other spring arm 78 acts against a different part of casing 18 . in this case keeper arm 62 is normally held by spring 76 in keeping engagement with the upper end of lever 43 by the action of spring 74 but is lifted to free the lever when solenoid 46 is energized . stop screw 79 is set to engage arm 63 of keeper member 44 before arm 62 can engage the solenoid core so that even when the solenoid is energized there will be a slight clearance between its core and arm 62 . mechanism 11 is set into a recess 91 in door frame 12 and may be held in position by conventional wood screws passed through counter - sunk holes 92 in front plate 22 . a groove 93 may be formed in the door frame to receive the projecting part of terminal block 86 and the external wiring . as shown in fig4 and 5 side plate 19 of casing 18 has an inturned lip 96 which abuts cam surface 51 of catch member 16 and as the catch member pivots the cylindrical surface 51 simply slides on lip 96 . thus , contact is maintained between catch member 16 and lip 96 at all times to seal off the interior of the casing and prevent tampering by insertion of an instrument between the catch member and the casing . fig1 and 11 show the heat responsive locking means which is incorporated in the mechanism in accordance with the present invention . this locking means comprises a stainless steel pin or plunger 101 which is located within a cavity 102 in catch member 16 and is biased by a helical compression spring 103 located within the cavity . cavity 102 is in the form of a deep cylindrical hole drilled in the outer corner part 49 of catch member 16 to extend parallel with the pivot axis of the catch member . it has an enlarged mouth 104 at one end of the catch member and this mouth is closed by a plug 105 of white metal which will melt at a selected temperature . the enlarged mouth of the cavity may be internally screw threaded and the plug may be in the form of a white metal grub screw with a driving slot 110 to screw into the threaded mouth . in normal service of the mechanism plug 105 retains plunger 101 within cavity 102 with biasing spring 103 held in a compressed condition . the casing wall portion 35 of the body 15 is provided with a recess 106 at such a location that it registers with the plugged cavity 102 of the catch member when the catch member is in the operative position shown in fig1 and 4 . recess 106 may be formed by drilling a hole through casing wall portion 35 and then plugging the outer end of this hole with a plug 107 held in place by a transverse pin 108 . during normal service of the mechanism the locking means illustrated in fig1 and 11 is inoperative . however , plug 105 has a much lower fusing temperature than the other parts of the mechanism such as the body 15 , catch member 16 and plunger 101 which may all be made of high melting temperature steels . thus , if a fire should occur and cause heating of the mechanism , plug 105 will melt at such a stage that plunger 101 will be extended under the influence of biasing spring 103 to enter recess 106 in casing wall portion 35 and so provide locking interengagement between catch member 16 and the body of the mechanism . the catch member will then be locked in the operative or locking position regardless of the electrical or physical condition of the other components of the mechanism . the composition of white metal plug 105 is chosen to have a fusing temperature appropriate to the particular application . this temperature will generally be in the range of 300 °- 900 ° f . so that when the plug melts there would normally be no survivors within the space closed by the fire door . thus , the design will be such that the mechanism can be released electrically to open the door during conditions when people may have to escape through the door but the catch member subsequently becomes permanently locked in position even should the electrical components be burned out and the lever and keeper mechanism be damaged . the dead lock 13 can , of course , always be operated manually to provide for emergency exit . since the mechanism is designed to be used with fire doors , casing 18 and front plate 22 are both constructed of stainless steel . catch member 15 is an investment casting of non - magnetic stainless steel . lever 43 is also made of non - magnetic stainless steel and keeper member 44 is made of a magnetic steel . the illustrated mechanism has been advanced by way of example only and it could be modified considerably . for example , although the illustrated arrangement of a lever and keeper arm is preferred in order to allow a very compact and robust mechanism other actuator means are possible . australian patent specification no . 426 , 474 describes one alternative in which a lever which normally holds the catch member in its operative position is acted on directly by an electromagnet . it is to be understood that the heat responsive locking means of the present invention may be fitted to such mechanisms and accordingly that many variations will fall within the scope of the appended claims . | 8 |
in accordance with the present invention , a pharmaceutical composition is provided which includes a medicament which may degrade in a low ph environment but which is prevented from doing so by the addition of a buffering agent . accordingly , the pharmaceutical composition of the invention includes drugs which are chemically unstable in an acidic environment , such as pravastatin sodium . the invention provides immediate release pravastatin formulations which provide alternatives to the prior art formulations which require the presence of a basifying agent which have a ph of at least 9 . unlike the prior art basifying agent requirement , the invention favorably influences stability by the addition of a buffer which can be an alkaline reacting organic compound , a hydroxide of an alkali metal , an alkaline salt of phosphoric acid , carbonic acid or silicic acid or an alkaline ammonium salt representative examples of these buffers are described in u . s . pat . no . 6 , 013 , 281 which is incorporated herein by reference . basifying agent , as the term is used herein , refers to compounds capable of raising the ph to above 7 . they are added to formulations of pravastatin to improve chemical and physical stability . according to previous pravastatin formulations containing basifying agents , tablets should retain 80 - 90 % of active ingredient at the end of one year in the presence of stabilizers . the stability of these formulations without a basifying agent was tested in accordance with and exceeding current pharmaceutical industry standards for storage ( i . e ., 4 to 12 weeks at about 40 ° c . and about 75 % relative humidity ). formulations of the present invention stored under these conditions retain at least 90 % of the pravastatin in the composition at the time of storage . standard procedures such as hplc or uv spectroscopic methods may be used to determine the amount of active ingredient remaining after storage . the final dosage form most preferably retains assay limits of 90 to 110 percent of the original assay value when stored under controlled room temperature conditions . the design of the stability studies was in compliance with the general requirements suggested by the fda stability guidelines . the total amount of inactive ingredients in the formulations is preferably 30 % or more of the weight of the pravastatin . the tablets are prepared by the direct compression method . the invention is particularly adaptable to pharmaceutical compositions containing pravastatin . pharmaceutical compositions of the present invention generally contain 10 - 40 mg or an amount with the range of about 2 to about 50 % of pravastatin by weight , and preferably from about 4 to about 25 % by weight of the composition . more preferred compositions of the invention contain 40 mg of active ingredient and may be in the form of tablets , caplets or capsules . the pharmaceutical formulations of the present invention provide a stable environment for drugs which require an alkaline environment by utilizing a buffer . the formulations contain a buffering agent present in an amount within the range of about 3 to about 10 % by weight of the composition . examples of other suitable buffering agents include sodium acetate , sodium citrate , sodium tartrate , sodium fumerate , sodium maleate , sodium succinate , combinations of sodium or potassium hydroxide with sodium or potassium acid phosphate . the preferred buffering agent is tromethamine , a weak base amino - alcohol , also known as 2 - amino - 2 hydroxymethyl - 1 , 3 - propanediol , ( tris ( hydroxymethyl ) aminomethane ) or tris . tromethamine has a greater buffering capacity than bicarbonate ; pka 7 . 82 versus 6 . 1 , respectively . tromethamine has been found to have excellent stabilizing effects on solid dosage forms containing drugs with limited water solubility which need to be solubilized in buffer to avoid otherwise solubilizing the drug in large quantities of granulating media . tromethamine has been discovered to be most advantageous when a therapeutically - effective buffer - soluble drug has a solubility at 25 ° c . of less than 1 mg of drug per ml of water at ph 7 . 0 or lower . an advantage of tromethamine lies in its water solubility and , accordingly , it blends well with an excipient like lactose . tromethamine as used herein is preferably present in the range of about 1 to 10 %, more preferably , 2 to about 6 % of the pravastatin sodium drug granulation , and most preferably , 4 % by weight of the composition . another preferred buffering agent is dibasic sodium phosphate ( na 2 hpo 4 ), which is very soluble in water and widely used as a buffering agent for pharmaceuticals . pharmaceutical compositions of the present invention as in example 1 below , may contain one or more fillers in a range from about 30 to about 95 % by weight and preferably from about 60 to about 80 % by weight . anhydrous lactose which is considered an inert pharmaceutical excipient is added as a directly compressible tableting excipient . anhydrous lactose is also used as a diluent to achieve content uniformity of the finely divided active ingredients . the release rate of anhydrous lactose increases as the particle size of the sugar decreases . in the preferred embodiment , the optimal amount of lactose is found to be 73 weight % of the granules and 73 % of the total tablet weight . examples of other suitable excipients known to those skilled in the art which may be used include , sucrose , dextrose , lactose , cellulose derivatives such as microcrystalline cellulose , calcium carbonate , calcium sulfate , magnesium carbonate , corn starch , modified corn starch , mannitol , xylitol , fructose , sorbitol , and mixtures thereof . the optimal concentration of the fillers for pravastatin granules was determined to be a mixture of 1 : 6 . 5 ( wt ./ wt .). the optimal concentration of the fillers for the pravastatin sodium tablets was determined to be a mixture of 1 : 3 . an effective amount of any generally accepted pharmaceutical tableting lubricant , may be added to compress the tablets . if a lubricant is added it should be present in an amount within the range from about 0 . 05 to about 6 %, preferably 0 . 5 to about 2 % by weight may be added . tablet lubricants present are preferably from the group consisting of glyceryl monostearates , magnesium stearate , palmitic acid , talc , carnauba wax , calcium stearate , sodium or magnesium lauryl sulfate , calcium soaps , zinc stearate , polyoxyethylene monostearates , calcium silicate , silicon dioxide , hydrogenated vegetable oils and fats , or stearic acid . most preferably , magnesium stearate is present as a lubricant to prevent the powder from agglomerating during processing on a high speed rotary press . magnesium stearate is added to the granulation to assist compression . a preferred lubricant is magnesium stearate . in the preferred embodiment shown in example 1 , magnesium stearate is used in an amount of less than 2 % of the tablet . one or more binders may be present in a range of about 0 - 20 %, preferably 5 to about 15 %, and most preferably about 10 %. examples of suitable binders may include , but are not limited to cellulose compounds , ( such as microcrystalline cellulose , methyl cellulose , hydroxymethyl cellulose , hydroxypropyl methyl cellulose ), acrylates , methacrylates , polyvinylpyrrolidone , and other materials known to have cohesive and desirable binding properties which are known to one of ordinary skill in the art . in the preferred embodiment , microcrystalline cellulose is used . a tablet disintegrant is added to the direct compression process for its wicking ( i . e ., the ability of particles to draw water into the porous network of a tablet ) and swelling ability . some of these disintegrants also serve as excellent binders and are able to substantially improve the mechanical strength of the formulation . suitable disintegrants are carboxymethyl cellulose sodium , carboxymethyl cellulose calcium , crospovidone , sodium starch glycolate , corn starch , insoluble cationic - exchange resins such as polyacrylin , microcrystalline cellulose , croscarmellose . disintegrants are added at concentrations ranging from 0 . 5 - 10 %. croscarmellose sodium ( cross - linked carboxymethyl cellulose ) preferably at a concentration of 2 - 6 %, and most preferably at a concentration of 5 % is preferred . croscarmellose is not compatible with hygroscopic excipients and soluble salts of metals . a colorant may be added to the lactose forming the pravastatin sodium granules and the directly compressed powders . alternatively , colorant may be added to the tableting process . the colorant may include various soluble synthetic dyes and insoluble pigments such as fd & amp ; c colors including aluminum lakes . in the preferred embodiment , lake blend purple is utilized . the tablets of the invention may also include a film or sugar coating layer . the film or sugar coating influences the tablet moisture , surface roughness , and coating efficacy and uniformity . the film or sugar coating formulation which may be 1 - 6 % of the total formulation . in a preferred embodiment the pravastatin is granulated with the filler , the binding agent and the buffer solution . the pravastatin granules preferably comprise 50 - 90 % of the total tablet weight , more preferably 60 - 80 %, and most preferably 70 - 75 %. the preferred pravastatin granule composition of the invention is given below : the ph there granules should be less than 9 , preferably less than 8 . 5 and most preferably less than 8 . the manufacture of tablets of the present invention involves dissolving tromethamine in water and using the solution to granulate a mixture of anhydrous lactose , microcrystalline cellulose , and pravastatin . filler ( preferably anhydrous lactose ) and binder ( preferably microcrystalline cellulose ) are separately screened or milled to break up agglomerates . the screened materials and drug ( pravastatin ) are then granulated in the following order : fraction of the filler ( less than 50 %), drug , binder , remaining filler ( less than 40 %). a buffer in solution is added and mixed . granulation cycle is initiated until the desired consistency of granulation is achieved . the granules are then passed through a 25 mesh screen , dried by conventional methods and passed through a fitzmill . the drug granulation is then blended with sufficient quantity of filler to bulk up for tablet compression . the filler is screened through a 25 mesh screen . the drug granules are placed into a blender with screened filler . the lubricant is then screened and added to the blender followed by the coloring agent which is screened and added to the blender . the powders are then compressed into tablets using appropriate conventional tools such as a suitable tableting press to form the tablet of the invention . each tablet in the above procedure preferably contains a therapeutically effective amount of pravastatin sodium and the following excipients : alternatively , the tablets may also be formulated by a wet granulation technique where a mixture of the medicament , buffer , filler , and binder is granulated using an aqueous binder solution such as polyvinyl pyrrolidone . the following examples are illustrative of the present invention , and the examples should not be considered as limiting the scope of this invention in any way , as these examples and other equivalents thereof win become apparent to those versed in the art in the light of the present disclosure , and the accompanying claims . tablet formulations containing 40 mg of pravastatin sodium are made with the following ingredients in the following amounts : two seperate portions of anhydrous lactose , along with microcrystalline cellulose are individually sifted through a 25 mesh screen . the sifted ingredients are then placed in a granulator in the following order : 1 . the larger portion of anhydrous lactose 2 . pravastatin sodium 3 . microcrystaline cellulose 4 . the smaller portion of anhydrous lactose after each addition , the granulator is started and allowed to mix the dry materials . after , the addition of the final portion of anhydrous lactose , the material is granulated with tromethamine solution , using conventional means . the granulate is dryed in any acceptable manner for pharmaceutical processing . drying continues until the moisture content is below about 2 %. most preferably , the granules are dryed until the moisture content is below about 1 . 8 %. the dried granules are passed through a screen of 25 mesh approximate size . the screening of the granules may be through any desired machine or mechanism as is commonly known in the art . a pharmaceutical formulation is then prepared as follows using the pravastatin granules comprising approximately , by weight : after screening the anhydrous lactose , it is charged together with the pravastatin granules into a suitable blender . after sifting through a 25 mesh screen , the resultant granulation is then lubricated . in the following order , croscarmellose sodium , magnesium stearate , and lake blend purple are added to the blender . the blend was compressed into tablets using any conventional manner . in the same manner as described in example 1 , a tablet containing 20 mg of pravastatin sodium is made with the ingredients and amounts indicated below : ingredient mg / tablet pravastatin sodium 22 anhydrous lactose , nf 75 anhydrous lactose , nf 70 tris ( tromethamine ), usp 8 microcrystalline cellulose , nf 20 in the same manner as described in example 1 , a tablet containing 10 mg of pravastatin sodium is made with the ingredients and amounts indicated below : 2 . combining the screened lactose with the pravastatin sodium granules into a suitable blender . 3 . allowing the blender to combine the granules with lactose until a uniform blend is achieved . 4 . pass the crosscarmellose sodium , magnesium stearate , and lake blend purple through a 25 mesh screen . 5 . add the crosscarmellose sodium , magnesium stearate , and lake blend purple to the blender containing the granules with lactose . the ph of this tablet is approximately 8 . 35 and was determined by dissolving 1 tablet in 900 ml of deionized water . the ph of this tablet is approximately 8 . 00 and was determined by dissolving 1 tablet in 900 ml of deionized water . ingredient mg / tablet pravastatin sodium granules 100 anhydrous lactose 18 croscarmellose sodium , nf 5 magnesium stearate 1 lake blend purple 1 pravastatin sodium tablets with tromethamine were subjected to an accelerated stability test the tablets were exposed to 40 ° c . ( 75 % relative humidity ) for 3 months time . at the end of 3 months time , the amount of pravastatin sodium that had degraded to lactones were determined by hplc analysis . the stability tests indicate that replacing the basifying agent magnesium oxide with the buffer tromethamine increases the stability of pravastatin sodium tablets . while certain preferred and alternative embodiments of the invention have been set forth for purposes of disclosing the invention , modifications to the disclosed embodiments may occur to those who are skilled in the art . accordingly , the appended claims are intended to cover all embodiments of the invention and modifications and variations may be made herein , in accordance with the inventive principles disclosed , without departing from the spirit and scope of the invention . | 0 |
fig1 shows a dishwasher 10 having a cabinet 12 and an openable door 14 . a wash chamber 16 of the cabinet 12 houses dish supporting racks 18 and a rotating spray arm 20 . a control panel 22 is provided with a plurality of controls 24 for pre - selecting the desired cycle of operation for the dishwasher . since the dishwasher 10 embodying the principles of the present invention may be a countertop style dishwasher , a water inlet hose 26 is shown as being connected to a kitchen faucet 28 and a drain hose 30 is shown as being directed toward a kitchen sink drain 32 . of course , the dishwasher 10 could be a built - in unit , in which case the water inlet line 26 and the drain line 30 would be permanently connected to the house plumbing . as seen in fig1 there is a dish rack 18 provided in the dishwasher . the rack may be provided with rollers 33 ( fig5 and 6 ) for easy movement of the racks . preferably , the rack is formed of welded wire with a plastic coating . the wire form of the dish rack is designed so as to minimize interference of the rack with spray from the spray arm 20 . fig2 shows a schematic illustration of the fluid flow patterns within the dishwasher 10 . in the schematic illustration the water inlet line 26 is shown at the far right , where it is seen that water first passes through a fill valve 34 which is operated by the dishwasher control 24 . the inlet water then passes through a vacuum break 36 and into a settling chamber / drain sump 38 . from the settling chamber / drain sump 38 , water flows through an opening 40 in a separating wall 41 into a spray sump 42 . from the spray sump 42 water is drawn by a spray pump 43 driven by a motor 44 ( fig4 ) and directed to the spray arm 20 within the wash chamber 16 through a connecting conduit 45 . water from the wash chamber 16 partially flows to a first trough 46 through an opening 74 and into the settling chamber / drain sump 38 and partially to a second trough 48 through an opening 81 back to the spray sump 42 . at various times during the wash cycle , when it is desired that the wash liquid be removed from the dishwasher , a drain pump 50 driven by a motor 51 ( fig4 ) draws wash liquid from the settling chamber / drain sump 38 and directs it to the drain line 30 . during a drying portion of the wash cycle , room air is drawn in by a blower or fan 52 operated by the spray pump motor 44 . the air is directed in through the second trough 48 to flow through the wash chamber 16 to be vented through an opening 54 preferably located near the front top portion of the dishwasher cabinet 12 . as best seen in fig3 and 5 , wash liquid drains from the wash cavity 16 by means of a depressed area or sump 62 which preferably is molded into a bottom wall 63 of the wash chamber . the depressed area 62 is divided into the two troughs 46 , 48 by a dividing wall 68 which extends along most but not the entire length of the depressed area 62 . there is a communicating opening 70 through the wall 68 between the two troughs 46 , 48 which assists in the draining of the dishwasher . the two trough are of unequal size , and the larger trough 48 leads to the spray sump 42 , and is covered with a filter screen 72 which permits passage of liquid , but which inhibits passage of food particles . the screen 72 is sloped downwardly toward the smaller trough 46 , and thereby assists in the movement of soil particles toward the first trough . also , the spray arm 20 has at least one downwardly directed nozzle opening 73 which directs a spray of wash liquid against the screen 72 ( fig6 ) to assist in the cleaning of the screen and directing food particles to the first trough 46 . spray arm rotation is set so that the cleaning spray can sweep soil directly off of the filter screen 72 and into the first trough 46 leading to the settling chamber / drain sump 38 . the first trough 46 leads to an opening 74 communicating with the settling chamber / drain sump 38 which is located at the lowest elevation of the dishwasher cabinet . the settling chamber / drain sump 38 is crucial to the operation of the dishwasher , in that it enables the dishwasher to achieve an acceptable level of wash results with just four fills and one detergent addition . the settling chamber / drain sump 38 removes both lighter - than - water and heavier - than - water soils from the recirculating wash liquid . these soils are trapped in the settling chamber / drain sump 38 , in which the drain pump 50 is located , so that they are disposed of quickly during the pump - out process . the settling chamber / drain sump 38 includes an isolated chamber 39 to which soil - laden water is directed from the trough 46 in the dishwasher base unit . the entry opening 74 to the settling chamber / drain sump 38 has its top 74a above the operating wash liquid level . this allows floating soil to enter the chamber and prevents it from being trapped in the main washing compartment 16 . the flow through the settling chamber / drain sump 38 is carefully controlled to reduce turbulence and allow soils to settle ( or float ) out of the wash / rinse fluid . within the settling chamber / drain sump 38 there is a baffle wall 75 which prevents turbid fluid from the wash chamber 16 from flowing directly into the isolated chamber 39 . during the wash cycle as fluid flows through the trough 46 into the settling chamber / drain sump 38 , it is permitted to flow then into the spray sump 42 through the opening 76 , which is in the form of a v - shaped notch ( fig3 and 8 ) formed in the wall 41 that isolates the settling chamber / drain sump from the spray sump . the v - notch 76 is sized so that a flow rate of approximately one half gallon per minute is maintained through the v - notch when the spray pump 43 is operating . the flow of wash liquid from the settling chamber / drain sump 38 to the spray sump 42 is directed through an opening 77 ( fig7 ) under an appropriately spaced wall 78 so that floating soil is trapped in the settling chamber / spray sump before it gets to the v - notch 40 . a bottom 80 of the v - notch 40 is high enough to trap heavy soil that has settled to the bottom of the isolated chamber 39 . the flow velocity through the settling chamber / drain sump 38 is normally relatively slow , thus allowing heavier - than - water soils to settle , and lighter - than - water soils to rise . the screen 72 provides a small impedance of the flow of wash liquid from the wash cavity sump 62 , through an opening 81 communicating with the spray sump 42 . this impedance produces a wash liquid level that is higher in the settling chamber / drain sump 38 than the level in the spray sump 42 , and provides the driving force that gives the above - mentioned one half gallon per minute separator flow . the system described is self - regulating . in the exemplary embodiment , the settling chamber / drain sump 38 is designed for a one half gallon per minute flow of relatively clean wash liquid . when heavy soils are encountered , the protecting filter screen 72 may become partially blocked . this increases the flow impedance to the spray pump 43 and creates a greater fluid level difference between the spray sump 42 and the isolated chamber 39 of the settling chamber / drain sump 38 . as the fluid level in the spray sump 42 drops , the effective fluid passage area through the v - notch 40 increases . the result is that the fluid flow rate through the v - notch 40 increases until the heavy soil is pulled from the surface of the screen 72 and into the settling chamber / drain sump . as a result , the filter screen blockage has been eliminated , flow impedance is returned to normal , and then flow through the settling chamber / drain sump returns to the one - half gallon per minute rate . the result is very rapid removal of large soil particles from the wash water followed by removal of the fine soil particles . the slow relatively turbulence - free flow through the settling chamber / drain sump 38 also minimizes the suspension and homogenizing action that occur between detergent and soil in a highly agitated system . the result is that little detergent is used by the soil trapped in the settling chamber / drain sump 38 . this means that more detergent remains available in the water for cleaning of the dishes , or , alternatively , less detergent addition is needed to perform the cleaning function . at appropriate times during the wash cycle the wash liquid within the dishwasher is pumped by drain pump 50 through the drain line 30 to remove wash liquid and collected soil particles from the dishwasher . a soil chopper 82 ( fig4 ), including a single wire pressed at a right angle through an extension 84 of the pump impeller , is located just below an impeller opening 86 of the drain pump 50 . the proximity of the chopper 82 to the impeller opening 86 is chosen such that the chopper 82 chops all soil to a size that can pass through both the pump 50 and the drain hose 30 of the system . a pump capacity of approximately one gallon per minute has been determined to be sufficiently large to provide the necessary pump out operation . a separate drain line 90 ( fig4 ) is provided between the spray conduit 45 and the drain pump 50 to permit a pump out of all wash liquid within the system . the drain line 90 includes a check valve 92 which is closed when the spray pump 43 is in operation , but which moves to an open position , allowing draining to the settling chamber / drain sump 38 , when the spray pump 43 is not in operation . both the spray pump 43 and drain pump 50 of the power system are designed to operate without pump seals . this is facilitated by the fact that both of the motors are well above the operating wash liquid level . to facilitate the no - seal design , impellers 94 , 96 of the pumps 50 , 43 have pumping elements or impeller blades 98 , 100 on both sides . the pumping element 100 on the motor side of the impeller counteracts the pressure developed by the main impeller pumping element 98 . this prevents pressurized water from escaping through a clearance space 102 between a motor shaft 104 and the pump body 106 . this design eliminates both manufacturing and service costs associated with pump seals . it also allows the pumps to be run &# 34 ; dry &# 34 ; with no chance for seal damage . since running dry is possible , the spray pump motor 44 is fitted with the fan 52 that serves both to cool the motor and to provide forced air for drying within the dishwasher . a cover 108 is provided which surrounds the motors 44 , 51 and fan 52 , and which is secured to a subassembly base 110 carrying the motors 44 , 51 by an appropriate fastener arrangement such as a tab in groove connection 112 at one end 114 and a wire rod clip 116 secured between the cover 108 and the dishwasher base 118 at an opposite end 120 . the subassembly base 110 has a passage 122 molded therein which permits air from outside the cover 108 to be drawn into an area 124 enclosed by the cover 108 . more particularly , the air is drawn through the passage 122 into openings 126 which are within a separate cover 128 enclosing the motor 44 . the air is then drawn through an opening 130 in the motor cover 128 into the fan 52 which then pressurizes the area 124 within the cover 108 . two air outlets are provided for the pressurized air . a first outlet 132 is one or more small vent openings in the cover 108 leading back into the area enclosed by the dishwasher cabinet 12 . a second outlet 134 ( fig9 ) leads to the washing chamber 16 ; however , this outlet is designed so that no air can flow through the washing compartment 16 when the machine is operating in a wash or rinse mode . this is accomplished by providing an air duct 136 having an inlet opening 137 open to the interior of the cover 108 and an outlet opening 138 open to the spray sump 42 . the outlet opening 138 to the spray sump 42 is covered by wash ( or rinse ) liquid at level l2 or higher when the machine is in the wash ( or rinse ) mode of operation . when the liquid is pumped out of the sumps 38 , 42 , the liquid level therein drops below the outlet opening 138 , thus permitting air from the interior of the housing 108 to flow through the air duct 136 . since the outlet opening 138 provides a larger cross - sectional area for air flow than the first cutlet 132 , most of the air flow generated by the fan 52 passes through the air duct 136 and into the spray sump 42 . from the spray sump 42 , the air flows directly into the washing chamber 16 through the channel 48 and through the screen 72 , thus drying the screen . further , since the motor 44 that runs the fan 52 also runs the pump 43 , air will be pumped through the spray arm 20 and will therefore dry out the interior of the spray arm . air control through the wash chamber 16 is needed since it is undesirable to have air flowing through the dishwasher during washing and rinsing . excessive moisture and heat losses would occur should pressurized air be introduced into the wash cavity during the wash or rinse mode . when the machine is washing or rinsing , the spray pump fan 52 still provides cooling air for the pump motor 44 . the air path through the wash chamber ( drying air ) presents significantly lower resistance to airflow than the vent openings in the cover 108 ; hence the air path through the wash chamber is the principal path used when the machine contains no wash liquid . in order to reduce manufacturing costs , the dishwasher may be constructed in a modular fashion with many of the structural components molded as a unit . for example , the washing compartment may be molded as a single unit . also a molded base unit 139 may be provided which contains both the settling chamber / drain sump 38 and the spray sump 42 as well as the above described walls 75 , 41 . a power module 140 ( carried on the subassembly base 110 ) may be provided which carries the drain pump 50 and its motor 51 , the spray pump 43 , its motor 44 , and the fan 52 , as well as other components such as an overfill protect float 142 ( fig3 and 9 ) and fill valve 34 and vacuum break 36 ( fig4 ). the power module 140 can be assembled onto the base unit 139 by a minimum of fasteners , such as a clip 144 and the connecting rod 116 with a seal 146 being provided between the two units . a seal member 147 is also provided where an outlet 148 of the spray pump 43 joins the connecting conduit 45 leading to the spray arm 20 . the spray pump 43 , located at the front of the power module 140 , is centered in the spray sump 42 molded in the base unit 139 . the pump 43 is surrounded by a tubular electrical heating element 150 . the heating element 150 is formed in a simple geometric shape to heat fluid throughout the sump 42 , and is carefully located so that it is spaced away from direct contact with any of the molded plastic parts of the system . in the exemplary embodiment , heating element power is 1200 watts and provides a temperature rise of about 3 ° fahrenheit per minute . the spray pump flow rate is approximately eight gallons per minute . the control system may either be electronic or electromechanical . in the illustrated embodiment , the control is designed for a timed - fill with a float switch overfill protection . the control is designed to be a complete subassembly located at the dishwasher front to the right of the washing compartment 16 . the control provides a temperature hold on selected parts of the cycle . a 140 ° fahrenheit temperature hold thermostat 152 is installed in the machine power module along with a second safety thermostat 154 that shuts off the water heater element 150 in the event of an over - temperature condition . the safety thermostat 154 operates independently of the control module . as is apparent from the foregoing specification , the invention is susceptible of being embodied with various alterations and modifications which may differ particularly from those that have been described in the preceding specification and description . it should be understood that we wish to embody within the scope of the patent warranted hereon all such modifications as reasonably and properly come within the scope of our contribution to the art . | 0 |
fig1 illustrates one preferred embodiment of an internal pedicle insulator apparatus 10 . the internal pedicle insulator apparatus 10 comprises an inner insertion rod 12 , an outer insertion rod 14 , and an internal pedicle insulator implant 16 . the inner insertion rod 12 has a bottom end 18 and an opposing top end 20 . it is preferable that the inner insertion rod 12 has a substantially round cross - section . however , it should be noted that the inner insertion rod 12 can comprise any suitable configuration . the inner insertion rod 12 can comprise any suitable material , such as titanium , as merely one example . the outer insertion rod 14 has a lower end 11 and an opposing upper end 13 . an opening 15 is disposed at the lower end 11 . an optional handle 17 can be disposed toward the upper end 13 of the outer insertion rod 14 to facilitate use of the internal pedicle insulator apparatus 10 . an opening at the upper end 13 of the outer insertion rod 14 through which the inner insertion rod 12 can pass can also be included ( not shown ). it is preferable that the outer insertion rod 14 has a substantially round cross - section . it should be noted , however , that the outer insertion rod 14 can comprise any suitable cross - section . the outer insertion rod 14 can comprise titanium , however , it should be understood that the outer insertion rod 14 can comprise any suitable material . the outer insertion rod 14 is arranged and configured to receive the inner insertion rod 12 through the opening 15 disposed at the lower end 11 of the outer insertion rod 14 . the inner insertion rod 12 is preferably slidably inserted into the outer insertion rod 14 such that the upper end 13 of the outer insertion rod 12 substantially corresponds to the top end 20 of the inner insertion rod 12 . similarly , the lower end 11 of the outer insertion rod 14 substantially corresponds with the bottom end 18 of the inner insertion rod 12 . the inner insertion rod 12 is laterally slidable within the outer insertion rod 14 . referring next to fig1 a , in one embodiment it is preferable that the outer insertion rod 14 is defined by a diameter d o . the inner insertion rod 12 is defined by a diameter d i . it is preferable that d o is greater than d i to facilitate the inner insertion rod 12 being slidably disposed within the outer insertion rod 14 . it is further preferable that d o is less than d i such as to leave a space 22 having a thickness t s when the inner insertion rod 16 is disposed within the outer insertion rod 14 . as shown in fig1 b , in one embodiment the internal pedicle insulator implant 16 is substantially rectangular in shape and curved . it should be understood , however , that the internal pedicle insulator implant 16 can comprise any suitable shape and configuration . in this embodiment it is preferable that the internal pedicle insulator implant 16 is curved as defined by a radius r i . it is preferable that the radius r i of the internal pedicle insulator implant 16 substantially corresponds to a pedicle screw 104 with which the internal pedicle insulator implant 16 is to be used . the internal pedicle insulator implant 16 is also defined by a thickness t i . it is preferable that the thickness t is greater than the thickness t s of space 22 . the internal pedicle insulator implant 16 preferably comprises poly ether ether - ketone , but can comprise any suitable material . fig2 and 2 a illustrate another embodiment of an internal pedicle insulator implant 30 . the internal pedicle insulator implant 30 is substantially tubular in shape and comprises a wall 34 . the internal pedicle insulator implant 30 has a substantially circular cross - section , defined by a diameter d i . the diameter d i is preferably arranged and configured to substantially correspond to a pedicle screw 104 with which the internal pedicle insulator implant 30 is to be used . although a substantially circular cross - section is illustrated , it should be understood that the internal pedicle insulator can have any desired cross - sectional shape . the internal pedicle insulator 30 optionally comprises at least one anti - rotation fin 32 extending outward from the wall 34 . the anti - rotation fins 32 can extend the length of the wall 34 of internal pedicle insulator 30 or only a portion of the length . the anti - rotation fins 32 can comprise any configuration that discourage rotation of the internal pedicle insulator 30 when disposed in a desired position . in one embodiment , a thickness t w of the wall 34 of the internal pedicle insulator implant 30 in addition to a height t h of an anti - rotation fin 32 extending from the wall 34 is greater than thickness t s of the space 22 between the inner insertion rod 12 and the outer rotation rod 14 when the inner insertion rod 12 is disposed within the outer rotation rod 14 . in another embodiment the internal pedicle insulator implant 30 includes no anti - rotation fin 32 ( not shown ). in this embodiment , it is preferable that a thickness t w of a wall of the internal pedicle insulator implant 30 is greater than the thickness t s of the space 22 formed by the inner insertion rod 12 and the outer insertion rod 14 when the inner insertion rod 12 is disposed inside the outer insertion rod 14 . fig3 illustrates the internal pedicle insulator apparatus 10 in use . a pedicle screw with which the internal pedicle insulator implant 16 is to be used is first removed from its position within the vertebral body . the inner insertion rod 12 is positioned as desired in the vertebral body 100 , such as in a channel created by the pedicle screw 104 . the internal pedicle insulator implant 16 is positioned adjacent the inner insertion rod 12 . the outer insertion rod 14 is positioned around the inner insertion rod 12 via the opening 15 disposed at the lower end 11 of the outer insertion rod 14 . the outer insertion rod 14 is moved in direction c toward the bottom end 18 of the inner insertion rod 12 . as the outer insertion rod 14 is moved in direction c , the outer insertion rod 14 is moved toward the internal pedicle insulator implant 16 until the outer insertion rod 14 engages the internal pedicle insulator 16 . pressure is applied to the outer insertion rod 14 in direction c to slide the internal pedicle insulator 16 along the inner insertion rod 12 toward the vertebral body 100 until the internal pedicle insulator 16 is appropriately positioned within the vertebral body 100 . the internal pedicle insulator implant 16 is held in position by friction applied to its curved configuration when properly inserted into position . after the internal pedicle insulator implant 16 is disposed in a desired position , the pedicle screw 104 is returned to its position within the vertebral body . fig4 illustrates one embodiment of an internal pedicle insulator implant 16 in a desired position . as shown , the internal pedicle insulator implant 16 is positioned between an affected nerve root 102 and a jagged hole 106 in the vertebral body 100 resulting from a compromised pedicle screw 104 . fig5 illustrates another embodiment of an internal pedicle insulator implant 16 . in this example , however , the implant is located to prevent cement , e . g ., pmma , from contacting the nerve root 102 . notably , the cement 110 is provided to anchor the pedicle screw 104 . in other embodiments , various other types of materials can be prevented from contacting a nerve by using an implant . such a material can be an injectable biological substance , for example . although cement can be provided externally with respect to the screw , the embodiment of fig5 involves a screw that incorporates holes or fenestrations e . g ., fenestration 112 . as such , the cement can be injected into the screw and then a portion of that cement can be pass through the fenestrations and into the surrounding tissue . thus , the implant 16 serves as a physical barrier to prevent the cement from impinging upon the nerve root . it should be emphasized that the above - described embodiments of the present invention , particularly , a “ preferred ” embodiment , are merely possible examples of implementations , merely set forth for a clear understanding of the principles of the invention . many variations and modifications may be made to the above - described embodiment ( s ) of the invention without departing substantially from the spirit and principles of the invention . all such modifications and variations are intended to be included herein with the scope of this disclosure and the present invention and protected by the following claims . | 0 |
various embodiments according to the present invention will now be described in more detail , by way of example only , with reference to the accompanying drawings , in which briefly described : fig1 a and 1b illustrate a composite coupling for joining cylindrical substrates that differ in diameter ; fig2 illustrates another form of composite coupling for joining cylindrical substrate ; fig4 illustrates yet another composite device for coupling cylindrical substrates ; fig1 a and 1b illustrate the use of a composite device according to the present invention for joining tubular substrate . as shown in fig1 a , tapered insert 1 to heat recoverable driver 2 has a constant outside diameter but is tapered internally from a maximum internal diameter at its ends to a minimum internal diameter near its center . as a result of this internal taper , each end of insert 1 is capable of receiving tubular substrates 3 and 4 which may be of the same or different diameter . also by reason of its taper , insert 2 is capable of accommodating a wider range of substrate diameters than would an insert of constant internal diameter . as shown in fig1 b , insert member 1 may be provided with serrations or teeth to enable it to better grip the substrate when recovery has occured . insert member 2 may also be made of a gall - prone metal relative to the substrate . for optimal attainment of the advantage conferred by the use of gall - prone inserts , the surface roughness of the insert is desirably made like that of one or more of the surfaces it adjoins in the particular application . for example , for the hydraulic conduitry for which the composite couplings are preferably employed , the generally uniform surface of the insert preferably exhibits profilometer roughness not greater than about 125 micro - inches , most preferably not greater than about 63 micro - inches . another device according to the present invention after its recovery is shown in fig2 in which the insert comprises two members 5 and 6 . the outer member 5 is tapered internally from a maximum internal diameter at one end to a minimum internal diameter at the other . as shown , member 5 is provided with longitudinal slots 7 at the end of maximum internal diameter to facilitate its deformation upon recovery . inner member 6 is provided with an outer taper complementary to that of member 5 in that it tapers from a maximum outside diameter at one end to a minimum at the other . member 6 is provided with terminal longitudinal slots 8 at either end to facilitate its deformation . as shown in fig2 inner member 6 is provided with teeth to inhibit the withdrawal of tubular members 9 and 10 after recovery by forming circumferential dents 11 and 12 . prior to recovery of driver 13 , members 5 and 6 are wedged closely together , member 5 acting upon member 6 to compensate for variations in the substrate &# 39 ; s outside diameter or substrate ovalness . another device according to the present invention that will accommodate cylindrical substrates having a large variation in outside diameter is shown in fig3 . as shown , the insert is comprised of three tapered parts , 14 , 15 and 16 . outer member 14 is provided with threaded end portions 17 and 18 and tapers internally between the threaded portions to a minimum inside diameter at its center . as shown , member 14 is provided with longitudinal slots between its threaded sections to facilitate is deformation by the driver upon its recovery . inner members 15 and 16 are tapered on their outside from a maximum outside diameter at one end to a minimum at the other and preferably are provided with terminal longitudinal slots as shown . as shown in fig3 the inner members can be provided with teeth to engage the substrate , tubular sections 19 and 20 . prior to recovery , the tubular substrates , which can have the same or different outside diameter are introduced into the aperture formed by members 15 and 16 . tightening nuts 21 and 22 provide means by which members 15 and 16 can be advanced into member 14 to initially engage substrate sections . it will be apparent that the furthest advance of members 15 and 16 is dictated by the diameter of the substrate sections . if the substrate is to carry fluid , o - ring type gaskets 23 and 24 can be provided for sealing purposes . to protect member 14 from a corrosive fluid , a toothed ring 25 can be inserted between members 15 and 16 to make the joint fluid tight . of course ring 25 must be of a material resistant to the fluid . between the tightening nuts and members 15 and 16 can be disposed washers 26 and 27 . when ring 25 is employed , gaskets 23 and 24 may be omitted . in fig4 there is shown a variant of the device of fig3 . as shown in fig4 the insert again comprises 3 parts . however , the inner member 28 of the insert has threaded ends 29 and 30 to receive tightening nuts 31 and 32 which are employed to advance tapered outer members 33 and 34 . by their advancement , insert members 33 and 33a force member 28 into close contact with substrate sections 34 and 35 prior to recovery of driver member 36 . preferably , the insert members are slotted to facilitate deformation . in the devices of both fig3 and 4 , the provision for oppositely tapered members provide means by which the inner member can be deformed prior to recovery of the driver to conform to the substrate . thus when recovery is caused to occur , a larger portion of the recovery force can be asserted to further engage the insert and substrate rather than being partially dissipated by having to first deform the insert . another device according to the present invention is depicted in fig5 . in that device , the inner member 37 of the insert is tapered from a maximum outer diameter at its ends to a minimum diameter at its center . as shown , it is provided with teeth and has longitudinal slots . outer members 38 and 39 are internally tapered to cooperate with member 37 . outer members 38 and 39 are threaded at their ends to receive tightening nuts 40 and 41 . the action of these nuts is to withdraw elements 38 and 39 which has the effect of deforming inner member 37 to cause it to engage substrates 42 and 43 . when this has been accomplished , recoverable driver 44 is warmed above its transition temperature to provide the final pressure required by the coupling . fig6 illustrates another variant of the present invention in which the insert comprises a single member 43 , preferably slotted , which is generally cylindrical and externally tapered from a minimum outside diameter at its ends to a maximum at its center . the insert is threaded from its ends to receive nuts 46 , and 47 which also functions as heat recoverable drivers , i . e . they are capable of recovering to a smaller dimension . center section 48 of insert 46 is provided with lugs to allow it to be held without rotation when the nuts are installed . preferably insert 46 is provided with internal teeth as shown . the nuts are rendered heat recoverable by mandrel expansion while the nut is at a temperature at which it exists in the martensitic state . the threads can be protected during expansion by providing the nut with a threaded liner of the same alloy that can be screwed into and out of the nut . the nut is preferably preconditioned after expansion to elevate the temperature at which it reverts to martensitic to insure that the transition does not prematurely occur during the installation of the coupling . once the substrates 49 and 50 have been inserted in the aperture defined by insert 45 , the nuts are tightened to initially deform the insert and adapt its conformation to the irregularities of the substrates . the nuts are then heated to occassion their recovery and thereby tightly engage the insert and substrates . the couplings previously described are but illustrative of the many forms the present invention may take . it will be apparent that the composite couplings of this invention are suited to many applications where the joining of cylindrical substrates is desired . for example , they might be employed to join solid or tubular structural members or cable . however , it is presently felt that the preferred application for these couplings is in the union of hollow member adapted to convey fluids , for example fluids in hydraulic systems or pipelines . | 5 |
referring to fig2 , this shows a battery cover fixing mechanism for use in an electronic device like a mobile phone ( not shown ), in accordance with a preferred embodiment of the present invention . the battery cover fixing mechanism is shown and detailed as follows for the purposes of providing a simple description of the preferred embodiment of the present invention , and the present invention and embodiments thereof are not to be construed as being limited to the following description . the battery cover fixing mechanism is for fixing a cover 1 onto a housing 2 , and includes a latching mechanism ( not labeled ), a blocking mechanism ( not labeled ), an opening 16 , a slot 20 and a cutout 24 . the latching mechanism includes a block 30 , two springs 32 , a sliding frame 34 forming at least two engagement means thereon for the latching mechanism , and a holder 36 . the cover 1 can be a single piece of shaped sheet material . the cover 1 has an inside surface 100 . the cover 1 also has a rearward section 102 , a central section 104 , and a front section 106 . the blocking mechanism includes a pair of rearward claws 10 , a pair of central claws 12 , and a pair of front claws 14 having a different forming orientation from the central claws 12 . the rearward claws 10 are symmetrically formed on the inside surface 100 of the cover 1 at the rearward section 102 . the central claws 12 symmetrically extend from two opposite edges of the inside surface 100 of the cover 1 at the central section 104 . the front claws 14 symmetrically extend from the inside surface 100 of the cover 1 at the front section 106 . the opening 16 is defined in the cover 1 between the front claws 14 . an end of each central claw 12 and each front claw 14 is chamfered , in order to facilitate installation of the cover 1 . the housing 2 typically contains electric elements such as printed circuit boards ( pcbs ), and can for example be a part of a cellphone body . a receptacle 21 formed by an opening and inner space of the housing is defined in the housing 2 to receive a component of the mobile phone like a battery ( not shown ). the cover 1 covers the receptacle 21 . two slots 20 are symmetrically defined in the housing 2 at one end thereof . the rearward claws 10 of the cover 1 engage in the slots 20 . the housing 2 has three sidewalls 22 around the receptacle 21 . said cutout 24 is defined in the housing 2 , and faces the slots 20 . referring also to fig3 , the block 30 is generally cuboidal . a pair of posts 300 extends from one main surface of the block 30 . a projection 302 extends from an opposite main surface of the block 30 . the projection 302 is slightly smaller than the opening 16 , while the block 30 is larger than the opening 16 . the springs 32 are helical and compressible . each spring 32 has a hook 320 at each of opposite ends thereof . the sliding frame 34 has a generally inverted ‘ u ’ shape , and is elastic . the sliding frame 34 comprises two opposite side portions 3402 , and a transverse portion 3400 perpendicularly interconnecting top ends of the side portions 3402 . the sliding frame 34 also comprises a blocking part ( not labeled ) as the at least two engagement means , which includes two first clasps 342 as a first engagement means and two second clasps 345 as a second engagement means . the second clasps 345 extend from the side portions 3402 respectively . an l - shaped catch piece 340 is formed on the middle of the transverse portion 3400 , corresponding to the cutout 24 . two holes 341 are defined in a vertical portion of the catch piece 340 . the posts 300 of the block 30 are inserted into the holes 341 . the first clasps 342 are symmetrically formed on the transverse portion 3400 , and a pair of grooves 343 is symmetrically defined in the transverse portion 3400 . each groove 343 is located between the catch piece 340 and a corresponding first clasp 342 . a first track 344 and a second track 347 are defined in each side portion 3402 . the first track 344 is adjacent the top end of the side portion 3402 near the transverse portion 3400 . the second track 347 is adjacent a bottom end of the transverse portion 3400 . a first catch 346 is formed on each side portion 3402 adjoining the second track 347 . the holder 36 includes a generally rectangular plate 3600 . two sidepieces 3602 are perpendicularly bent from two opposite long sides of the plate 3600 . a top piece 3604 is perpendicularly bent from a top side of the plate 3600 . a pair of inserting pieces 360 is vertically formed on the top piece 3604 . an aperture 361 is defined in the plate 3600 for receiving a sim ( subscriber identity module ) card . a first tab 363 is formed on an upper portion of each sidepiece 3602 . a second tab 365 is formed on each sidepiece 3602 below the first tab 363 . an l - shaped second catch 364 is formed on each sidepiece 3602 below the second tab 365 . a gap 366 is defined in each sidepiece 3602 immediately below where the second catch 364 adjoins the sidepiece 3602 . a vertical portion of the second catch 364 is located opposite an upper portion of the gap 366 . a process of assembling the latching mechanism on the housing 2 is as follows . firstly , the holder 36 is fixed to the housing 2 by conventional methods such as adhering or welding . for example , the sidepieces 3602 and a bottom side of the top piece 3604 of the holder 36 are adhered with the sidewalls 22 of the housing 2 . next , the sliding frame 34 is assembled on the holder 36 . the transverse portion 3400 and the side portions 3402 of the sliding frame 34 respectively abut the top piece 3604 and the sidepieces 3602 of the holder 36 . the inserting pieces 360 of the holder 36 are received in the grooves 343 of the sliding frame 34 . the first tracks 344 and the second tracks 347 are respectively longer than the first tabs 363 and the second tabs 365 . the first tabs 363 and the second tabs 365 of the holder 36 are slidably received in the first tracks 344 and the second tracks 347 of the sliding frame 34 , respectively . thus , the sliding frame 34 is slidable relative to the holder 36 . then the springs 32 are installed on the sliding frame 34 and the holder 36 . the springs 32 are first stretched , and then the hooks 320 of each spring 32 are respectively engaged on one first catch 346 of the sliding frame 34 and one second catch 364 of the holder 36 . finally , the posts 300 of the block 30 are inserted into the holes 341 of the sliding frame 34 , to thereby fix the block 30 in place . when assembling the cover 1 and the housing 2 together , the rearward claws 10 of the cover 1 are engaged in the slots 20 of the housing 2 firstly . then the cover 1 is pushed toward the housing 2 . the front claws 14 and the central claws 12 of the cover 1 are respectively engaged with the first clasps 342 and the second clasps 345 of the sliding frame 34 , and the projection 302 of the block 30 extends through the opening 16 of the cover 1 and protrudes out from a front of the cover 1 . the cover 1 is thereby assembled onto the housing 2 by the latching mechanism . when the cover 1 needs to be opened , the block 30 is pushed upward by a user . the block 30 forces the sliding frame 34 to slide relative to the holder 36 and the cover 1 . the springs 32 are further stretched , and the first clasps 342 and the second clasps 345 of the sliding frame 34 respectively disengage from the front claws 14 and the central claws 12 of the cover 1 . thereby , the cover 1 can be readily released from the housing 2 . finally , the cover 1 is taken away from the housing 2 by a user . thereupon , the springs 32 rebound , and the sliding frame 34 returns to its original position relative to the holder 36 under the elastic force of the springs 32 . in other exemplary embodiments , the springs 32 can be replaced by other elastic members such as rubber bars . the sliding frame 34 is not limited to having an inverted ‘ u ’ shape . for example , the sliding frame 34 can instead by a rectangular plate with suitable holes , slots and hooks . the block 30 and the sliding frame 34 can be a unitary component . that is , a protuberance such as a block can be integrally formed on the sliding frame 34 . the holder 36 and the housing 2 can be manufactured as a unitary whole , or manufactured separately . it is believed that the present embodiments and their advantages will be understood from the foregoing description , and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the invention or sacrificing all of its material advantages , the examples hereinbefore described merely being preferred or exemplary embodiments of the invention . | 7 |
referring to fig1 , a video controller 10 includes a video codec 8 , a display controller 18 , and a memory device 22 . the video codec 8 includes a video decoder 12 and a video encoder 14 . the video controller 10 receives an input encoded video 26 and generates an output encoded video 30 . the videos 26 and 30 can be sent as , for example , serial bit streams . the input and output encoded videos 26 and 30 may have frames that are encoded differently , such as according to different compression algorithms having different compression ratios or different resolutions . the display controller 18 generates a video signal 27 for a display 28 . each of the videos 26 and 30 includes a sequence of frames . during decoding , encoding , and displaying of the frames , certain frames are temporarily stored in the memory device 22 . the video decoder 12 , video encoder 14 , and the display controller 18 share the memory device 22 so that the number of frames that need to be simultaneously stored in the memory device 22 is fewer than for other systems . thus , a smaller memory device 22 suffices . the video decoder 12 , video encoder 14 , and display controller 18 process the frames in a particular sequence such that the frames do not need to be duplicated or moved from one memory location to another during decoding , encoding , and displaying , thereby reducing the number of frames that need to be simultaneously stored in the memory . the particular processing sequence takes into account the format of the input encoded video 26 ( e . g ., whether the frames in the video 26 are in a display order or an encode order ), the dependencies among the frames ( e . g ., b and p frames may depend on previous p and i frames ), whether the frames are displayed at the same time that the frames are being encoded , and the type of frames to be displayed ( e . g ., decompressed or reconstructed frames ). the video controller 10 also includes an audio encoder / decoder 16 that decodes and encodes audio signals , a memory controller 20 to control access to the memory device 22 , and a system controller 24 that coordinates operations of the video decoder 12 , video encoder 14 , audio encoder / decoder 16 , display controller 18 , and the memory controller 20 . the video controller 10 can be fabricated on a single integrated circuit or may include several integrated circuits and discrete components . the following describes six examples of using the video controller 10 to transcode ( or encode ) and display videos . referring to fig2 a , in example 1 , the input encoded video 26 is a higher bit - rate compressed video , and the output encoded video 30 is a lower bit - rate compressed video . the encoded videos 26 and 30 have the same resolution . both videos 26 and 30 have frames that are arranged in an encode order . the display controller 18 sends higher bit - rate decompressed frames arranged in the display order to the display 28 . the video controller 10 outputs a lower bit - rate compressed video 30 ( e . g ., for storage ) at the same time that the display 28 shows a higher bit - rate decompressed video . the frames of the videos 26 and 30 can be encoded , for example , according to an mpeg standard . in this description , a “ higher bit - rate compressed video ” has a higher bit rate relative to a “ lower bit - rate compressed video ,” and a “ higher bit - rate decompressed video ” has a higher bit rate relative to a “ lower bit - rate decompressed video .” the “ higher bit - rate compressed video ,” due to compression , can have a bit rate that is lower than the “ lower bit - rate decompressed video .” the resolution of a compressed video refers to the resolution of the decompressed frames . a “ higher resolution compressed video ” can be decompressed to generate decompressed frames that have a higher resolution relative to decompressed frames derived from a “ lower resolution compressed video .” fig2 b shows memory buffers that are allocated in the memory device 22 for storing frames that are generated during the decoding , encoding , and displaying processes . the memory device 22 includes an input buffer 100 , a reconstructed encode reference 1 buffer 102 , a reconstructed encode reference 2 buffer 104 , an encode stage 1 buffer 106 , an encode stage 2 buffer 108 , an encode stage 3 buffer 110 , an encode stage 4 buffer 112 , an encode stage 5 buffer 114 , and an output buffer 116 . the input buffer 100 stores a higher bit - rate compressed frame , and the output buffer 116 stores a lower bit - rate compressed frame ( e . g ., for delivery to a storage device ). the encode stage 1 buffer 106 , encode stage 2 buffer 108 , encode stage 3 buffer 110 , encode stage 4 buffer 112 , and encode stage 5 buffer 114 store higher bit - rate decompressed frames that are output from the video decoder 12 . the reconstructed encode reference 1 buffer 102 and the reconstructed encode reference 2 buffer 104 store lower bit - rate reconstructed frames that are generated by the video encoder 14 , and are used by the video encoder 14 during encoding of other frames . the video encoder may generate the lower bit rate decompressed frames by , for example , increasing a quantization level ( truncating more bits ) during encoding of the frames . the lower bit - rate reconstructed frames in buffers 102 , 104 are decompressed frames . in this example , the reconstructed frames have the same resolution as the higher bit - rate decompressed frames . fig2 c shows a time chart 140 indicating timing sequences in which the frames are stored in the buffers of the memory device 22 and shown on the display 28 . the frames are displayed in the order : i 0 , b 1 , b 2 , p 3 , b 4 , b 5 , p 6 , b 7 , b 8 , p 9 , b 10 , b 11 , p 12 , and so forth . rows 120 , 122 , 124 , 126 , 128 , 130 , to 132 indicate the contents of the buffers 102 , 104 , 106 , 108 , 110 , 112 , and 114 , respectively . row 134 indicates the time intervals at which the frames are encoded . row 136 indicates the time intervals at which the frames are fetched by the display controller 18 and shown on the display 28 . in this example , the encode stage 5 buffer 114 is not used . the memory device 22 has a large enough capacity to accommodate the encode stage 5 buffer 114 for use in other examples ( e . g ., examples 5 and 6 described below ). each column ( e . g ., 138 ) in the time chart 140 indicates the contents of the buffers , the frame that is encoded by the video encoder 14 , and the frame that is shown on the display 28 during a particular time interval t . as can be seen from the time chart 140 , each frame is accessed by only one of the video decoder 12 , the video encoder 14 , and the display controller 18 at any given time interval , so the video decoder 12 , the video encoder 14 , and the display controller 18 can share the frames stored in the memory buffers without conflict . each frame in the memory device 22 is stored once without duplication . the following describes the processes performed by the video decoder 12 , the video encoder 14 , and the display controller 18 at various time intervals . each time interval , such as t 0 , t 1 , t 2 , . . . , represents a frame period , which can be about 33 . 3 ms when the video is configured to have 30 frames per second . before time interval to ( not shown in fig2 c ), a higher bit - rate compressed i 0 frame is written to the input buffer 100 . similarly , during time intervals t 0 , t 1 , t 2 , t 3 , t 4 , t 5 , t 6 , t 7 , t 8 , t 9 , t 10 , t 11 , t 12 , . . . , higher bit - rate compressed frames p 3 , b 1 , b 2 , p 6 , b 4 , b 5 , p 9 , b 7 , b 8 , p 12 , b 10 , b 11 , . . . , respectively , are written to the input buffer 100 . during time interval t 0 , the video decoder 12 retrieves the compressed i 0 frame from the input buffer 100 , decodes the compressed i 0 frame to generate a higher bit - rate decompressed frame i 0 , and writes the decompressed i 0 frame to the encode stage 1 buffer 106 . during time interval t 1 , the video decoder 12 retrieves the compressed p 3 frame from the input buffer 100 , decodes the compressed p 3 frame and generates a decompressed p 3 frame , and writes the decompressed p 3 frame to the encode stage 2 buffer 108 . the video encoder 14 retrieves the higher bit - rate decompressed i 0 frame from the buffer 106 , encodes the i 0 frame to generate a lower bit - rate reconstructed i 0 ′ frame and a lower bit - rate compressed i 0 ′ frame , writes the reconstructed i 0 ′ frame to the reconstructed reference 1 buffer 102 , and writes the compressed i 0 ′ frame to the output buffer 116 . during time interval t 2 , the video decoder 12 decodes the higher bit - rate compressed b 1 frame to generate a higher bit - rate decompressed b 1 frame , and writes the decompressed b 1 frame to the encode stage 3 buffer 110 . the video encoder 14 retrieves the decompressed p 3 frame from the buffer 108 , encodes the decompressed p 3 frame to generate a lower bit - rate reconstructed p 3 ′ frame and a lower resolution compressed p 3 ′ frame , writes the reconstructed p 3 ′ frame to the reconstructed reference 2 buffer 104 , and writes the compressed p 3 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed i 0 frame from the buffer 106 and causes the i 0 frame to be shown on the display 28 . during time interval t 3 , the video decoder 12 decodes the higher bit - rate compressed b 2 frame to generate a higher bit - rate decompressed b 2 frame , and writes the decompressed b 2 frame to the encode stage 4 buffer 112 . the video encoder 14 retrieves the decompressed b 1 frame from the buffer 110 , encodes the decompressed b 1 frame to generate a lower bit - rate compressed b 1 ′ frame , and writes the compressed b 1 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed b 1 frame from the buffer 110 and causes the bi frame to be shown on the display 28 . during time interval t 4 , the video decoder 12 decodes the higher bit - rate compressed p 6 frame to generate a higher bit - rate decompressed p 6 frame , and writes the decompressed p 6 frame to the encode stage 1 buffer 106 . the video encoder 14 retrieves the decompressed b 2 frame from the buffer 112 , encodes the decompressed b 2 frame to generate a lower bit - rate compressed b 2 ′ frame , and writes the compressed b 2 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed b 2 frame from the buffer 112 and causes the b 2 frame to be shown on the display 28 . during time interval t 5 , the video decoder 12 decodes a higher bit - rate compressed b 4 frame to generate a higher bit - rate decompressed b 4 frame , and writes the decompressed b 4 frame to the encode stage 3 buffer 110 . the video encoder 14 retrieves the decompressed p 6 frame from the buffer 106 , encodes the decompressed p 6 frame to generate a lower bit - rate reconstructed p 6 ′ frame and a lower bit - rate compressed p 6 ′ frame , writes the reconstructed p 6 ′ frame to the buffer 102 , and writes compressed p 6 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed p 3 frame from the buffer 108 and causes the p 3 frame to be shown on the display 28 . during time interval t 6 , the video decoder 12 decodes the higher bit - rate compressed b 5 frame to generate a higher bit - rate decompressed b 5 frame , and writes the decompressed b 5 frame to the encode stage 4 buffer 112 . the video encoder 14 retrieves the decompressed b 4 frame from the buffer 110 , encodes the decompressed b 4 frame to generate a lower bit - rate compressed b 4 ′ frame , and writes the compressed b 4 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed b 4 frame from the buffer 110 and causes the b 4 frame to be shown on the display 28 . during time interval t 7 , the video decoder 12 decodes the higher bit - rate compressed p 9 frame to generate a higher bit - rate decompressed p 9 frame , and writes the decompressed p 9 frame to the encode stage 2 buffer 108 . the video encoder 14 retrieves the decompressed b 5 frame from the buffer 112 , encodes the decompressed b 5 frame to generate a lower bit - rate compressed b 5 ′ frame , and writes the compressed b 5 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed b 5 frame from the buffer 112 and causes the b 5 frame to be shown on the display 28 . during time intervals t 8 , t 9 , t 10 , and so forth , the video controller 10 operates in a manner similar to those described above . the operation of the video decoder 12 , the video encoder 14 , and the display controller 18 is designed such that a first frame is overwritten by a second frame only after the first frame will no longer be used by the video decoder 12 , the video encoder 14 , or the display controller 18 . for example , during and after the time interval t 4 , the i 0 frame is not used by the video decoder 12 , the video encoder 14 , or the display controller 18 , so the i 0 frame in the encode stage 1 buffer 106 can be overwritten by the p 6 frame during t 4 . similarly , during and after the time interval t 7 , the p 3 frame in the encode stage 2 buffer 108 is not used by the video decoder 12 , the video encoder 14 , or the display controller 18 , so the p 3 frame can be overwritten by the p 9 frame during t 7 . because the b - frames are not referenced by any other frame , it is not necessary to store lower bit - rate reconstructed b ′- frames in the memory device 22 . in example 1 , the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than four decompressed frames ( in buffers 106 , 108 , 110 , and 112 ) written by the video decoder 12 and two reconstructed frames ( in buffers 102 and 104 ) written by the video encoder 14 . because the reconstructed frames are decompressed frames , the memory 22 at any given time stores no more than six decompressed frames . the operations of the video decoder 12 , the video encoder 14 , and the display controller 18 are coordinated by the system controller 24 . for example , the system controller 24 may adjust pointers used by the video decoder 12 , the video encoder 14 , and the display controller 18 to control which memory buffer is accessed by the video decoder 12 , the video encoder 14 , and the display controller 18 . in example 2 , the lower bit - rate compressed video 30 has a lower resolution as compared to the higher bit - rate compressed video 26 . the compressed videos 26 and 30 may have the same or different compression ratios ( e . g ., quantization levels ). for example , the input encoded video 26 can have 1920 × 1080 resolution , and the output encoded video 30 can have 1366 × 768 resolution . both the encoded videos 26 and 30 have frames that are arranged in an encode order . the display controller 18 sends higher resolution frames arranged in the display order to the display 28 . thus , the video controller 10 outputs a lower bit - rate compressed video 30 having a lower resolution at the same time that the display 28 shows the video in a higher resolution . the allocation of memory buffers in the memory device 22 for example 2 is similar to that of example 1 , as shown in fig2 b . the input buffer 100 stores a higher resolution compressed frame , and the output buffer 116 stores a lower resolution compressed frame generated by the video encoder 14 . the encode stage 1 buffer 106 , encode stage 2 buffer 108 , encode stage 3 buffer 110 , encode stage 4 buffer 112 , and encode stage 5 buffer 114 store higher resolution decompressed frames that are output from the video decoder 12 . the reconstructed encode reference 1 buffer 102 and the reconstructed encode reference 2 buffer 104 store lower resolution reconstructed frames that are used by the video encoder 14 during the encoding process to generate the lower resolution compressed frames . a descaler can generate the lower resolution reconstructed frames by using a descaling process . the descaler can be part of the video decoder 12 or the video encoder 14 . the descaler can also be a component independent of the video decoder 12 and the video encoder 14 . the encoding and the descaling of the frames can be performed at the same time . timing sequences for example 2 is similar to that of example 1 , as shown in fig2 c . the processes performed by the video decoder 12 , the video encoder 14 , and the display controller 18 are similar to those described in example 1 , except that the frames i 0 ′, b 1 ′, b 2 ′, p 3 ′, b 4 ′, b 5 ′, p 6 ′, b 7 ′, b 8 ′, p 9 ′, b 10 ′, b 11 ′, and p 12 ′ are lower resolution reconstructed frames , and i 0 , b 1 , b 2 , p 3 , b 4 , b 5 , p 6 , b 7 , b 8 , p 9 , b 10 , b 11 , and p 12 are higher resolution decompressed frames . similar to example 1 , in example 2 , the video decoder 12 , the video encoder 14 , and the display controller share the memory 22 such that the memory 22 at any given time stores no more than six decompressed frames , including four decompressed frames written by the video decoder 12 and two reconstructed frames written by the video encoder 14 . referring to fig3 a , in example 3 , similar to example 1 , the input encoded video 26 is a higher bit - rate compressed video , and the output encoded video 30 is a lower bit - rate compressed video . the encoded videos 26 and 30 have the same resolution but different bit rates . both the encoded videos 26 and 30 have frames that are arranged in an encode order . the frames of the videos 26 and 30 can be encoded , for example , according to an mpeg standard . in example 3 , the display controller 18 sends lower bit - rate frames arranged in the display order to the display 28 . the video controller 10 outputs a lower bit - rate compressed video 30 at the same time that the display 28 shows a lower bit - rate decompressed video . fig3 b shows a time chart 150 indicating timing sequences in which the frames are stored in the buffers of the memory device 22 and shown on the display 28 . in this example , the encode stage 5 buffer 114 is not used . as can be seen from the time chart 150 , each frame is accessed by only one of the video decoder 12 , the video encoder 14 , and the display controller 18 at any given time interval , so that the video decoder 12 , the video encoder 14 , and the display controller 18 can share the frames stored in the memory buffers without conflict . each frame in the memory device 22 is stored once without duplication . the following describes the processes performed by the video decoder 12 , the video encoder 14 , and the display controller 18 at various time intervals . before time interval t 0 ( not shown in fig3 b ), a higher bit - rate compressed i 0 frame is written to the input buffer 100 . similarly , during time intervals t 0 , t 1 , t 2 , t 3 , t 4 , t 5 , t 6 , t 7 , t 8 , t 9 , t 10 , t 11 , t 12 , . . . , higher bit - rate compressed frames p 3 , b 1 , b 2 , p 6 , b 4 , b 5 , p 9 , b 7 , b 8 , p 12 , b 10 , b 11 , . . . , respectively , are written to the input buffer 100 . during time intervals t 0 and t 1 , the video decoder 12 and the video encoder 14 operate in a manner similar to those in example 1 , as shown in fig2 c . during time interval t 2 , the video decoder 12 and the video encoder 14 operate in a manner similar to those in example 1 , as shown in fig2 c . however , the display controller 18 does not cause any frame to be shown on the display 28 during t 2 . during time interval t 3 , the video decoder 12 decodes the higher bit - rate compressed b 2 frame to generate a higher bit - rate decompressed b 2 frame , and writes the decompressed b 2 frame to the encode stage 4 buffer 112 . the video encoder 14 retrieves the decompressed b 1 frame from the buffer 110 , encodes the decompressed b 1 frame to generate a lower bit - rate reconstructed b 1 ′ frame and a lower bit - rate compressed b 1 ′ frame , writes the reconstructed b 1 ′ frame to the buffer 110 , and writes the compressed b 1 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed i 0 ′ frame from the buffer 102 and causes the i 0 ′ frame to be shown on the display 28 . the higher bit - rate decompressed frame b 1 and the lower bit - rate reconstructed frame b 1 ′ have the same resolution ( i . e ., the same number of columns and rows ), so the decompressed frame b 1 and the reconstructed frame b 1 ′ have the same size ( i . e ., have the same number of bits ). the decompressed frame b 1 and the reconstructed frame b 1 ′ may have different image qualities . for example , the reconstructed b 1 ′ frame may not be as sharp as the decompressed b 1 frame , and block artifacts in the reconstructed b 1 ′ frame may be more visible than in the decompressed b 1 frame . during time interval t 4 , the video decoder 12 decodes the higher bit - rate compressed p 6 frame to generate a higher bit - rate decompressed p 6 frame , and writes the decompressed p 6 frame to the buffer 106 . the video encoder 14 retrieves the decompressed b 2 frame from the buffer 112 , encodes the decompressed b 2 frame to generate a lower bit - rate reconstructed b 2 ′ frame and a lower bit - rate compressed b 2 ′ frame , writes the reconstructed b 2 ′ frame to the buffer 112 , and writes the compressed b 2 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed b 1 ′ frame from the buffer 110 and causes the b 1 ′ frame to be shown on the display 28 . during time interval t 5 , the video decoder 12 decodes a higher bit - rate compressed b 4 frame to generate a higher bit - rate decompressed b 4 frame , and writes the decompressed b 4 frame to the encode stage 3 buffer 110 . the video encoder 14 retrieves the decompressed p 6 frame from the buffer 106 , encodes the decompressed p 6 frame to generate a lower bit - rate reconstructed p 6 ′ frame and a lower bit - rate compressed p 6 ′ frame , writes the reconstructed p 6 ′ frame to the buffer 102 , and writes compressed p 6 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed b 2 ′ frame from the buffer 112 and causes the b 2 ′ frame to be shown on the display 28 . during time interval t 6 , the video decoder 12 decodes the higher bit - rate compressed b 5 frame to generate a higher bit - rate decompressed b 5 frame , and writes the decompressed b 5 frame to the encode stage 4 buffer 112 . the video encoder 14 retrieves the decompressed b 4 frame from the buffer 110 , encodes the decompressed b 4 frame to generate a lower bit - rate reconstructed b 4 ′ frame and a lower bit - rate compressed b 4 ′ frame , writes the reconstructed b 4 ′ frame to the buffer 110 , and writes the compressed b 4 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed b 3 ′ frame from the buffer 110 and causes the b 3 ′ frame to be shown on the display 28 . during time interval t 7 , the video decoder 12 decodes the higher bit - rate compressed p 9 frame to generate a higher bit - rate decompressed p 9 frame , and writes the decompressed p 9 frame to the buffer 108 . the video encoder 14 retrieves the decompressed b 5 frame from the buffer 112 , encodes the decompressed b 5 frame to generate a lower bit - rate reconstructed b 5 ′ frame and a lower bit - rate compressed b 5 ′ frame , writes the reconstructed b 5 ′ frame to the buffer 112 , and writes the compressed b 5 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed b 4 ′ frame from the buffer 110 and causes the b 4 ′ frame to be shown on the display 28 . during time intervals t 8 , t 9 , t 10 , and so forth , the video controller 10 operates in a manner similar to those described above . in example 3 , similar to example 1 , the operations of the video decoder 12 , video encoder 14 , and display controller 18 are designed such that a first frame is overwritten by a second frame only after the first frame will not be used by the video decoder 12 , the video encoder 14 , or the display controller 18 . the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than six decompressed frames in buffers 102 , 104 , 106 , 108 , 110 , and 112 . in example 4 , the lower bit - rate compressed video 30 has a lower resolution as compared to the higher bit - rate compressed video 26 . the compressed videos 26 and 30 may have the same or different compression ratios ( e . g ., quantization levels ). for example , the input encoded video 26 can have 1920 × 1080 resolution , and the output encoded video 30 can have 1366 × 768 resolution . both the encoded videos 26 and 30 have frames that are arranged in an encode order . the display controller 18 sends lower resolution frames arranged in the display order to the display 28 . thus , the video controller 10 outputs a lower bit - rate compressed video 30 having a lower resolution at the same time that the display 28 shows the video in a lower resolution . the allocation of memory buffers in the memory device 22 for example 4 is similar to that of example 2 , as shown in fig3 b . the input buffer 100 stores a higher resolution compressed frame , and the output buffer 116 stores a lower resolution compressed frame generated by the video encoder 14 . a descaler may generate the lower resolution decompressed frames by using a de - scaling process . the encoding and the de - scaling of the frames may be performed at the same time . timing sequences for example 4 is similar to those of example 3 , as shown in fig3 b . the processes performed by the video decoder 12 , the video encoder 14 , and the display controller 18 are similar to those described in example 3 , except that the frames i 0 ′, b 1 ′, b 2 ′, p 3 ′, b 4 ′, b 5 ′, p 6 ′, b 7 ′, b 8 ′, p 9 ′, b 10 ′, b 11 ′, and p 12 ′ are lower resolution reconstructed frames , and i 0 , b 1 , b 2 , p 3 , b 4 , b 5 , p 6 , b 7 , b 8 , p 9 , b 10 , b 11 , and p 12 are higher resolution decompressed frames . similar to example 3 , in example 4 , the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than six decompressed frames in buffers 102 , 104 , 106 , 108 , 110 , and 112 . referring to fig4 a , in example 5 , the input encoded video 26 is a compressed higher bit - rate video from a video source , such as a high definition video camcorder . the frames in the input video 26 are arranged in the display order and are compressed according to , e . g ., digital video ( dv ) or jpeg format , which specifies that the compressed frames are all intra frames . the output encoded video 30 is a compressed lower bit - rate video in which the frames are arranged in the encode order . the frames of the output video 30 are encoded according to , e . g ., an mpeg standard . the input video 26 includes i frames arranged in the display order , and the output video 30 includes i , b , and p frames arranged in the encode order . the videos 26 and 30 have the same resolution but different bit rates . the display controller 18 sends higher bit - rate frames to the display 28 in the display order . fig4 b shows a time chart 160 indicating timing sequences in which the frames are stored in the buffers of the memory device 22 and shown on the display 28 . in this example , the encode stage 5 buffer 114 is used ( as compared to examples 1 - 4 in which the buffer 114 is not used ). as can be seen from the time chart 160 , each frame is accessed by only one of the video decoder 12 , the video encoder 14 , and the display controller 18 at any given time interval , so that the video decoder 12 , the video encoder 14 , and the display controller 18 can share the frames stored in the memory buffers without conflict . each frame that is stored in the memory device 22 is stored once without duplication . the following describes the processes performed by the video decoder 12 , the video encoder 14 , and display controller 18 at various time intervals . before time interval t 0 ( not shown in fig4 b ), a higher bit - rate encoded i 0 frame is written to the input buffer 100 . similarly , during time intervals t 0 , t 1 , t 2 , t 3 , t 4 , t 5 , t 6 , t 7 , t 8 , t 9 , t 10 , t 11 , t 12 , . . . , higher bit - rate encoded frames i 1 , i 2 , i 3 , i 4 , i 5 , i 6 , i 7 , i 8 , i 9 , i 10 , i 11 , . . . , respectively , are written to the input buffer 100 . during time interval t 0 , the video decoder 12 decodes the encoded i 0 frame to generate a higher bit - rate decompressed i 0 frame , and writes the decompressed i 0 frame to the encode stage 1 buffer 106 . during time interval t 1 , the video decoder 12 decodes the encoded i 1 frame and generates a higher bit - rate decompressed i 1 frame , and writes the decompressed i 1 frame to the encode stage 3 buffer 110 . during time interval t 2 , the video decoder 12 decodes the encoded i 2 frame to generate a higher bit - rate decompressed i 2 frame , and writes the decompressed i 2 frame to the encode stage 4 buffer 112 . the video encoder 14 encodes the higher bit - rate decompressed i 0 frame to generate a lower bit - rate reconstructed i 0 ′ frame and a lower bit - rate compressed i 0 ′ frame , writes the reconstructed i 0 ′ frame to the reconstructed reference 1 buffer 102 , and writes the compressed i 0 ′ frame to the output buffer 116 . during time interval t 3 , the video decoder 12 decodes the encoded i 3 frame to generate a higher bit - rate decompressed i 3 frame , and writes the decompressed i 3 frame to the encode stage 2 buffer 108 . the video encoder 14 encodes the higher bit - rate decompressed i 3 frame to generate a lower bit - rate reconstructed p 3 ′ frame and a lower bit - rate compressed p 3 ′ frame , writes the reconstructed p 3 ′ frame to the buffer 104 , and writes the compressed p 3 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed i 0 frame from the buffer 106 and causes the i 0 frame to be shown on the display 28 . during time interval t 4 , the video decoder 12 decodes the encoded i 4 frame to generate a higher bit - rate decompressed i 4 frame , and writes the decompressed i 4 frame to the encode stage 5 buffer 114 . the video encoder 14 encodes the higher bit - rate decompressed i 1 frame to generate a lower bit - rate compressed b 1 ′ frame , and writes the compressed b 1 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed i 1 frame from the buffer 110 and causes the i 1 frame to be shown on the display 28 . during time interval t 5 , the video decoder 12 decodes the encoded i 5 frame to generate a higher bit - rate decompressed i 5 frame , and writes the decompressed i 5 frame to the encode stage 3 buffer 110 . the video encoder 14 encodes the decompressed i 2 frame to generate a lower bit - rate compressed b 2 ′ frame , and writes the compressed b 2 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed i 2 frame from the buffer 112 and causes the i 2 frame to be shown on the display 28 . during time interval t 6 , the video decoder 12 decodes the encoded i 6 frame to generate a higher bit - rate decompressed i 6 frame , and writes the decompressed i 6 frame to the encode stage 1 buffer 106 . the video encoder 14 encodes the decompressed 16 frame to generate a lower bit - rate reconstructed p 6 ′ frame and a lower bit - rate compressed p 6 ′ frame , writes the reconstructed p 6 ′ frame to the buffer 102 , and writes the compressed p 6 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed i 3 frame from the buffer 108 and causes the i 3 frame to be shown on the display 28 . during time interval t 7 , the video decoder 12 decodes the encoded i 7 frame to generate a higher bit - rate decompressed i 7 frame , and writes the decompressed i 7 frame to the encode stage 4 buffer 112 . the video encoder 14 encodes the decompressed i 4 frame to generate a lower bit - rate compressed b 4 ′ frame , and writes the compressed b 4 ′ frame to the output buffer 116 . the display controller 18 retrieves the higher bit - rate decompressed i 4 frame from the buffer 114 and causes the i 4 frame to be shown on the display 28 . during time intervals t 8 , t 9 , t 10 , and so forth , the video controller 10 operates in a manner similar to those described above . in example 5 , the operations of the video decoder 12 , the video encoder 14 , and the display controller 18 are designed such that a first frame is overwritten by a second frame only after the first frame will not be used by the video decoder 12 , the video encoder 14 , or the display controller 18 . the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than seven decompressed frames , including five decompressed frames ( in buffers 106 , 108 , 110 , 112 , and 114 ) written by the video decoder 12 and two reconstructed frames ( in buffers 102 and 104 ) written by the video encoder 14 . in example 6 , the lower bit - rate compressed video 30 has a lower resolution as compared to the higher bit - rate compressed video 26 . for example , the input encoded video 26 can have 1920 × 1080 resolution , and the output encoded video 30 can have 1366 × 768 resolution . the encoded video 26 has frames that are arranged in a display order , whereas the encoded video 26 has frames that are arranged in an encode order . the display controller 18 sends higher resolution frames arranged in the display order to the display 28 . thus , the video controller 10 outputs a lower bit - rate compressed video 30 having lower resolution at the same time that the display 28 shows the video in higher resolution . the allocation of memory buffers in the memory device 22 for example 6 is similar to that of example 5 , as shown in fig4 b . the input buffer 100 stores a higher resolution compressed frame , and the output buffer 116 stores a lower resolution compressed frame generated by the video encoder 14 . the encode stage 1 buffer 106 , encode stage 2 buffer 108 , encode stage 3 buffer 110 , encode stage 4 buffer 112 , and encode stage 5 buffer 114 store higher resolution decompressed frames that are output from the video decoder 12 . the reconstructed encode reference 1 buffer 102 and the reconstructed encode reference 2 buffer 104 store lower resolution reconstructed frames that are generated by the video encoder 14 , and used by the video encoder 14 during encoding of other frames . a descaler may generate the lower resolution reconstructed frames by using a descaling process . the encoding and the descaling of the frames may be performed at the same time . timing sequences for example 6 is similar to that of example 5 , as shown in fig4 b . the processes performed by the video decoder 12 , the video encoder 14 , and the display controller 18 are similar to those described in example 5 , except that the frames i 0 ′, b 1 ′, b 2 ′, p 3 ′, b 4 ′, b 5 ′, p 6 ′, b 7 ′, b 8 ′, p 9 ′, b 10 ′, b 11 ′, and p 12 ′ are lower resolution reconstructed frames , and i 0 , b 1 , b 2 , p 3 , b 4 , b 5 , p 6 , b 7 , b 8 , p 9 , b 10 , b 11 , and p 12 are higher resolution decompressed frames . similar to example 5 , in example 6 , the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than seven decompressed frames , including five decompressed frames ( in buffers 106 , 108 , 110 , 112 , and 114 ) written by the video decoder 12 and two reconstructed frames ( in buffers 102 and 104 ) written by the video encoder 14 . referring to fig5 a , in example 7 , similar to example 5 , the input encoded video 26 is a compressed higher bit - rate video from a video source in which the frames are all intra frames and arranged in the display order . the output encoded video 30 is a compressed lower bit - rate video in which the frames are arranged in the encode order . the frames of the output video 30 may be encoded according to , e . g ., an mpeg standard . the videos 26 and 30 have the same resolution . the difference between examples 5 and 7 is that , in example 7 , the display controller 18 sends a lower bit - rate decompressed video 27 to the display 28 in the display order . fig5 b shows a time chart 170 indicating timing sequences in which the frames are stored in the buffers of the memory device 22 and shown on the display 28 . in example 7 , the reconstructed reference 1 buffer and 102 and the reconstructed reference 2 buffer 104 are not used ( as compared to examples 1 - 6 in which the buffers 102 and 104 were not used ). this is because the input video are all intra frames , so when encoding a frame i 0 , a reconstructed frame i 0 ′ can overwrite the frame i 0 because i 0 is not used in the decoding of subsequent frames . thus , the encode stage 1 buffer 106 can be used to store the decoded frame i 0 and the reconstructed frame i 0 ′. each frame that is stored in the memory device 22 is stored once without duplication . the following describes the processes performed by the video decoder 12 , video encoder 14 , and the display controller 18 at various time intervals . before time interval t 0 ( not shown in fig5 b ), a higher bit - rate encoded i 0 frame is written to the input buffer 100 . similarly , during time intervals t 0 , t 1 , t 2 , t 3 , t 4 , t 5 , t 6 , t 7 , t 8 , t 9 , t 10 , t 11 , t 12 , . . . , higher bit - rate encoded frames i 1 , i 2 , i 3 , i 4 , i 5 , i 6 , i 7 , i 8 , i 9 , i 10 , i 11 , . . . , respectively , are written to the input buffer 100 . during time interval t 0 , the video decoder 12 decodes the encoded i 0 frame to generate a higher bit - rate decompressed i 0 frame , and writes the decompressed i 0 frame to the encode stage 1 buffer 106 . during time interval t 1 , the video decoder 12 decodes the encoded i 1 frame and generates a higher bit - rate decompressed i 1 frame , and writes the decompressed i 1 frame to the encode stage 3 buffer 110 . during time interval t 2 , the video decoder 12 decodes the encoded i 2 frame to generate a higher bit - rate decompressed i 2 frame , and writes the decompressed i 2 frame to the encode stage 4 buffer 112 . the video encoder 14 encodes the higher bit - rate decompressed i 0 frame to generate a lower bit - rate reconstructed i 0 ′ frame and a lower bit - rate compressed i 0 ′ frame , writes the reconstructed i 0 ′ frame to the encode stage 1 buffer 106 ( thereby overwriting the decompressed i 0 frame ), and writes the compressed i 0 ′ frame to the output buffer 116 . during time interval t 3 , the video decoder 12 decodes the encoded i 3 frame to generate a higher bit - rate decompressed i 3 frame , and writes the decompressed i 3 frame to the encode stage 2 buffer 108 . in some examples , the video encoder 14 starts to encode the data in the buffer 108 after the video decoder 12 decodes a certain amount of data , so that during period t 3 , the buffer 108 is accessed by both the video decoder 12 and the video encoder 14 . the video encoder 14 encodes the higher bit - rate decompressed 13 frame to generate a lower bit - rate reconstructed p 3 ′ frame and a lower bit - rate compressed p 3 ′ frame , writes the reconstructed p 3 ′ frame to the buffer 108 ( thereby overwriting the decompressed i 3 frame ), and writes the compressed p 3 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed i 0 ′ frame from the buffer 106 and causes the i 0 ′ frame to be shown on the display 28 . during time interval t 4 , the video decoder 12 decodes the encoded i 4 frame to generate a higher bit - rate decompressed i 4 frame , and writes the decompressed i 4 frame to the encode stage 5 buffer 114 . the video encoder 14 encodes the higher bit - rate decompressed b 1 frame to generate a lower bit - rate reconstructed b 1 ′ frame and a lower bit - rate compressed b 1 ′ frame , writes the reconstructed b 1 ′ frame to the buffer 110 , and writes the compressed b 1 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed b 1 ′ frame from the buffer 110 and causes the b 1 ′ frame to be shown on the display 28 . during time interval t 5 , the video decoder 12 decodes the encoded i 5 frame to generate a higher bit - rate decompressed i 5 frame , and writes the decompressed i 5 frame to the encode stage 3 buffer 110 . the reconstructed b 1 ′ frame can be overwritten because it has already been displayed during t 4 , and will not be used in the future . the video encoder 14 encodes the decompressed b 2 frame to generate a lower bit - rate reconstructed b 2 ′ frame and a lower bit - rate compressed b 2 ′ frame , writes the reconstructed b 2 ′ frame to the buffer 112 , and writes the compressed b 2 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate reconstructed b 2 ′ frame from the buffer 112 and causes the b 2 ′ frame to be shown on the display 28 . during time interval t 6 , the video decoder 12 decodes the encoded i 6 frame to generate a higher bit - rate decompressed i 6 frame , and writes the decompressed i 6 frame to the encode stage 1 buffer 106 . the video encoder 14 encodes the decompressed i 6 frame to generate a lower bit - rate reconstructed p 6 ′ frame and a lower bit - rate compressed p 6 ′ frame , writes the reconstructed p 6 ′ frame to the buffer 106 ( overwriting the decompressed i 6 frame ), and writes the compressed p 6 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate decompressed p 3 ′ frame from the buffer 108 and causes the p 3 ′ frame to be shown on the display 28 . during time interval t 7 , the video decoder 12 decodes the encoded i 7 frame to generate a higher bit - rate decompressed i 7 frame , and writes the decompressed i 7 frame to the encode stage 4 buffer 112 . the video encoder 14 encodes the decompressed i 4 frame to generate a lower bit - rate reconstructed b 4 ′ frame and a lower bit - rate compressed b 4 ′ frame , writes the reconstructed b 4 ′ frame to the buffer 114 , and writes the compressed b 4 ′ frame to the output buffer 116 . the display controller 18 retrieves the lower bit - rate decompressed b 4 ′ frame from the buffer 114 and causes the b 4 ′ frame to be shown on the display 28 . during time intervals t 8 , t 9 , t 10 , and so forth , the video controller 10 operates in a manner similar to those described above . in example 7 , the operations of the video decoder 12 , video encoder 14 , and display controller 18 are designed such that a first frame is overwritten by a second frame only after the first frame will not be used by the video decoder 12 , the video encoder 14 , or the display controller 18 . the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than five decompressed frames in buffers 106 , 108 , 110 , 112 , and 114 . in example 8 , the lower bit - rate compressed video 30 has a lower resolution as compared to the higher bit - rate compressed video 26 . for example , the input encoded video 26 can have 1920 × 1080 resolution , and the output encoded video 30 can have 1366 × 768 resolution . the encoded video 26 has frames that are arranged in a display order , whereas the encoded video 26 has frames that are arranged in an encode order . the display controller 18 sends lower resolution frames arranged in the display order to the display 28 . thus , the video controller 10 outputs a lower bit - rate compressed video 30 having lower resolution at the same time that the display 28 shows the video in a lower resolution . the allocation of memory buffers in the memory device 22 for example 8 is similar to that of example 7 , as shown in fig5 b . the input buffer 100 stores a higher resolution compressed frame , and the output buffer 116 stores a lower resolution compressed frame generated by the video encoder 14 . the encode stage 1 buffer 106 , encode stage 2 buffer 108 , encode stage 3 buffer 110 , encode stage 4 buffer 112 , and encode stage 5 buffer 114 may store higher resolution decompressed frames and lower resolution reconstructed frames . a descaler may generate the lower resolution reconstructed frames by using a descaling process . the encoding and the descaling of the frames may be performed at the same time . timing sequences for example 8 is similar to that of example 7 , as shown in fig5 b . the processes performed by the video decoder 12 , the video encoder 14 , and the display controller 18 are similar to those described in example 7 , except that the frames i 0 ′, b 1 ′, b 2 ′, p 3 ′, b 4 ′, b 5 ′, p 6 ′, b 7 ′, b 8 ′, p 9 ′, b 10 ′, b 11 ′, and p 12 ′ are lower resolution reconstructed frames , and i 0 , i 1 , i 2 , i 3 , i 4 , i 5 , i 6 , i 7 , i 8 , i 9 , i 10 , i 11 , and i 12 are higher resolution decompressed frames . similar to example 7 , in example 8 , the video decoder 12 , the video encoder 14 , and the display controller 18 share the memory 22 such that the memory 22 at any given time stores no more than five decompressed frames in buffers 106 , 108 , 110 , 112 , and 114 . in examples 1 - 8 described above , the system controller 24 coordinates the operations of the video decoder 12 , the video encoder 14 , and the display controller 8 according to the formats of the input and output signals . the video controller 10 may include firmware that includes code for controlling the operations of various components . the firmware may include code to cause the display 28 to show menu options to allow a user to specify , for example , the input and output formats , whether to display higher or lower resolution video , and the resolution and the bit rate of the output encoded video 30 . in the description above , the videos are encoded / decoded according to a jpeg , dv , or mpeg standard . the videos can also be encoded / decoded using other standards , such as international telecommunications union ( itu ) h . 261 , h . 263 , or h . 264 standard . the video controller 10 can be used to transcode a lower bit - rate video to a higher bit - rate video . the video controller 10 can be used to transcode a lower resolution video to a higher resolution video . if the video is not shown on a display , each of the time intervals t 0 , t 1 , t 2 , . . . , does not necessarily have to be equal to a frame period . the duration of the time intervals depend on the speed on decoding and encoding . the video controller 10 can be incorporated in , for example , a video recorder ( which can store video programs to tapes , optical media , hard drives , or other non - volatile storage ), a television or set - top box having a built - in mass storage , a portable video player / recorder , and a cell phone capable of playing / recording video . in examples 1 - 4 , the memory device 22 can be made smaller by omitting the buffer 114 , which is not used . in examples 7 and 8 , the memory device 22 can be made smaller by omitting the buffers 102 and 104 , which are not used . the display controller 18 may be omitted from the video controller 10 if the video is not shown on a display . | 7 |
with reference to the attached drawing a fuel gas , typically a gaseous hydrocarbon such as methane , ethane , propane and the like , and a source of oxygen , typically air and stream are combined in a reducing gas generator 10 where there is formed a reducing gas stream containing as hydrogen equivalents , hydrogen and carbon monoxide . the water present in the feed serves to reduce the formation of soot . it is also available to generate hydrogen by reaction with carbon monoxide in a subsequent catalysis zone and to suppress the formation of cos and cs 2 . the reducing gas generator 10 operates at an elevated temperature yielding by partial oxidation an effluent gas stream typically ranging in temperature from about 1400 to about 1600 ° f or more . liquid fuels such as kerosine , diesel fuel or other fuel oils may be used with burners designed to suppress the formation of soot . solid fuel such as coal or coke may alternatively be used as the source of hydrogen and carbon monoxide . the gas stream enters sulfur vaporizer 12 containing a pool of molten sulfur 14 supplied by molten sulfur reservoir tank 16 . the gas stream in passing through the molten sulfur vaporizes the sulfur and passes it to a catalytic reactor 18 where hydrogen and sulfur react to form hydrogen sulfide and carbon monoxide and water react to yield additional hydrogen for reaction with sulfur to yield hydrogen sulfide . the amount of sulfur vaporized , calculated as s 1 independent of its dimeric or polymeric forms , should be equal to or less than the amount of hydrogen equivalents present in the gas stream exiting the gas generator . preferably , the net gas should contain hydrogen equivalents in the form of hydrogen and carbon monoxide in an amount sufficient to provide excess hydrogen equivalents in an amount of from about 1 . 5 to about 3 mole per cent to insure complete conversion of the vaporized sulfur to hydrogen sulfide and to eliminate any sulfur dioxide which may tend to form . the control of sulfur vaporization can be accomplished in several ways . one is by injecting stream or water into the vapor space of vessel 12 , thereby cooling the vapor and condensing excess sulfur vapor . the same result may be accomplished by cooling the sulfur pool 14 by an external coolant ( not shown ) to again limit the temperature of the gas above the pool of molten sulfur . another means as shown in the drawing is to cool the gas stream above the pool of molten sulfur by the introduction of an external coolant through a coil or tube to limit gas temperature and thereby the partial pressure of sulfur in gas which is in thermal equilibrium with the molten sulfur head . whichever expedient is employed the net gas stream containing the reducing agents , water to suppress the thermal formation of cos and cs 2 and vaporized sulfur are passed to catalytic convertor 18 . as shown , converter 18 contains two catalytic beds 20 and 22 with cooling between the beds . the catalysts employed in the beds are those containing the metals of group va , via , viii and the rare earth series of the periodic table as defined by mendeleef and published as the &# 34 ; periodic chart of the atoms &# 34 ; by w . n . welch manufacturing company as published in business week , apr . 10 , 1965 edition , on page 56 incorporated therein by reference . the metals are preferably supported on conventional supports such as silica , alumina , alumina - silica and the zeolites . alumina is the preferred support . the preferred catalysts are those containing one or more the metals cobalt , molybdenum , iron , chromium , vanadium , thoria , nickel , tungsten ( w ) and uranium ( u ). a cobalt - molybdate catalyst where support is alumina is particularly preferred . catalytic zone 18 is maintained at a temperature from about 500 ° to about 800 ° f . as shown in the drawing bed 20 principally serves for the hydrogenation of sulfur although some hydrolysis of any cos and cs 2 introduced will also occur . to remove the exothermic heat of reaction a coolant can be circulated between beds 20 and 22 . preferably , in addition to or as an alternative to the circulation of an external coolant , water is injected into the gas stream in line 24 . water serves to quench the reaction by removing heat and to promote hydrolysis of cos and cs 2 in bed 22 which also serves to convert any residual sulfur to hydrogen sulfide . to minimize the carbon - sulfur compounds , it is preferred that the gas stream entering catalysis zone 18 have an effective water vapor content of about twenty - five mole percent or more , if the end use of the h 2 s containing product gas permits a larger content of cos and cs 2 , then a lesser content of water vapor is permissible . the lower limit is about ten mole percent . reaction occurs in catalytic zone 18 at a pressure ranging from about 1 to about 10 atmospheres or more . the gas stream exiting reactor 18 is passed through sulfur cooler 24 which is made available for start - up and upset conditions to remove any excess sulfur which may be present in the gas stream . again , because of low operating temperatures , ordinary material of construction can be used since corrosion ceases to be a problem . the gas stream still above the dew point of water is then passed to heat exchanger 26 where the gas stream is cooled to a temperature below the dew point of water at operating pressures . water is collected in knock - out pot 28 and removed from the system . with reference to the drawing there is fed to the reducing gas generator 10 gas streams indentified as 1 , 2 and 3 in table i below which show operating pressures and temperatures at the several points in the process , as calculated by conventional methods . in reducing gas generator 10 , methane and oxygen react to provide hydrogen and the oxides of carbon with attendant production of water . the gas leaving the reactor at point 4 is of the composition shown in table i and at a temperature of 1507 ° f . molten sulfur at a temperature of 280 ° f is fed from reservoir 16 to vaporizer 12 at the rate of 6208 pounds per hour , which is equal to the rate of sulfur vaporization . the feed to reactor 18 , containing cobalt and molydenum on alumina as the catalyst , is of the composition shown as item 5 in table i and at a temperature of 665 ° f . to remove the heat of reaction and promote hydrolysis of cos and cs 2 there is introduced water in line 24 at a temperature of 100 ° f . and at a rate of 200 pound moles per hour . a portion of the introduced water and water present at the reaction feed are consumed in a production of additional hydrogen by reaction with carbon monoxide to yield hydrogen and to hydrolyze cos and cs 2 . the effluent from the reactor is at a temperature of 750 ° f . and is of the composition in point 6 . the composition of product gas after removal of water is shown at point 7 . the gas stream leaving reactor 18 is free of sulfur dioxide . the concentration of cos is 1210 ppm and the concentration of cs 2 is 0 . 2 ppm . table i__________________________________________________________________________stream no . 1 2 3 4 5 6 7 fuel air red &# 39 ; g reactor reacted productname gas ( dry ) steam gas feed mix gas__________________________________________________________________________pound molech . sub . 4 76 . 4 0 . 09 0 . 09 0 . 02 0 . 02h . sub . 2 140 . 3 140 . 3 7 . 02 7 . 02co 60 . 7 60 . 7 0 . 26 0 . 26co . sub . 2 15 . 5 15 . 5 75 . 43 75 . 42h . sub . 2 o 25 . 6 37 . 6 37 . 6 177 . 60 32 . 60o . sub . 2 51 . 9 0 . 00 0 . 00 0 . 00 0 . 00n . sub . 2 197 . 5 197 . 5 197 . 5 197 . 50 197 . 50h . sub . 2 s 193 . 42 193 . 41cos 0 . 58 0 . 58cs . sub . 2 0 . 00 0 . 00so . sub . 2 0 . 00 0 . 00s . sub . vapor . sup . 1 97 . 0 0 . 00 0 . 00total 76 . 4 249 . 4 25 . 6 451 . 69 548 . 69 651 . 83 506 . 81total . sup . 2 474 . 23 474 . 21temp . ° f 300 300 300 1507 665 750 100press . ata 1 1 1 1 1 1 1parts permillion ( dry basis ) cos 1210cs . sub . 2 0 . 2so . sub . 2 0 . 0__________________________________________________________________________ . sup . 1 as equivalent s . sub . 2 . sup . 2 dry basis | 2 |
to facilitate an understanding of the preferred embodiment , the general architecture and operation of a conventional taut wire intrusion detection system will initially be described with reference to fig1 . the specific architecture and operation of the supporting post arrangement of a preferred embodiment will then be described with reference to the general architecture and operation of a taut wire intrusion detection system . referring now to fig1 which illustrates one section of a prior art taut wire intrusion detection system , two anchor posts 101 a and 101 b are mounted at opposite ends of the section . multiple taut wires 104 , which may be in the form of barbed wires , are attached to and held under tension by the anchor posts 101 . a sensor post 103 is mounted at the center of the section between the two anchor posts 101 . the sensor post contains tension sensors ( not shown ) that are used to monitor the tensions of the taut wires 104 . such sensor posts and anchor posts are available from safeguards technology of hackensack , n . j . the taut wires 104 are connected to tension sensors in the sensor post 103 . slider posts 102 , positioned between an anchor post 101 and the sensor post 103 , are placed adjacent to the taut wires 104 to provide additional vertical support as to prevent a bowing of the taut wires 104 . the slider posts 102 also serve as a mechanism to convert vertical and horizontal force exerted on the taut wires into longitudinal movement . the taut wires 104 are secured to the anchor post 101 by link rods 106 . the displacement requirement of a sector in the prior art taut wire systems is not uniform over the distance from one anchor post to the other . rather , the displacement requirement of a prior art taut wire system such as that of fig1 is location dependent , as can be appreciated from fig2 a - 2f . fig2 a is a simplified diagram of a taut wire system including a pair of anchor posts 101 a , 101 b , a sensor post 103 , and four taut wire segments 208 , 210 , 212 , 214 . the taut wire segments are monitored by sensors ( not shown ) on the sensor post 103 . fig2 b illustrates the displacement requirement of taut wire segment 208 over the distance between a first anchor post 101 a and a second anchor post 101 b . as may be appreciated , the displacement requirement of the taut wire segment is at a maximum ( resulting in minimum sensitivity ) near the first anchor post 101 a . the displacement requirement of the taut wire segment 208 decreases as the contact point approaches the sensor post 103 . the displacement requirement is at a minimum ( resulting in maximum sensitivity ) near the sensor post 103 . the displacement requirement of the taut wire segment 208 increases as the contact point moves toward the second anchor post 101 b . the displacement requirement is again at a maximum near the second anchor post 101 b . the variance in displacement requirement is mainly due to the elasticity of the wound steel strand or barbed wire making up the taut wire . as the point of contact moves away from the sensor , more taut wire is available between the contact point and the sensor . the increase in taut wire length results in a greater proportion of the taut wire displacement resulting in an elongation of the taut wire as opposed to a displacement of the sensor taut wire connector element . fig2 c - 2e represent the similar displacement requirement exhibited by the other taut wire segments 210 , 212 , 214 , along the distance from the first anchor post 101 a to the second anchor post 101 b . fig2 f is an illustration of the average displacement requirement of the taut wire sector , which is calculated by combining the displacement requirements of the taut wire segments and dividing by the number of taut wire segments . the force requirement of a sector in a typical taut wire system likewise is not uniform along the distance from one anchor post to another . rather , the threshold force , which must be applied to the taut wires in a sector of a typical taut wire system , increases as the contact point moves towards the anchor posts , as can be appreciated from fig3 a - 3f . fig3 a is a simplified diagram of a taut wire system as was illustrated in fig2 a . fig3 b illustrates the force requirement of one of the taut wire segments 208 along the distance between a first anchor post 101 a and a second anchor post 101 b . as may be appreciated , the force requirement of the taut wire segment is at a maximum ( resulting in minimum sensitivity ) near the first anchor post 101 a , demonstrated by the higher level of force that must be applied to the taut wire at the location . the force requirement of the taut wire segment 208 decreases as the contact point approached the sensor post 103 , demonstrated by the lower level of force that must be applied to the taut wire near the sensor post . the force requirement is at a minimum ( resulting in maximum sensitivity ) near the sensor post 103 . the force requirement of the taut wire segment 208 then increases as the contact point moves toward the second anchor post 101 b . the variance in force requirement is the result of the increase in displacement distance required and the decrease in distance from the fixed anchor connection . since the displacement requirement of the taut wire increases as the contact point approaches the anchor posts , the force required also increases since the taut wire acts as a spring such that the force exerted by the taut wire increases as the wire is stretched . also , in order to move the sensor taut wire attachment the taut wire portion on the anchor side of the contact point must also move . since the anchor side of the contact point is fixed in position , the only movement that is possible is the stretching of the taut wire as opposed to a displacement of the anchor element . as the contact point nears the anchor element , less taut wire is available on the anchor side of the contact point . the force required to stretch a segment of taut wire increases as the length of the segment decreases . therefore , as the contact point moves closer to the anchor post , the force requirement increases . as the point of contact moves away from the anchor post , more taut wire is available between the contact point and the anchor post to provide a longer segment of taut wire to stretch , timely reducing the force requirement . additionally , some increase in force results from the increase in friction between the taut wire and the slider posts between the contact point and the sensor post . as the contact point moves away from the sensor post , more slider posts are between the contact point and the sensor , where the taut wire is displaced . therefore , a greater area of the taut wire is in contact with slider posts and a greater friction force is applied to the taut wire when the contact point moves away from the sensor post . fig3 c - 3e represent the similar force requirement exhibited by the other taut wire segments 210 , 212 , 214 , over the distance between the first anchor post 101 a and the second anchor post 101 b . fig3 f is an illustration of the force requirement of the taut wire sector , which is calculated by combining the displacement requirement of the taut wire segments and dividing by the number of taut wire segments . because the force requirement increases as the contact point moves toward the anchor posts , greater force can be applied to the taut wires near the anchor posts without producing an alarm condition . as a result , with a very long sector , the force requirement may be high enough so as to support the weight of an intruder , allowing intruders to use the taut wires to step over the fence near the anchor posts . therefore , the length of the taut wire sectors is limited by the level of increase in force requirement near the anchor posts . additionally , for a given combination of sensors , taut wire material , and taut wire tension , there will always be a sector length for which the average displacement requirement of taut wires is too great for a reasonably secure system . at this distance , the taut wires near the anchor posts can be displaced far enough as to allow an intruder to pass through the fence . some attempts to address these weakness have included using anchoring elements that break when vertical force above a certain threshold is applied , or using vertical force sensors as the anchor elements . these attempted solutions increase the cost of a system and require additional maintenance because more components that require service are introduced to the system . even with these attempted solutions , sectors of the more effective taut wire intrusion detection systems , such as the system of fig1 which employs breaking anchor elements , can generally only extend up to approximately 200 feet in length . beyond the approximate maximum length , the increase in force requirement and increase in displacement requirement are too great for a reliable system . increasing the overall sensitivity of the sensor posts of the system does not solve the problem as the rate of false alarms increases because the taut wire is very sensitive near the sensor posts . fig4 a - 4b is an illustration of four sections taut wire system constructed in accordance with the present invention . the term section is used herein to refer to a portion of the taut wire system that includes a variable number of supporting posts and a pair of anchor posts . anchor posts ( represented by the character a ) are provided at the ends of each section so as to provide a termination function for the supporting posts adjacent to the anchor post because some of the elements on the supporting posts are sensors . the anchor posts 401 , 408 , are preferably positioned outside the secured area , as shown , such that the sensitivity of the taut wire segments extending to the anchor posts does not affect the performance of the system . the supporting posts 402 , 404 , 406 , 407 , are provided between the anchor posts 401 , 408 , along intervals generally occupied in prior systems by both anchor and sensor posts . in another embodiment , the supporting posts are provided outside the secured area , before the anchor post . fig5 is an illustration of a portion of the system of fig4 that includes four supporting posts 402 , 404 , 406 , 407 . the supporting posts 402 , 404 , 406 , 407 , preferably contain , in an alternating arrangement , sensors and anchor elements . taut wire segments terminate at the anchor elements on every other supporting post as can be seen from a first taut wire segment 410 of the system . the taut wire segment 410 is anchored by a first anchor element 412 on a first supporting post 402 and a second anchor element 414 on a third supporting post 406 . the taut wire segment 410 is monitored by a sensor 416 on a second supporting post 404 . each sensor of the illustrated embodiment monitors a single taut wire although sensors that monitor more than one taut wire can be used . as a second example , a second taut wire segment 418 is anchored by a first anchor element 420 on the second supporting post 404 and a second anchor element 422 on a fourth supporting post 407 . the taut wire segment 418 is monitored by a sensor 424 on the third supporting post 406 . other taut wire segments are either monitored by sensors on adjacent supporting posts or kept in tension by anchor elements on adjacent supporting posts . conventional anchor elements , posts , and sensors can be used to provide the configuration illustrated by fig5 . for example , the breakable anchor elements used to prevent intruders from climbing the fence by using the anchor elements on the anchor posts of a typical taut wire system can be used as the anchor elements in the section illustrated in fig5 . alternatively , the anchor elements may be extruded cylinders whereby the taut wire is wrapped around the inner cylindrical portion of the anchor elements and is locked in place by a cover that is attached to the base of the cylinder . by using cylindrical anchoring elements a single segment of taut wire can extend between several anchor elements . the sensors of fig5 may be electromechanical taut wire sensors such as those available from safeguards technology , of hackensack n . j . the sensors may also be sensors that employ fiber optics or piezo - electric detection elements . sectors of typical taut wire intrusion systems , such as that of fig1 can extend as much as 200 feet in length between a first anchor post and a second anchor post . when an alarm condition is communicated from a sensor to a control center , the entire sector , from the first anchor post to the second anchor post , must be manually inspected to isolate the cause of the alarm . therefore , the scope of detection in such prior systems is the distance between three posts of the system , two anchor posts and one sensor post . in the system illustrated in fig3 the scope of detection is likely to be two posts of the system , or about one half the distance for the reasons set forth below . when an intruder attempts to bypass the taut wire system either by climbing over the fence or cutting through the fence , at least two taut wire segments will likely be engaged . the system of fig3 is assumed to be implemented as a one wire per sensor system although the discussion below is equally applicable to multiple wire per sensor configurations . first , when an intruder climbs over the fence , it is highly likely that the intruder exerts force on at least two taut wires segments since the fence cannot generally be scaled in a single step . second , when an intruder cuts through the fence , the intruder is likely to cut at least two adjacent taut wire segments because the distance between adjacent taut wire segments is generally too small for an intruder to fit through twice that distance . when supporting posts are provided , in a configuration such as that of fig4 there is a high likelihood that the two taut wire segments engaged by the intruder are not both anchored or monitored at the same post , because the intruder may not be aware of the location of sensors and anchor elements on the supporting post . the intruder may not be able to distinguish between the sensors and anchor elements since both can be made to have the same appearance . further , the sensors and anchor elements can be hidden from an intruder by using a cover on the supporting posts . when an intruder cuts taut wires , the likelihood that two different sensors are monitoring the two wires is high , especially when using an alternating arrangement such as that of fig4 . when two taut wire segments , monitored by sensors on different supporting posts , are engaged , two sensor posts will communicate an alarm condition instead of the single sensor post of a typical systems . the intrusion location can then be precisely identified as the area between the two supporting posts . narrowing down the possible zone of intrusion may reduce the response time taken in isolating the cause of an alarm , thereby providing a higher level of performance . the cost of the system need not be increased significantly , if at all , despite the increase in accuracy of detection . the arrangement of the sensors and anchor elements within the supporting posts of the system of fig5 may be modified to prevent an intruder from scaling the fence by stepping over every other taut wire segment such that only the segments anchored at the supporting post are engaged . an alternating arrangements of groups of two sensors and two anchor elements can prevent the scaling of the fence by stepping on only the anchored taut wire segments . other arrangements providing similar advantages can be used such as providing a non - uniform distribution of sensors and anchor elements such that a large group of sensors or a large group of anchor elements are provided at various locations on the supporting post . fig6 a - 6f illustrate the displacement requirement of taut wire segments of the system constructed in accordance with the present invention that is illustrated in fig5 . fig6 a is a simplified illustration of the system of fig4 which includes three supporting posts 402 , 404 , 406 . taut wire segments 508 , 510 , 512 , 514 are provided between the supporting posts as described with reference to fig4 . fig5 b illustrates the displacement requirement of a taut wire segment 514 over the distance between a first supporting post 402 and a third supporting post 406 . taut wire segment 514 is anchored at the first supporting post 402 , connected to a sensor on the second supporting post 404 , and anchored at the third supporting post 406 . the displacement requirement of the taut wire segment 514 decreases as the contact point approaches the second supporting post 404 where it is monitored by a sensor . the displacement requirement of the taut wire segment 514 increases as the contact point moves away from the second supporting post 404 toward the first and third supporting posts 402 , 406 . fig6 c illustrates the displacement requirement of a second taut wire segment 512 over the distance between the first supporting post 402 and the second supporting post 406 . the taut wire segment 512 is connected to a sensor on the first supporting post 402 , anchored at the second supporting post 404 , and connected to a sensor on the third supporting post 406 . the displacement requirement of the taut wire segment 512 increases as the contact point approaches the second supporting post 404 where it is anchored . the displacement requirement of the taut wire segment 512 decreases as the contact point moves away from the second supporting post 404 toward the first and third supporting posts 402 , 406 where it is connected to sensors . the two other taut wire segments 508 , 510 will behave similarly as is illustrated by fig6 d and 6e . fig6 f illustrates the displacement requirement of the section over the distance between the first supporting post 402 and the third supporting post 406 . as can be appreciated , the average displacement requirement at contact points along the section is substantially uniform . this uniformity of displacement requirement provides a taut wire intrusion detection system that can be adjusted without creating weak areas or high false alarm rates . fig7 a - 7f illustrate the force requirement of the taut wire segments of the system illustrated in fig5 . fig7 a is the same illustration as that of fig6 a . fig7 b illustrates the force requirement of a taut wire segment 514 along the distance between a first supporting post 402 and a third supporting post 406 . the taut wire segment 514 is anchored at the first supporting post 402 , connected to a sensor on the second supporting post 404 , and anchored at the third supporting post 406 . the force requirement of the taut wire segment 514 decreases as the contact point approaches the second supporting post 404 where it is monitored by a sensor . the force requirement of the taut wire segment 514 increases as the contact point moves away from the second supporting post 404 toward the first and third supporting posts 402 , 406 . fig7 c illustrates the force requirement of a second taut wire segment 512 along the distance between the first supporting post 402 and the third supporting post 406 . the taut wire segment 512 is connected to a sensor on the first supporting post 402 , anchored at the second supporting post 404 , and connected to a sensor on the third supporting post 406 . taut wire segment 512 is anchored by anchor elements on supporting posts adjacent to the first and third supporting posts 402 , 406 . the force requirement of the taut wire segment 512 increases as the contact point approaches the second supporting post 404 where it is anchored . the force requirement of the taut wire segment 512 decreases as the contact point moves away from the second supporting post 404 toward the first and third supporting posts 402 , 406 where it is connected to sensors . the two other taut wire segments 508 , 510 will display a similar behavior as is illustrated by fig7 d and 7e . fig7 f illustrates the force requirement of the section along the distance between the first supporting post 402 and the second supporting post 406 . as can be appreciated , the force requirement at contact points along the portion that is illustrated is substantially uniform . this uniformity of force requirement provides a taut wire intrusion detection system that can be adjusted without creating loopholes in the system or increasing the rate of false alarms . the present invention can be used to increase the distance between supporting posts of a taut wire system since no areas of the system are overly susceptible to intrusion . one factor substantially limiting the length of sectors in prior systems is the sensitivity variance of the system as discussed above . since the present invention can be used to provide a more uniform sensitivity , sectors of the system can employ supporting posts that are further apart than sensor posts and anchor posts of prior systems . the use of longer sections would decrease the required number of supporting posts in the system . therefore , the use of the method of the present invention can lead to a significant reduction in the cost of taut wire intrusion detection systems . the present invention is also applicable to systems that employ no anchor elements . since sensors are generally more sensitive when only one sensor monitors a taut wire segment at a time , systems that employ more than one sensor to monitor a single taut wire as to avoid the sensitivity variance will benefit from the method of the present invention . the sensors can be used while only one sensor monitors a taut wire segment to provide better detection capabilities while eliminating the sensitivity variance problem . although the invention has been described in terms of certain preferred embodiments , other embodiments that are apparent to those of ordinary skill in the art , including embodiments which do not provide all of the features and advantages set forth herein , are also within the scope of this invention . accordingly , the scope of the invention is intended to be defined by the claims that follow . | 6 |
with reference now to the figures , fig1 depicts a pictorial representation of a network of data processing systems in which the present invention may be implemented . network data processing system 100 is a network of computers in which the present invention may be implemented . network data processing system 100 contains a network 102 , which is the medium used to provide communications links between various devices and computers connected together within network data processing system 100 . network 102 may include connections , such as wire , wireless communication links , or fiber optic cables . in the depicted example , server 104 is connected to network 102 along with storage unit 106 . in addition , clients 108 , 110 , and 112 are connected to network 102 . these clients 108 , 110 , and 112 may be , for example , personal computers or network computers . in the depicted example , server 104 provides data , such as boot files , operating system images , and applications to clients 108 , 110 and 112 . clients 108 , 110 and 112 are clients to server 104 . network data processing system 100 may include additional servers , clients , and other devices not shown . in the depicted example , network data processing system 100 is the internet with network 102 representing a worldwide collection of networks and gateways that use the tcp / ip suite of protocols to communicate with one another . at the heart of the internet is a backbone of high - speed data communication lines between major nodes or host computers , consisting of thousands of commercial , government , educational and other computer systems that route data and messages . of course , network data processing system 100 also may be implemented as a number of different types of networks , such as for example , an intranet , a local area network ( lan ), or a wide area network ( wan ). fig1 is intended as an example , and not as an architectural limitation for the present invention . referring to fig2 a block diagram of a data processing system that may be implemented as a server , such as server 104 in fig1 is depicted in accordance with a preferred embodiment of the present invention . data processing system 200 may be a symmetric multiprocessor ( smp ) system including a plurality of processors 202 and 204 connected to system bus 206 . alternatively , a single processor system may be employed . also connected to system bus 206 is memory controller / cache 208 , which provides an interface to local memory 209 . i / o bus bridge 210 is connected to system bus 206 and provides an interface to i / o bus 212 . memory controller / cache 208 and i / o bus bridge 210 may be integrated as depicted . peripheral component interconnect ( pci ) bus bridge 214 connected to i / o bus 212 provides an interface to pci local bus 216 . a number of modems may be connected to pci local bus 216 . typical pci bus implementations will support four pci expansion slots or add - in connectors . communications links to network computers 108 , 110 and 112 in fig1 may be provided through modem 218 and network adapter 220 connected to pci local bus 216 through add - in boards . additional pci bus bridges 222 and 224 provide interfaces for additional pci local buses 226 and 228 , from which additional modems or network adapters may be supported . in this manner , data processing system 200 allows connections to multiple network computers . a memory - mapped graphics adapter 230 and hard disk 232 may also be connected to i / o bus 212 as depicted , either directly or indirectly . those of ordinary skill in the art will appreciate that the hardware depicted in fig2 may vary . for example , other peripheral devices , such as optical disk drives and the like , also may be used in addition to or in place of the hardware depicted . the depicted example is not meant to imply architectural limitations with respect to the present invention . the data processing system depicted in fig2 may be , for example , an ibm e - server pseries system , a product of international business machines corporation in armonk , n . y ., running the advanced interactive executive ( aix ) operating system or linux operating system . with reference now to fig3 a block diagram illustrating a data processing system is depicted in which the present invention may be implemented . data processing system 300 is an example of a client computer . data processing system 300 employs a peripheral component interconnect ( pci ) local bus architecture . although the depicted example employs a pci bus , other bus architectures such as accelerated graphics port ( agp ) and industry standard architecture ( isa ) may be used . processor 302 and main memory 304 are connected to pci local bus 306 through pci bridge 308 . pci bridge 308 also may include an integrated memory controller and cache memory for processor 302 . additional connections to pci local bus 306 may be made through direct component interconnection or through add - in boards . in the depicted example , local area network ( lan ) adapter 310 , scsi host bus adapter 312 , and expansion bus interface 314 are connected to pci local bus 306 by direct component connection . in contrast , audio adapter 316 , graphics adapter 318 , and audio / video adapter 319 are connected to pci local bus 306 by add - in boards inserted into expansion slots . expansion bus interface 314 provides a connection for a keyboard and mouse adapter 320 , modem 322 , and additional memory 324 . small computer system interface ( scsi ) host bus adapter 312 provides a connection for hard disk drive 326 , tape drive 328 , and cd - rom drive 330 . typical pci local bus implementations will support three or four pci expansion slots or add - in connectors . an operating system runs on processor 302 and is used to coordinate and provide control of various components within data processing system 300 in fig3 . the operating system may be a commercially available operating system , such as windows 2000 , which is available from microsoft corporation . an object oriented programming system such as java may run in conjunction with the operating system and provide calls to the operating system from java programs or applications executing on data processing system 300 . “ java ” is a trademark of sun microsystems , inc . instructions for the operating system , the object - oriented operating system , and applications or programs are located on storage devices , such as hard disk drive 326 , and may be loaded into main memory 304 for execution by processor 302 . those of ordinary skill in the art will appreciate that the hardware in fig3 may vary depending on the implementation . other internal hardware or peripheral devices , such as flash rom ( or equivalent nonvolatile memory ) or optical disk drives and the like , may be used in addition to or in place of the hardware depicted in fig3 . also , the processes of the present invention may be applied to a multiprocessor data processing system . as another example , data processing system 300 may be a stand - alone system configured to be bootable without relying on some type of network communication interface , whether or not data processing system 300 comprises some type of network communication interface . as a further example , data processing system 300 may be a personal digital assistant ( pda ) device , which is configured with rom and / or flash rom in order to provide non - volatile memory for storing operating system files and / or user - generated data . the depicted example in fig3 and above - described examples are not meant to imply architectural limitations . for example , data processing system 300 may also be a notebook computer or hand held computer in addition to taking the form of a pda . data processing system 300 also may be a kiosk or a web appliance . the present invention provides an apparatus and method that allow one bookmark to replace another . the invention may be local to client systems 108 , 110 and 112 of fig1 or to the server 104 or to both the server 104 and clients 108 , 110 and 112 . consequently , the present invention may reside on any data storage medium ( i . e ., floppy disk , compact disk , hard disk , rom , ram , etc .) used by a computer system . to better understand the invention , an example will be provided . suppose a user accesses an instruction or tutorial manual over the internet and bookmarks its url . in addition , suppose the tutorial is organized by topics having each its own url . suppose further that after reading a few topics , the user decides to resume the reading of the tutorial at a later time . the user may then want to bookmark the topic where reading is to resume . if not , when the user is ready to resume reading , the user may have to access the tutorial at the location previously bookmarked ( in this example , it would be at the beginning of the tutorial ). web browsers have a feature that indicates to users previously visited urls . ordinarily , the previously visited urls are of a different color than the ones that have not previously been visited . consequently , the table of contents listing the different topics may be used to access the next topic to be read ( the list of topics , in this case , is usually a list of links ). therefore , accessing the tutorial from the beginning may not be too burdensome . however , if a user accidentally went to a previously unread topic and upon realizing the mistake went to the intended topic , the topic accidentally accessed will be marked as read . furthermore , the feature that indicates previously visited topics is time - definite . thus , if the user takes too long to re - access the tutorial for the continued reading , the feature may have timed out and all topics may be shown as unread . moreover , it is quite common for several related web pages to have the same or very confusing bookmark titles , albeit pointing to different urls . for all the above reasons , the user may have to access a few already read topics before finding the last topic read . consequently , a user may each time choose to bookmark the location where reading is to resume . but , if the user does not delete previous related bookmarks and if the user accesses and bookmarks related web pages frequently , the bookmark folder may quickly become very unmanageable . the present invention provides a tool to quickly and effortlessly manage the bookmark folder . note that the method of bookmarking a web page will not be herein explained since it is well known in the field . the invention will be disclosed in conjunction with fig4 and 5 . [ 0034 ] fig4 is a flow diagram illustrating a process used by the invention . when a user accesses a web page through a bookmarked url , the process of the invention starts ( step 400 ). a test is continuously being made as to whether the user accesses a link from the displayed web page ( step 405 ). note that , the test may be continually being made as the user jumps from one web page to another , so long as the presently displayed web page emanated from a succession of links from a previously displayed bookmarked web page . if the user decides to bookmark the link ( step 410 ), the user will be prompted as to whether the previously bookmarked url is to be replaced by the url of the link ( steps 415 and 420 ). if so , the url of the link will be bookmarked and the previously bookmarked url deleted ( step 430 ). if not , the url of the link will be bookmarked without deleting the previously bookmarked url ( step 425 ). [ 0036 ] fig5 illustrates another embodiment of the invention . in fig5 the process will start as soon as the web browser is accessed ( step 500 ). a check is then continuously made as to whether the user wants to bookmark a web page ( step 505 ). if so , the invention compares all urls of presently bookmarked pages for similarities with the url of the new web page to be bookmarked ( step 510 ). in this case , a bookmarked url is similar to a url to be bookmarked , if they differ by one branch . for example , if a bookmarked url is : www . gtk . org / tutorial / ch - introduction . html and the url to be bookmarked is : www . gtk / tutorial / ch - gettingstarted . html , they differ by one branch . note that the invention may be designed to regard urls of two web pages as similar if they differ by n branches , where n is an integer . alternatively , the invention may be designed to compare root urls or root plus n branched urls for similarity , again n is an integer . in this example , www . gtk . org is a root url . furthermore , the invention may be designed to use only top level bookmarks ( i . e ., no subfolder bookmarks ) or bookmarks all the way down to the nth level for the comparison , here too , n is an integer . in any case , if the url of the web page to be bookmarked is not similar to an existing url of a bookmarked page , the url of the web page will be bookmarked ( steps 515 and 520 ). if there is a similarity with an existing bookmarked url , the user is prompted as to whether the new url is to replace the bookmarked url . if so , the url is bookmarked and the existing bookmarked url is deleted ( steps 525 , 530 and 535 ). if the user chooses not to replace the existing bookmarked url by the new url , the new url is simply bookmarked without deleting the previously bookmarked url ( steps 525 , 530 and 520 ). in the case where a root url is compared with the url of the web page to be bookmarked , before actually bookmarking the new url , a check may also be done to determine whether the title of the new web page is identical to the title of an already bookmarked web page . if so , the new url may possibly replace the url of the already bookmarked page . the description of the present invention has been presented for purposes of illustration and description , and is not intended to be exhaustive or limited to the invention in the form disclosed . many modifications and variations will be apparent to those of ordinary skill in the art . for example , more than one background search may be performed with the invention . the embodiment was chosen and described in order to best explain the principles of the invention , the practical application , and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated . | 6 |
as will become apparent from the following disclosure , a pipette tip , including a diaphragm , in combination with a novel piston linear actuation mechanism , may be configured as pan of a high - resolution pipette assembly , that can dispense volumes of fluid as small as one nanoliter . the components function via a volume deamplification concept in which a pipette piston displaces a volumetric amount of a working fluid on one side of the diaphragm placed in the tip and in which the diaphragm displaces a smaller volumetric amount of fluid at an opposite side of the diaphragm via direct contact with the fluid . this displacement reduction from one side of the diaphragm to the other may be characterized by a deamplification ratio that can span multiple orders of magnitude . one or more portions of a fluid chamber that encloses the working fluid may undergo elastic deformation to facilitate the deamplification . additionally or alternatively , the working fluid may be compressible to contribute to the deamplification . the deamplification ratio and resolution may also be adjustable . referring to fig1 , a schematic cross - sectional view of the nanoliter pipette is shown . the pipette assembly 10 consists of a tip 12 , a housing , 14 , a piston and accompanying mechanism 16 , and a diaphragm 18 constrained in the tip . the piston and diaphragm define an adjustable fluid chamber , 20 . the working fluid 22 is in contact with the piston 16 and the chamber side 24 of the diaphragm . the piston 16 is movable and displaces the working fluid 22 within the chamber 20 . the illustrated embodiment is not to scale . the tip 12 consists of several separate pieces that are used to form a fluid tight seal with the diaphragm 18 and the housing 14 , using sealing methods known to those skilled in the art . in operation , still referring to fig1 , the piston 16 moves to displace a volumetric amount of working fluid 22 within the fluid chamber 20 . the volume displaced , v p , by the piston 16 is equal to the product of the surface area of surface 26 and the distance 28 the piston has moved . the piston 16 is shown in this displaced position after being moved from its initial position shown in dashed lines . the volume displacement , v p , causes a corresponding volume displacement , v d , by the diaphragm 18 . due to the small volumes the tip 12 will be handling , a novel piston and accompanying mechanism 16 has been designed . details of how the piston and piston mechanism 16 deflect the diaphragm 18 to aspirate and dispense fluid can be seen in fig2 a - 2 d , cross - sectional schematics of the pipette tip . in step 1 in fig2 a , 30 , the operator sets the stop to determine volume to dispense , v d . in step 2 in fig2 b , 32 , the operator depresses the piston 16 to the bottom of its stroke , deflecting the diaphragm 18 to its maximum position . at this point , a three dimensional feature 34 contacts the fluid . because the pipette is dispensing fluids as small as 1 nl , evaporation becomes a concern . if proper design considerations are not made , a large percentage of aspirated fluid can evaporate in the time it takes to aspirate the fluid and dispense it in the appropriate container . an orifice 36 on the pipette tip 12 was designed to be extremely small , limiting evaporation . however , as this orifice 36 becomes smaller and smaller , the more difficult it becomes to aspirate and dispense fluid accurately due to an increase in capillary pressure . therefore , the fluid facing surface of the diaphragm 18 is designed with a three dimensional feature 34 . during step 2 ( fig2 b ), 32 of the pipetting process , this feature comes in contact with the working fluid . the diaphragm 18 , the three dimensional feature 34 and the interior cavity of the tip 12 are configured to be wetting such that retraction of the diaphragm to a controlled position allows fluid to fill the cavity defined by the deflection of the diaphragm 18 and the retraction of the piston mechanism 16 . this is the motivation behind the design of the piston mechanism 16 . the diaphragm 18 must be deflected to its maximum position 32 first in order to come in contact with the fluid . then in step 3 , fig2 c , 38 , the piston 16 is retracted to the position shown in order to aspirate fluid volume , v d . in step 4 , fig2 d , 40 , the diaphragm 18 is once again deflected to its maximum position to dispense all the fluid . the working fluid 20 may be a compressible fluid such as air or some other gas . the compressible working fluid 22 compresses when the piston 16 moves against the working fluid 22 to displace it , resulting in an increased fluid chamber pressure . here , the working fluid acts to temporarily store a portion of the work energy transferred thereto by the piston . in one embodiment , the diaphragm 18 undergoes elastic deformation and the working fluid is compressed when the piston 16 moves against the working fluid 22 to displace it . thus , diaphragm elasticity and working fluid compressibility may be used in various combinations to arrive at the desired deamplification ratio . a set of three nanoliter pipette tips 12 has been designed to exhibit the configuration stated above . each tip 12 possesses different dimensions and initial conditions . fig3 illustrates which dimensions can be varied . the diaphragm radius , 42 , the diaphragm thickness , 44 , the diaphragm shear modulus . 46 , the diaphragm pre - stretch , 48 , and the size of the fluid chamber 20 . changing the dimensions allows the pipette assembly 10 to behave differently based on which tip 12 is selected by the operator . different tips can cause the pipette 10 to have different volume ranges and resolutions . fig4 - 7 illustrate our initial embodiment of the nanoliter pipette tip 12 . this tip can dispense volumes ranging from 1 - 10 nl . fig4 is a front view of the tip 12 . the tip 12 will screw onto the housing 14 and form a fluid tight seal . fig5 is a cross section of the 10 nl tip 12 . the tip 12 is composed of several key components , all critical to the assembly and functionality of the tip . the tip 12 is composed of two main pieces , tip bottom 50 and tip top 52 . an exploded view of tip bottom 50 and its mating components can be seen in fig6 . the diaphragm 18 is secured to the membrane clamp 54 via adhesive 56 . the adhesive makes assembly easier and holds the diaphragm pre - stretch 48 . a detailed view of tip bottom 50 , membrane clamp 54 , the diaphragm 18 , the adhesive 56 , and the three dimensional diaphragm feature 34 can be seen in fig7 . in one embodiment , the raised feature 34 on the diaphragm is a glass microsphere that will be secured to the diaphragm via an adhesive , or can be formed as a monolithic feature of the diaphragm such as by a molding technique . fig5 also features many other components in an example embodiment . a machined nut 58 secures the assembly and provides pre - load by compressing a spring 60 . the preload allows for fine tuning of the compressive forces on the membrane 18 . a pet washer 62 acts as a thrust bearing to prevent any torsional stress from getting to the membrane 18 via the nut 58 . a gasket 64 acts to seal tip top 52 and tip bottom 50 . fig1 delineates the specifics of the piston cam mechanism 92 - 98 and the chamber 78 , which corresponds with the housing 14 in fig1 . the chamber 78 holds a sealed working volume , v o , that comes in direct contact with the diaphragm 18 in the tip 12 . v o can be adjusted to the correct volume via a side screw 76 . the side screw 76 is preloaded via the side spring 74 to ensure that the screw does not move during operation . additionally , a side o - ring 66 provides a fluid seal to ensure that there is no leakage in the system . the chamber 78 is connected to the tip 12 and the exterior body 86 via threads , m6 and ⅞ ″- 14 respectively . similarly to the side screw 76 , the tip 12 is sealed via a gasket 64 and the exterior body is sealed via the top o - ring 80 . above the chamber is the dynamic portion of the mechanism as parts 82 , 84 , 88 , 90 , 92 , 94 and 104 are all in motion , both vertical and rotational . the piston 82 fits into the chamber 78 and when its motion is directly coupled to that of v p . it is also press fit into the interior cap 88 . around the piston 82 , is the piston spring 84 . the piston spring 84 , compresses during operation and provides an upward bias to the cams , 92 & amp ; 94 , via the interior cap 88 and lead screw 104 . the lead screw 104 is fitted into the top of interior cap 88 and is mated with the threaded bushing 90 . the threaded bushing 90 is press fit into the variable cam 92 . the motion and dynamics of four cams mechanisms , 92 - 98 are described below . the exterior cams 96 & amp ; 98 are held in place via a shoulder in the exterior body 86 and a top spacer 100 . the top spacer is bolted into the exterior body 86 via four 4 - 40 screws of length 0 . 3125 ″ 102 . the thumb push 110 is coupled to the thumb connector 106 via a bearing 108 that is press fit onto both pieces . in the exterior body 86 rests the cam mechanisms 92 - 98 , which along with the actual piston 82 correspond to 16 in fig1 . these series of cams provide the repeatability and adjustability required to handle the small volumes of fluid . the cam mechanisms are made up of the exterior cam top 98 , exterior cam bottom 96 , interior cam 94 and the variable cam 92 . the exterior cams 96 , 98 fit together with mirrored offsets and rest on a shoulder in the exterior body 86 . these two cams do not move during the pipetting process . during operation the interior cam 94 and variable cam 92 move up and down and rotate about the vertical axis . before operation , the two cams can move independent of each other through the use of the lead screw 104 and the threaded bushing 90 . rotation of the lead screw , which is done manually by turning the thumb connector 106 , moves the variable cam 92 up and down relative to the interior cam 94 . fig1 a - 13 - h show an 8 - step breakdown of the cam mechanism in operation . the interior and variable cams 92 , 94 start in position i ) continue as follows : 1 ) the thumb push 110 is depressed causing the interior and variable cams 92 , 94 to move down until the top face of the exterior cam 96 comes in to contact with the face of the interior cam 94 2 ) the interior and variable cams 92 , 94 continue to move down and rotate 22 . 5 degrees due to the angular face mate to arrive at position c , 3 ) the thumb push 110 is released and the bottom face of the exterior cam 96 comes in to contact with the face of the variable cam 92 , 4 ) the interior and variable cams 92 , 94 continue to move up and rotate another 22 . 5 degrees to arrive at position e , 5 ) the thumb push 110 is again depressed and the interior and variable cams 92 , 94 move down until the top face of the exterior cam 96 comes in to contact with the face of the interior cam 94 , 6 ) the interior and variable cams 92 , 94 continue to move down and rotate 22 . 5 degrees due to the angular face mate to arrive at position g , 7 ) the thumb push 110 is released and the bottom face of the exterior cam 96 comes in to contact with the face of the interior cam 92 , 8 ) the interior and variable cams 92 , 94 continue to move up and rotate another 22 . 5 degrees to arrive back at position i ). note : all rotation is counterclockwise . fig1 shows the pressure relief system that is used to calibrate the pipette before every use or adjustment . it is necessary for the pipette to have this capability so that the desired deamplification ratio can be achieved . the relief slider 68 can be easily pulled down to expose a relief cavity that connects directly to the inside of the sealed working fluid 20 in the chamber 78 . this relief cavity is sealed by an o - ring that is not pictured in the figures . the relief slider 68 is held in place by a thin shim 70 that is mounted to the chamber 78 via two 4 - 40 screws with a length of 0 . 25 ″ 72 . the volume deamplification principles described above and the design of a pipette tip 12 and piston mechanism 16 in accordance with the present teachings is guided by a mathematical model detailed in our earlier patent application us20130283884 a1 . using this model , pipette tip values can be selected to achieve desired pipetting performance . three different pipette tips have been designed and manufactured . all three tips are compatible with the same chamber 78 and piston / cam mechanism 82 , 92 - 98 . the first tip has the ability to dispense fluids in the range of 1 - 10 nl . a graph of the calculated relationship v d vs v p can be seen in fig8 . it has a volume deamplification ratio v d / v p === 49600 . the second tip was designed to dispense volumes within the range of 10 - 100 nl . its graph can be seen in fig9 . it has a volume deamplification ratio v d / v p = 4960 . finally . fig1 presents the final pipette tip which can dispense volumes of 100 - 1000 nl . it possesses a volume deamplification ratio of v d / v p = 496 . as can be seen in the fig8 - 10 , the function v d ( v p ) is most accurately modeled as a third order polynomial , but with careful selection of pipette tip parameters , the diaphragm radius 42 , the diaphragm thickness 44 , the diaphragm shear modulus 46 , the diaphragm pre - stretch 48 , and the initial volume of the fluid chamber 20 , v d ( v p ) acts approximately linear over the entire stroke of the pipette . linearity of this function is crucial to making the pipette intuitive to use , simplifying mechanical design , and thus lower costs . it can be appreciated that , based on the principles above and using suitable fabrication methods known to those skilled in the art , the design may be scaled to manipulate volumes smaller or larger than ˜ 1 - 1000 nl . the pipette device could also be used to manipulate materials other than liquids , or liquids containing soft solids , for example biological cells . other considerations may include electrical contact to the diaphragm and / or tip , such that electrical signals can be applied when the tip is in contact with solids and / or liquids . the design may also be employed in other configurations , such that multiple tips are arrayed in close proximity , driven by one or more piston mechanisms , which may be manual or motorized . in one example , an array of diaphragms , each within its own tip , is in contact with a single piston via a common volume of working fluid . the characteristics of the diaphragms within the array may be chosen to be the same , or to vary in a prescribed manner . additional information about the present invention may be found in “ universal handheld micropipette ” review of scientific instruments 87 , 115112 ( 2016 ) and in united states published patent application us2013 / 0283884 . the contents of both of these references are incorporated herein by reference in their entirety . it is recognized that modifications and variations of the present invention will be apparent to those of ordinary skill in the art and it is intended that all such modifications and variations be included within the scope of the appended claims . | 1 |
the present application provides a component extraction module for removing a component from a mixed flow of gas or liquid ( e . g ., water from an ethanol / water mixture ). each module comprises a plurality of elements or vessels each having outer jackets connected together in series , parallel , or any combination thereof and supported by a frame . of course , more or fewer “ vessels ” may comprise the “ module ,” depending on the dimensions , flow rates , incoming fluid composition and output required , among other things . fig1 is a perspective view of an exemplary component extraction module 20 of the present application having six elongated tubular vessels 22 connected in series and supported by an external frame 24 . fig1 a illustrates a single tubular vessel 22 having inlet and outlet flanges 30 a , 30 b oriented 180 ° from each other . as will be seen below , the relative orientation inlet and outlet flanges 30 varies depending on the position of the tubular vessel 22 within the overall module 20 . as will be explained in greater detail below , each tubular vessel 22 houses a plurality of rigid flow tubes that extend longitudinally therewithin . each of the inner flow tubes , in turn , receives a tubular membrane formed of the material that can separate water from a liquid or gas mixture to obtain a high - concentration organic solvent . the tubular membranes extend substantially the entire length of the vessels and are sealed at end caps so as to create a negative pressure gradient across the membranes and pull water inward . the tubular vessels 22 are arranged in parallel adjacent to one another and supported by the frame 24 so as to form a more compact module 20 . the vessels 22 are connected in series so that the liquor or gas mixture passes through the connected inner flow tubes and the water can gradually be removed from the liquid or gas mixture . fig2 a is a schematic end view of the component extraction module 20 of fig1 showing the general direction of flow through the six vessels 22 connected in series , while fig2 b is a schematic perspective view of the module showing the overall direction of flow through the six vessels connected in series . in the exemplary embodiment , the six vessels 22 are arranged in a 2 × 3 combination , with three of the vessels supported on an upper level 32 and three of the vessels supported on a lower level 34 . the module 20 has a single inlet port 36 at one end of one of the vessels 22 on the upper level 32 , and a single outlet port 38 at the same end of one of the vessels 22 on the lower level 34 . as indicated by the flow arrows in fig2 a and 2b , the aqueous liquid or gas mixture enters the inlet port 36 and passes along each one of the six vessels 22 in sequence before exiting the outlet port 38 . two side flanges 30 are provided on each one of the vessels 22 to provide flow connections between the vessels . four of the tubular vessels 22 have side flanges 30 that are oriented 180 ° from each other , as seen in fig1 a , while the other two have side flanges 30 that are oriented 90 ° sign from each other . these latter two vessels 22 enable flow between the upper level 32 and the lower level 34 . it should be clear that the flange connections between sequential vessels 22 are at opposite ends , with the flow continuing through the module in a serpentine fashion . details of the vessel construction as well as the placement and assembly of the membranes therein are shown in the attached figures . as will be appreciated by those of skill in the art , the number and arrangement of the tubular vessels 22 within the module 20 may vary , such as providing all six of the tubular vessels on one level , or reversing the flow to go from the lower level 34 to the upper level 32 . likewise , the capacity of the system can be increased by increasing the number or size of vessels 22 , such as by providing a 3 × 3 or 4 × 4 array . indeed , any conceivable array configuration is possible . an alternative component extraction module 20 ′ is shown in fig2 c and 2d like parts will be given like numbers . instead of six vessels 22 in series , as above , the module 20 ′ has vessels 22 connected both in series and in parallel . an inlet 36 is provided at one end of an outside vessel 22 on both the upper level 32 and the lower level 34 . flow passes in series through first and second groups of three vessels 22 on each level , and exits through respective outlets 38 . although not shown , a y - connector or other such piping to join the two inlets 36 as well as the two outlets 38 can be provided to simplify the plumbing . this configuration illustrates just one alternative , and the present application encompasses a plurality of separate vessels each having component extraction membranes therein connected in series , in parallel , or a combination of the two . fig3 a and 3b are two different perspective views of one end of the component extraction module 20 of fig1 . fig4 a is an enlarged perspective view of the ends of two of the tubular vessels 22 , and fig4 b has an outer jacket 40 removed from one of the vessels to show a membrane housing 42 and four inner component extraction membranes 44 extending therefrom to an end cap 46 . as will be explained in greater detail below , there are preferably four flow tubes provided within each membrane housing 42 , which may comprise a tube ( of stainless steel or other suitable material ) having an od of 4 ″ or greater . there may be between 1 - 50 of the flow tubes within each membrane housing 42 , and they may be made of a variety of rigid materials ( e . g ., stainless steel , non - corrosive metal alloys , plastic , etc .). a tubular component extraction membrane 44 extends through each of the flow tubes such that four membranes extend to the end cap 46 . the terminal ends of each of the component extraction membranes 44 are each sealed from the larger space within the vessel jacket 40 . each membrane housing 42 includes a radial plate 48 on each end to which the inner flow tubes attach . the inner diameter of each of the flow tubes is larger than the outer diameter of the component extraction membranes 44 to create an annular space therebetween . the aqueous liquid or gas can thus flow longitudinally through these four annular spaces during which time a negative pressure gradient pulls water into the central lumen of the component extraction membranes 44 . a vacuum hose 50 connected to each end cap 46 maintains the negative pressure gradient and removes the separated water , collecting the aggregate in a common discharge pipe 51 ( fig3 a ). the vacuum hoses 50 comprise flow connectors that enable communication of a source of vacuum to the interior lumens of the extraction membranes 44 . desirably the hoses 50 merge into one , though other arrangements are possible . the aqueous liquid or gas thus flows into one of the side flanges 30 of each vessel 22 , coming into contact with the four exposed sections of the component extraction membranes 44 . subsequently , because of a positive flow pressure , the liquid or gas passes axially through the four annular spaces around the component extraction membranes 44 and within the flow tubes of the membrane housing 42 . the liquid or gas , now somewhat dehydrated , then exits through the other flange 30 of the first vessel 22 and into the second vessel , and continues in this manner through all of the vessels . fig5 - 9 illustrates in greater detail components of the exemplary tubular vessel 22 of fig1 a . fig5 a and 5b illustrate the outer jacket 40 having the two flanges 30 a , 30 b extending from the sides in opposite directions , and the end caps 46 secured thereto with flanges and bolts . longitudinal section b - b from fig5 a as seen in fig6 illustrates the membrane housing 42 within the outer jacket 40 and two of the four flow tubes 52 therein . radial section a - a from fig5 b as seen in fig7 again shows the four flow tubes 52 with component extraction membranes 44 positioned therein , and fig7 a is an enlargement that shows the annular space 54 therebetween . the aqueous liquid or gas flows through the annular space 54 and a vacuum created within the lumen 56 of the membrane 44 pulls water through the membrane . with reference to fig1 - 11 , the overall length l of each tubular outer jacket 40 is desirably greater than 2 × the length of each membrane 44 , since the membranes are loaded from each end . in the exemplary embodiment , the length is about 2 . 2 m ( i . e ., greater than 2 × the 1 m length of the membranes 44 ). the system is applicable to any membrane length . the length l of the membrane housing 42 is somewhat shorter to expose the opposite ends of the membranes 44 , and in an exemplary embodiment is about 1 . 8 m . the outer jacket 40 is desirably tubular for the sake of economy , although other cross - sectional shapes may be used . likewise , the inner membrane housing 42 is also desirably tubular with the radial plates 48 on each end being circular . the four flow tubes 52 are distributed evenly around the membrane housing 42 square pattern , such as seen in fig1 b . in the embodiment shown , the radial plate is a solid , thick , 4 ″ diameter stainless steel plate machined with 4 threaded holes , though it can be any diameter , with any number of holes , threaded or not threaded . no dividers are required because each group of 4 flow tubes is in a separate vessel . it is much cheaper to replicate the 4 - hole plate than it is to create a larger plate for a larger vessel holding more tubes . it is more reliable and more serviceable too , because one flaw in the big plate ( or any of its attached tubes ) renders the entire vessel unusable , whereas a flaw in one of the small vessels only affects that vessel . the preferred module has six 4 ″ od stainless steel tubular membrane housings 42 connected in sequence within the larger jackets 40 . each 4 ″ tubular membrane housing 42 features four 1 ″ od stainless steel flow tubes 52 . each individual membrane 44 is a hollow ceramic ( e . g ., zeolite ) tube formed of two separate membranes of 1 m in length having ends that are in contact with each other so as to form a single tubular length of membrane 2 m long and loaded into a 1 ″ flow tube from each end of the membrane housing 42 to form a single membrane unit therein . the ethanol / water vapor ( at about 90 % ethanol , 10 % water ), at some positive pressure , enters the first membrane housing and travels through the annular spaces between the inner walls of the 1 ″ flow tubes and the outer walls of the membranes therein . a vacuum is applied to the inner core of the membrane to create a negative inward pressure gradient , and water vapor selectively permeates the membrane . the water vapor ( with approximately 4 % ethanol ) is called permeate and can be recycled in the plant . the ethanol / water vapor passes through the six vessels 22 , steadily losing water through the membranes 44 . the exhaust vapor out of the 6th vessel 22 is anhydrous grade fuel ethanol ( 99 . 2 %). fig8 is a vertical sectional view taken through two of four inner separation membranes 44 in one of the tubular vessels 22 taken along line c - c of fig7 . as mentioned previously , the component extraction membranes 44 extend axially beyond the membrane housing 42 to an end cap 46 . the lumen 56 of each of the membranes 44 is open to a hemispherical chamber 58 within the end cap 46 , and as mentioned a vacuum is pulled through a hose attached to a nipple 60 . the ends of each of the membranes 44 are sealed from a volume 62 within the outer jacket 40 and adjacent a side flange 30 . specifics of the seal are shown exploded in fig9 , with the end cap 46 separated from the outer jacket 40 . each membrane 44 passes through one of four holes in a generally circular and axially thick end plate 70 . as seen in cross - section in fig8 , the four holes each receive a number of washers and seals ( shown exploded in fig9 ) that prevent ingress of fluid from within the inner volume 62 of the jacket to the hemispherical chamber 58 . in preferred embodiments there is a relatively thin rigid ( e . g ., stainless steel ) washer 72 , an o - ring 74 of a suitable elastomer such as epdm rubber , a second washer 76 of a polymer such as ptfe , and a relatively thick rigid ( e . g ., stainless steel ) washer 78 , all secured within the holes of the end plate 70 with a threaded sealing cap 80 . a larger o - ring 82 extends around the outer edge of the end plate 70 and is sealed between two flanges of the jacket 40 and end 46 by a plurality of clamp assemblies 84 . the particular membrane material depends on the separation process . in general , the membrane would be selectively permeable for at least one component of a liquid or gas stream . ceramics are often used to separate water from hydrous organics solvents , and some permit gasses such as co 2 to pass through . for separation of water from hydrous ethanol , the membrane is desirably a porous tube of zeolite containing an alumina as a main component and an attachment member disposed in a connection position of the porous tube , wherein the porous tube and the attachment member are bonded by a ceramic oxide - based bonding agent containing 17 to 48 wt % of sio 2 , 2 to 8 wt % of al 2 o 3 , 24 to 60 wt % of bao , and 0 . 5 to 5 wt % of zno as essential components and containing at least one of la 2 o 3 , cao , and sro , and a zeolite layer is formed on a surface of the porous tube . for example , the separation membranes used in the hds ® ( hitz dehydration system ) from hitachi zosen may be suitable , as are those described in u . s . patent publication no . 2011 / 0174722 to yano , et al ., the disclosure of which is expressly incorporated by reference herein . the membrane material is hydrophilic and thus facilitates the removal of water from the vapor stream . the coating on the surface of the membrane facing the vapor stream is highly sensitive to scratching and has a significant impact on the efficacy of the membrane and its usage . it should be noted that though the preferred membrane is hydrophilic and pulls water out of liquid , an alternative hydrophobic membrane may be used with a reverse function . that is , a membrane that prevents water passage but permits solvent passage could be used in the system with the solvent being collected in the membrane lumens . one of the advantages of the present system is that smaller membrane “ elements ” ( or vessels 22 ), can be mixed and matched to provide any number of membrane tubes and passes to create the same capacity as in the hitz dehydration system , which utilizes one larger vessel . for example , one system operates at a vapor supply pressure of approximately 1 psig , with a vacuum of 29 ″ hg on the membrane &# 39 ; s inner cores . the modular design includes six passes through each of 4 membrane tubes ( actually 8 membranes because two are always placed end - to - end ) per pass . the six elements connected together in series provided exactly the same flow path as in a large module design such as the hitz dehydration system , which places 24 tubes inside one outer vessel . throughout this description , the embodiments and examples shown should be considered as exemplars , rather than limitations on the apparatus and procedures disclosed or claimed . although many of the examples presented herein involve specific combinations of method acts or system elements , it should be understood that those acts and those elements may be combined in other ways to accomplish the same objectives . with regard to flowcharts , additional and fewer steps may be taken , and the steps as shown may be combined or further refined to achieve the methods described herein . acts , elements and features discussed only in connection with one embodiment are not intended to be excluded from a similar role in other embodiments . | 2 |
referring now to the figures of the drawings in detail and first , particularly , to fig1 thereof , there is seen a diagrammatic illustration of a first exemplary embodiment of a device 1 according to the invention for providing a reducing - agent - containing gas flow . the device 1 includes a duct or channel 2 which is formed in a jacket 3 . the jacket 3 surrounds a rod - shaped heating element 4 . the rod - shaped heating element 4 has at least one first heat conductor 5 and one second heat conductor 6 . a first zone 7 can be heated through the use of the first heat conductor 5 , and a second zone 8 can be heated through the use of the second heat conductor 6 . the heat conductors 5 , 6 are preferably self - regulating heat conductors , such as for example ptc conductors . a sleeve 9 , which is also provided , is pushed over the device in the direction of an arrow 10 . the sleeve 9 has a constriction 11 which , in the assembled device 1 , lies at a boundary between the first zone 7 and the second zone 8 . the constriction 11 reduces the exchange of heat between the two zones 7 , 8 through the sleeve 9 . further measures for reducing or preventing such exchange of heat may be provided . during operation , a reducing agent precursor 12 , preferably urea , is added in particular in the form of an aqueous urea solution , into the duct 2 and is preferably completely evaporated there in the first zone 7 . a gas flow , which is then formed and which includes at least one reducing agent precursor , then flows onward through the duct 2 and is heated . in particular , the heating especially takes place at least partially in the region of the second zone 8 . the gas flow 13 then leaves the duct 2 . depending on the construction of the device 1 and on the implementation of the method , the gas flow 13 includes a reducing agent precursor and / or a reducing agent , which is generated in particular in the region of the second zone 8 through the use of thermolysis . the duct 2 may , at least in partial regions of the first zone 7 and the second zone 8 , have a hydrolysis catalyst coating , that is to say a coating which catalyzes the hydrolysis of the reducing agent precursor to form reducing agent . fig2 shows a device 1 according to the invention as a part of a device for the selective catalytic reduction of nitrogen oxides in the exhaust gas of an internal combustion engine . the device 1 has a first zone 7 and a second zone 8 in this case too . the zones 7 , 8 are heated by the heating devices 5 , 6 ( not shown in fig2 ) which are controlled by a control device 14 that can be connected by first lines 15 to the corresponding first heat conductor 5 of the first zone 7 and by second lines 16 to the second heat conductor 6 of the second zone 8 . the heating power both in the first zone 7 as well as in the second zone 8 can thus be regulated and controlled independently of one another . the control device 14 may at the same time include a voltage or current supply . if self - regulating first and second heat conductors 5 , 6 are used , it is possible to dispense with the control device 14 . instead , it is possible for merely a current or voltage supply to be provided for each of the heat conductors 5 , 6 . a device 17 for delivering a solution of at least one reducing agent precursor is also provided . in this exemplary embodiment , the device 17 includes a pump 19 in addition to a reservoir 18 for a solution of a reducing agent precursor . the pump 19 may for example be a dosing pump , through which in each case defined quantities of the solution are introduced into the first zone . it is also possible for the pump 19 to be constructed as a conventional pump , for example as a diaphragm pump , with a valve 20 then advantageously being provided . the supply of the solution of the reducing agent precursor to the first zone 7 is regulated through the use of the valve 20 . the valve 20 may advantageously be connected through third lines 21 to the control device 14 . a hydrolysis catalytic converter 22 is provided downstream of the second zone 8 . during operation , an at least partial hydrolysis of the reducing agent precursor to form the reducing agent takes place in the hydrolysis catalytic converter 22 . in this way , the reducing agent is generated outside an exhaust line 23 . a reducing - agent - containing gas flow 24 generated in the device 1 is introduced into the exhaust line 23 , where the gas flow 24 is mixed with an exhaust - gas flow 25 of an internal combustion engine . the mixture of the two gas flows then flows through an scr catalytic converter 26 , in which nitrogen oxides contained in the exhaust - gas flow 25 are converted with the reducing agent . a gas flow having an no x content which has been reduced then leaves the scr catalytic converter 26 . fig3 diagrammatically shows a further exemplary embodiment of the device 1 according to the invention . in this case , a reducing agent precursor solution is not evaporated . instead , a device 27 for the quasi - continuous transportation of at least one reducing agent precursor as solid matter 28 is provided . in this case , a type of strand of the reducing agent precursor 28 or of a solid matter 28 including a reducing agent precursor is pressed into a first zone 7 . this takes place , for example , through the use of a hydraulic cylinder 29 which can be controlled correspondingly . the reducing agent precursor 28 is melted , with simultaneous or subsequent evaporation , in the first zone 7 having the first heating element 5 . the vapor which is generated in this way is heated further in the second zone 8 , which is heated by the second heating element 6 . heating to an even higher temperature takes place in a third zone 31 which includes a third heat conductor 30 . the gas mixture which is generated then flows through the hydrolysis catalytic converter 22 . depending on the make up of the solid matter 28 which includes the reducing agent precursor , it may be necessary for water to also be provided in the hydrolysis catalytic converter 22 . this may take place , for example , by introducing a certain amount of exhaust - gas flow upstream of the hydrolysis catalytic converter or else through the use of the simultaneous evaporation of water , for example of condensation water . the hydrolysis catalytic converter 22 is optional , in particular if the temperatures of the first zone 7 , second zone 8 and third zone 31 are selected in such a way that a substantially complete thermolysis of the reducing agent precursor to form ammonia takes place . in the present embodiment , the hydrolysis catalytic converter 22 is flange - mounted directly onto the exhaust line 23 at right angles . after infiltrating into the exhaust line 23 , the exhaust - gas flow 25 , which is then enriched with reducing agent , then flows through the scr catalytic converter 26 . an exhaust - gas flow having a nitrogen oxide content which has been reduced in relation to the exhaust - gas flow upstream of the scr catalytic converter 26 , then leaves the scr catalytic converter 26 . fig4 diagrammatically shows a further embodiment of a device 1 according to the invention as a part of a device for the selective catalytic reduction of nitrogen oxides in the exhaust gas of an internal combustion engine . in contrast to the embodiments discussed above , this exemplary embodiment has a device 32 for the discontinuous transportation of a solid matter which includes a reducing agent precursor . the device 32 includes a reservoir 33 which stores solid matter particles 34 that include at least one reducing agent precursor , such as for example urea pellets . a separating device 35 is provided between the reservoir 33 and the first zone 7 . it can be ensured through the use of the separating device 35 that during operation only one solid matter particle 34 passes into the first zone 7 . in this embodiment , the device 1 optionally also has a further supply line 36 , through which a water - containing gas can be supplied . the water - containing gas may be used to promote the hydrolysis in the hydrolysis catalytic converter 22 . fig5 diagrammatically shows a portion of a duct 2 . the duct 2 has a first zone 7 with a first cross section and a second zone 8 with a second cross section . the cross section of the second zone 8 is larger than the cross section of the first zone 7 . furthermore , the duct 2 includes fittings 37 which act as a type of impact plate and which ensure that no droplets , resulting from an incomplete evaporation in the first zone , pass through the second zone 8 , but that such droplets instead impact against the fittings 37 . it is generally advantageous to provide at least one change in direction of the gas flow in the second zone 8 , for example through the use of deflections , duct radius constrictions , fittings or the like . the method according to the invention and the device 1 according to the invention advantageously permit the provision of a reducing - agent - containing gas flow 13 , the quantity of which can be controlled in a simple manner and can be adapted to dynamic changes in situation as often occur in particular in the exhaust - gas system of mobile applications , such as for example in automobiles . it has been proven to be advantageous in particular for the method to be implemented in such a way that the temperature of the first zone 7 is held at approximately 150 ° c . or slightly lower , while the temperature of the second zone 8 is held at over 300 ° c . as a result of the supply of the reducing agent precursor in the form of vapor to the hydrolysis catalytic converter 22 , the hydrolysis catalytic converter 22 experiences virtually no cooling , such that the implementation of the method is positively influenced in this case as well . | 8 |
the present invention will now be described more fully hereinafter with reference to the accompanying drawings . the present invention has been made according to the result of the analysis of reasons by which a thin film capacitor has decrease in capacitance and degradation in bdv characteristics . that is , during simultaneous heat treatment of a metal foil and a dielectric layer , the metal foil is recrystallized . this causes defects in the interface between the metal foil and the dielectric layer , thereby deteriorating bdv characteristics . furthermore , the oxidation of the metal foil results in the decrease of capacitance . to overcome such problems associated with the recrystallization of the metal foil , a dielectric material having a low crystallization temperature may be used or a metal having a high recrystallization temperature may be used for a metal electrode . however , the former has a problem in that there are no dielectric materials known to crystallize at a temperature lower than the recrystallization temperature of metal . for the latter , some metals such as pt and pd are adoptable , but they are expensive . accordingly , the present invention has adopted recrystallization heat treatment of the metal foil . while several problems resulting from the oxidation of the metal foil have been reported up to the present , there are no reports about the heat treatment of the metal foil in terms of recrystallization . us patent application publication no . 2002 / 0195612 discloses pre - heating or pre - annealing of a cu foil prior to the formation of a dielectric layer . however , the pre - heating is not performed in terms of recrystallization . rather , the pre - heating is performed merely in terms of preventing cu atoms from diffusing into the dielectric layer , at a high or low temperature . in case of the low temperature , heat treatment is carried out for a long time period . in this technology , it is presumed that a thin oxide layer restrains cu ions from diffusion . through experiments , the inventors have found that heat treatment when performed for a long time period inevitably results in capacitance decrease even though performed at a low temperature in an anaerobic atmosphere . furthermore , while the ni layer as a barrier has a thickness on the order of 0 . 1 μm to 2 . 0 μm according to this technology , experiments of the inventors have observed that the nickel layer thickness is reduced owing to volatilization during the heat treatment . accordingly , the inventors have adopted recrystallization heat treatment capable of preventing the oxidation of a metal foil to overcome decrease in capacitance and deterioration in bdv characteristics . such features will be described in detail step - by - step . according to the present invention , first , a metal foil is recrystallized via heat treated for or recrystallization heat treated . the metal foil is a substrate supporting a capacitor , acting as a lower electrode . the metal foil is preferably made of cu or cu alloy which is cheap and easily handled . a barrier layer may be additionally formed on the metal foil . such a barrier layer may be formed on one side surface or both side surfaces of the metal foil . the barrier layer functions to prevent oxidation , and adopts any types of metals which can perform such a function . examples of the adoptable metal include ni , in which 3 % to 15 % of p may be contained . the barrier layer may be formed for example via plating or deposition . for the plating , any of electrolytic plating and electroless plating can be adopted . in a case where ni is adopted for the barrier layer , it may volatilize in the heat treatment . the ni barrier layer may be provided preferably at a thickness of 0 . 8 μm or more , and more preferably , at a thickness ranging from 0 . 8 μm to 4 μm . after the formation of the barrier layer , the recrystallization heat treatment is performed . since the recrystallization heat treatment of the metal foil with or without the barrier layer is supposed to recrystallize the metal foil , this process can be performed for a short time period at a relatively lower temperature . accordingly , even if the recrystallization heat treatment is performed in an ambient atmosphere , there is no worry about the oxidation of the metal foil . the recrystallization heat treatment is performed preferably at a temperature ranging from 100 ° c . to 450 ° c . more preferably , the recrystallization heat treatment may be performed for a short time period at a relatively higher temperature for example in the range from 400 ° c . to 450 ° c . performing this process for a long time period may deteriorate dielectric characteristics of capacitance owing to oxidation . treatment time is not limited in a temperature range from 100 ° c . to 400 ° c ., but set preferably in the range from 5 mins to 30 mins in a higher temperature range from 400 ° c . to 450 ° c . since oxidation may take place in this range . recrystallization does not take place when the recrystallization heat treatment is performed at a too low temperature or for a too short time period . if the recrystallization heat treatment temperature is too high or the recrystallization heat treatment time exceeds 30 mins at a higher temperature range from 400 ° c . to 450 ° c ., oxidation may take place . at a low temperature range under 400 ° c ., oxidation would rarely take place even if the treatment time is prolonged more or less . when the recrystallization heat treatment of the invention is performed , its atmosphere is not specifically controlled . for example , the recrystallization heat treatment may be performed in an ambient atmosphere . this is because that there is no worry about oxidation since the recrystallization heat treatment is performed at a low temperature or for a short time period at a temperature range from 400 ° c . to 450 ° c . the ambient atmosphere is easier in terms of process management than anaerobic atmosphere . after the recrystallization heat treatment , a dielectric layer is formed on the metal foil with or without the barrier layer formed thereon . the dielectric layer may be formed via sol - gel method , spin coating or deposition . examples of the deposition include physical vapor deposition ( pvd ), atomic layer deposition ( ald ) and chemical vapor deposition cvd . the dielectric layer is formed preferably at a thickness in the range from 10 nm to 1 , 000 nm . the dielectric layer may be made of any typical dielectric material used for thin film capacitors , and preferably , of a ferroelectric material . examples of the ferroelectric material include pzt ( pb ( zr , ti ) o 3 ) or plzt (( pb , la ) ( zr , ti ) o 3 ), bto ( batio 3 ) and the like . after the dielectric layer is formed , heat treatment is performed . the heat treatment is performed at a temperature necessary for the recrystallization of the dielectric layer . then , an upper electrode is formed on the top surface of the crystallized dielectric thin film . the upper electrode may be made of any metal which is adoptable to thin film capacitors . examples of the adoptable metal may include pt , au , ag , cu , ni , pd and the like . the upper electrode may be formed via deposition and plating alone or in combination . examples of the deposition may include pvd , cvd and the like , and examples of the plating may include electroless plating , electrolytic plating and the like . the thickness of the upper electrode is preferably in the range from 0 . 1 μm to 100 μm . the thin film capacitor manufactured according to this invention is suitable to be embedded in a pcb . the thin film capacitor of the invention may be stacked on at least one laminated layer . for example , a pcb may be fabricated by layering a polymer substrate on a copper clad laminate ( ccl ), stacking a thin film capacitor of the invention on the polymer substrate , and compressing the thin film capacitor against the polymer substrate . accordingly , the thin film capacitor manufactured according to the invention can be embedded in the pcb according to a typical fabrication process of the pcb . hereinafter the invention will be described in more detail with reference examples . a ni layer ( containing 8 % to 12 % of p ) was formed to a thickness of 4 μm on a cu foil via electroless plating . the ni - plated cu foil was recrystallized via heat treatment ( or recrystallization heat treated ) at 300 ° c . for 10 mins in an ambient atmosphere . then , ferroelectric sol of pzt was spin - coated at 3000 rpm for 20 secs on the top of the ni layer to form a dielectric layer . crystallization was performed via heat treatment at 450 ° c . for 10 mins and then at 550 ° c . for 30 mins in a nitrogen atmosphere . during the heat treatment in the nitrogen atmosphere , temperature was raised at a rate of 2 ° c . per min , and nitrogen gas was introduced at a rate of 5 liter per min . au was deposited on the top of the heat - treated dielectric layer by using a dc sputterer . by using the au deposition as an upper electrode , electric properties were measured . the electric properties measured are reported in fig1 . as shown in fig1 ( a ), a conventional example without a recrystallized metal layer showed low leakage current characteristics but the leakage current increased with the voltage rising . dielectric breakdown was observed in the range from 6v to 8v . such dielectric breakdown indicates that a dielectric material loses its dielectric properties . on the contrary , when the recrystallization heat treatment was performed according to the invention , bdv characteristics were maintained up to 10v . fig1 ( b ) shows capacitance density characteristics according to frequencies . it can be observed that capacitance characteristics were improved in example 1 where the recrystallization heat treatment was performed according to the invention than the conventional example without the recrystallization heat treatment . a ni layer ( containing 8 % to 12 % of p ) was formed to a thickness of 4 μm on a cu foil via electroless plating . the ni - plated cu foil was recrystallized via heat treatment ( or recrystallization heat treated ) in an ambient atmosphere according to conditions reported in fig2 . after the recrystallization heat treatment , a ferroelectric sol of pzt was spin - coated on the ni layer at 3000 rpm for 20 secs to form a dielectric layer . crystallization was performed via heat treatment at 450 ° c . for 10 mins and then at 550 ° c . for 30 mins in a nitrogen atmosphere . during the heat treatment in the nitrogen atmosphere , temperature was raised at a rate of 2 ° c . per min , and nitrogen gas was introduced at a rate of 5 liter per min . au was deposited on the top of the heat - treated dielectric layer by using a dc sputterer . by using the au deposition as an upper electrode , electric properties were measured . the electric properties measured are reported in fig2 . as shown in fig2 , capacitance characteristics were most excellent when heat treated at 300 ° c . for 10 mins . when heat treated at 400 ° c . for 60 mins , leakage current characteristics were good but capacitance characteristics were not so good . while the present invention has been described with reference to the particular illustrative embodiments and the accompanying drawings , it is not to be limited thereto but will be defined by the appended claims . it is to be appreciated that those skilled in the art can substitute , change or modify the embodiments into various forms without departing from the scope and spirit of the present invention . for example , while examples of the invention use pzt as a dielectric material , a ferroelectric material used for an embedded capacitor can be used either . as set forth above , the present invention performs recrystallization heat treatment in such a manner of preventing the oxidation of a metal foil , by which a dielectric layer can be heat treated at a high temperature , thereby improving electric properties of a thin film capacitor and the reliability of a product . | 7 |
in the following detailed description , only certain exemplary embodiments of the present invention are shown and described , by way of illustration . as those skilled in the art would recognize , the invention may be embodies in many different forms and should not be construed as being limited to the embodiments set forth herein . also , in the context of the present application , when a first element is described as being “ coupled to ” a second element , the first element may be directly coupled to the second element or may also be indirectly coupled to the second element with one or more intervening elements interposed there between . further , some of the elements that are not essential to the complete understanding of the invention are omitted for clarity . also , like reference numerals refer to like elements throughout the specification . while the present invention has been described in connection with certain 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 , and equivalents thereof . hereinafter , embodiments of the present invention will be described in more detail with reference to fig1 to 8 so that those skilled in the art can easily implement the present invention . fig1 is a diagram showing one frame period according to an embodiment of the present invention . referring to fig1 , one frame 1 f according to the embodiment of the present invention includes a reset period rp , a compensation period cp , and an emission period ep . during the reset period rp , an initial voltage is supplied to an anode electrode of an organic light emitting diode ( oled ) included in each of the plurality of pixels . during the reset period , each of the plurality of pixels is set to a non - emission state . a threshold voltage of a driving transistor is compensated for in each of the plurality of pixels during the compensation period cp . that is , during the compensation period cp , each of the pixels is charged with a voltage corresponding to the threshold voltage of the driving transistor . during the compensation period cp , each of the pixels is set to the non - emission state . during the emission period ep , each of the pixels emits light having a luminance determined by the current flowing through the organic light emitting diode of each pixel . since the threshold voltage of the driving transistor is compensated for during the compensation period cp , the current flowing through the organic light emitting diode is independent of the threshold voltage of the driving transistor . thus , an image having a uniform luminance is displayed during the emission period ep regardless of any variability in threshold voltage among the driving transistors included in each of the pixels that make up the organic light emitting display device . in the above - mentioned embodiment of the present invention , a period of the compensation period cp is set to sufficiently compensate for the threshold voltage of the driving transistor . that is , in an embodiment of the present invention , the compensation period cp can be set to sufficiently compensate for the threshold voltage of the driving transistor , even when the driving transistor is driven by a frequency of 120 hz or more . thus , an image having a uniform luminance may be displayed . further , in an embodiment of the present invention , since each of the pixels is switched into an emission or non - emission state at the same time , a first control line and a second control line that control emission or non - emission may be connected to each of the pixels , thereby simplifying both structure and driving . in an embodiment of the present invention , a frame period may include only a compensation period cp and an emission period ep to correspond to a structure of a pixel . a detailed description thereof will be described below with reference to the structure of the pixel . fig2 is a diagram showing an organic light emitting display device according to an embodiment of the present invention . referring to fig2 , the organic light emitting display device according to an embodiment of the present invention includes a plurality of pixels 140 positioned to access a plurality of scan lines s 1 to sn and data lines d 1 to dm ; a scan driver 110 for driving the scan lines s 1 to sn ; a data driver 120 for driving the data lines d 1 to dm ; a first power supply 160 for generating a first power elvdd ; a control line driver 170 for driving a first control line cl 1 and a second control line cl 2 ; and a timing controller 150 for controlling the scan driver 110 , the data driver 120 , the first power supply 160 , and the control line driver 170 . the scan driver 110 supplies a scan signal to the scan lines s 1 to sn during a second period of the reset period rp . further , the scan driver 110 sequentially supplies the scan signal to the scan lines s 1 to sn during the compensation period cp . the data driver 120 supplies a reset voltage to the data lines d 1 to dm during the reset period rp . further , the data driver 120 supplies a data signal to the data lines d 1 to dm . the data signal is synchronized with the scan signal during the compensation period cp . the first power supply 160 supplies a first low power ( or a first power at a low level ) elvdd_l , also called an initial voltage , having a low level during the reset period rp and supplies a first high power ( or a first power at a high level ) elvdd_h having a high level during the compensation period cp and the emission period ep . herein , the first low power elvdd_l is set to a voltage lower than the voltage of the data signal . in addition , the first high power elvdd_h is set to a voltage higher than both the data signal voltage vdata and the reference voltage vref . the control line driver 170 supplies a second control signal to the second control line cl 2 during the compensation period cp and the second period of the reset period rp . in addition , the control line driver 170 supplies a first control signal to the first control line cl 1 during the emission period ep and a first period of the reset period rp . herein , supplying the first control signal and the second control signal refers to supplying voltages at sufficient levels to transistors to switch on the transistors that are coupled to the first control line cl 1 and the second control line cl 2 . the timing controller 150 controls the scan driver 110 , the data driver 120 , the first power supply 160 , and the control line driver 170 to correspond to synchronization signals supplied from an outside source . a pixel unit 130 receives the first power elvdd , a second power elvss and the reference voltage vref from an outside source and supplies each to each of the plurality of pixels 140 . each of the plurality of pixels 140 sets the voltage of the anode electrode of the organic light emitting diode oled to the first low power elvdd_l during the reset period rp . in addition , each of the pixels 140 is charged with a voltage corresponding to a threshold voltage of a driving transistor during the compensation period cp and emits light corresponding to the data signal during the emission period ep . meanwhile , the first high power elvdd_h , the first low power elvdd_l , the data signal voltage vdata , and the reference voltage vref are set as shown in equation 1 . referring to equation 1 , the first low power elvdd_l is set to a voltage lower than the data signal voltage vdata . actually , the first low power elvdd_l is set to a voltage lower than a voltage resulting from subtracting the threshold voltage of the driving transistor from the data signal voltage vdata . in addition , the reference voltage vref is set to a voltage equal to or higher than the data signal voltage vdata . the first high power elvdd_h is set to a voltage higher than the reference voltage vref . fig3 is a diagram showing a pixel 140 according to a first embodiment of the present invention . in fig3 , the pixel 140 connected to the n - th scan line sn and the m - th data line dm is shown for convenience of description . referring to fig3 , the pixel 140 according to the first embodiment of the present invention includes the organic light emitting diode oled and a pixel circuit 142 that is connected to the data line dm , the scan line sn , the first control line cl 1 , and the second control line cl 2 . each of the data line dm , the scan line sn , the first control line c 11 , and the second control line cl 2 contribute to the control of the organic light emitting diode oled . an anode electrode of the organic light emitting diode oled is connected to the pixel circuit 142 , and a cathode electrode of the organic light emitting diode oled is connected to the second elvss . the organic light emitting diode oled emits light having a luminance that is determined by a current supplied from the pixel circuit 142 . the pixel circuit 142 initializes the anode electrode of the organic light emitting diode oled to the first low power elvdd_l during the reset period rp and charges voltage corresponding to the data signal and the threshold voltage of the driving transistor during the compensation period cp . in addition , the current corresponding to the voltage charged during the emission period ep is supplied to the organic light emitting diode oled . for this , the pixel circuit 142 includes first to fourth transistors m 1 , m 2 , m 3 and m 4 , a first capacitor c 1 , and a second capacitor c 2 . a gate electrode of the first transistor m 1 , also called a driving transistor , is connected to a first node n 1 , and a first electrode of the first transistor m 1 is connected to the first power elvdd . in addition , a second electrode of the first transistor m 1 is connected to the anode electrode of the organic light emitting diode oled . that is , the second electrode of the first transistor m 1 is connected to the organic light emitting diode oled at a third node n 3 . the voltage at the first node n 1 controls the first transistor m 1 , which in turn controls the amount of current supplied to the organic light emitting diode oled . the amount of current supplied to the organic light emitting diode oled corresponds with the voltage of the first power elvdd and the voltage at the first node n 1 . a gate electrode of the second transistor m 2 is connected to the scan line sn and a first electrode of the second transistor m 2 is connected to the data line dm . in addition , a second electrode of the second transistor m 2 is connected to the first node n 1 . the second transistor m 2 is switched on when the scan signal is supplied to the scan line sn . when the second transistor m 2 is switched on , the first node n 1 is electrically connected to the data line dm . a gate electrode of the third transistor m 3 is connected to the first control line cl 1 , and a second electrode of the third transistor m 3 is connected to the first node n 1 . because the first node n 1 is connected to the gate electrode of the first transistor m 1 , the second electrode of the third transistor m 3 is connected to the gate electrode of the first transistor m 1 . in addition , a first electrode of the third transistor m 3 is connected to the second node n 2 . the third transistor m 3 is switched on when the first control signal is supplied to the first control line cl 1 . when no first control signal is supplied to the first control line cl 1 , the third transistor m 3 is switched off . a gate electrode of the fourth transistor m 4 is connected to the second control line cl 2 , and a first electrode of the fourth transistor m 4 is connected to the reference voltage vref . in addition , a second electrode of the fourth transistor m 4 is connected to the second node n 2 . the fourth transistor m 4 is switched on when the second control signal is supplied to the second control line cl 2 . when no second control signal is supplied to the second control line cl 2 , the fourth transistor m 4 is switched off . a first capacitor c 1 and a second capacitor c 2 are connected in series between a first node n 1 and a third node n 3 . the second node n 2 , located between the first capacitor c 1 and the second capacitor c 2 is also connected to the first electrode of the third transistor m 3 and the second electrode of the fourth transistor m 4 . herein , the second capacitor c 2 and the third transistor m 3 are connected between the first node n 1 and the second node n 2 in parallel . fig4 a to 4d are waveform diagrams showing an embodiment of a driving method of a pixel 140 shown in fig3 with pixel circuit 142 . herein , an operation process is described in more detail . first , the first control signal cl 1 is supplied during a first period t 1 of the reset period rp as shown in fig4 a . when the first control signal cl 1 is supplied , the third transistor m 3 is switched on , such that the first node n 1 and the second node n 2 are electrically connected to each other . the initial voltage vint , also called the first power elvdd_l , is supplied during the reset period rp . thereafter , as shown in fig4 b , the scan signal is simultaneously supplied to each of the plurality of scan lines s 1 to sn during a second period t 2 of the reset period rp . further , a reset voltage vr is supplied to each of the plurality of data lines d 1 to dm during the second period of the reset period rp . herein , the reset voltage vr is set to a voltage at which the first transistor m 1 included in the pixel 140 can be switched on . in addition , the second control signal is supplied to the second control line cl 2 during the second period t 2 of the reset period rp . when the scan signal is supplied to the scan lines s 1 to sn , the second transistor m 2 is switched on . when the second transistor m 2 is switched on , the reset voltage vr from the data line dm is supplied to the first node n 1 . at this time , the first transistor m 1 is switched on , such that the first low power elvdd_l is supplied to the third node n 3 . the first low power elvdd_l is set to a voltage at which the organic light emitting diode oled can be turned off , such that unnecessary light is not emitted from the organic light emitting diode oled . when the second control signal is supplied to the second control line cl 2 , the fourth transistor m 4 is switched on . when the fourth transistor m 4 is switched on , the voltage of the reference voltage vref is supplied to the second node n 2 . during the compensation period , as shown in fig4 c , the scan signal is supplied to the scan lines s 1 to sn in sequence , and the second control signal is supplied to the second control line cl 2 . in addition , the data signal is supplied to the data lines d 1 to dm . the data signal is synchronized with the scan signal . further , the first power supply 160 supplies the first high power elvdd_h . when the second control signal is supplied to the second control line cl 2 , the fourth transistor m 4 is switched on . in this case , the second node n 2 maintains the voltage of the reference voltage vref . when the scan signal is supplied to the scan line sn , the second transistor m 2 is switched on . when the second transistor m 2 is switched on , the data signal is supplied from the data line to the first node n 1 . at this time , the data signal voltage vdata is applied to the first node n 1 . when the data signal voltage vdata is applied to the first node n 1 , the voltage of the third node n 3 gradually increases up to a voltage resulting from subtracting the threshold voltage vth of the first transistor m 1 from the data signal voltage vdata . more specifically , the first low power elvdd_l applied during the reset period rp is set to a voltage lower than the voltage resulting from subtracting the threshold voltage vth of the first transistor m 1 from the data signal voltage vdata . accordingly , when the data signal voltage vdata is applied to the first node n 1 , the voltage at the third node n 3 gradually increases up to the voltage resulting from subtracting the threshold voltage vth of the first transistor m 1 from the data signal voltage vdata . actually , even after the scan signal to the scan line sn is no longer supplied , thereby switching off the second transistor m 2 , the first node n 1 is maintained at the data signal voltage vdata due to the second capacitor c 2 . this results in the voltage at the third node n 3 increasing up to the voltage resulting from subtracting the threshold voltage vth of the first transistor m 1 from the data signal voltage vdata . in an embodiment of the present invention , for stable driving , a sufficient time is allocated to the compensation period cp so that the voltage at the third node n 3 included in each of the plurality of the pixels 140 increases up to the voltage resulting from subtracting the threshold voltage of the first transistor m 1 , vth ( m 1 ), from the data signal voltage vdata . meanwhile , during the compensation period cp , a voltage vref − vdata is charged in both ends of the second capacitor c 2 , and a voltage vref − vdata + vth ( m 1 ) is charged in both ends of the first capacitor c 1 . during the emission period ep , as shown in fig4 d , the first control signal cl 1 is supplied . when the first control signal cl 1 is supplied , the third transistor m 3 is switched on . when the third transistor m 3 is switched on , the first node n 1 and the second node n 2 are electrically connected to each other . in this case , a difference in voltage of both terminals of the second capacitor c 2 is set to 0 . a voltage vgs ( m 1 ), which corresponds to the voltage between the gate electrode and the source electrode , also called the second electrode , of the first transistor m 1 , is set to the voltage charged in the first capacitor c 1 . that is , the voltage between the gate electrode and the second electrode of the first transistor m 1 vgs ( m 1 ) is set as shown in equation 2 . the amount of current flowing to the organic light emitting diode oled , i oled , is set as shown in equation 3 by the voltage vgs of the first transistor m 1 , where β is a constant . ioled = β ( vgs ( m 1 )− vth ( m 1 )) 2 = β {( vref − v data + vth ( m 1 ))− vth ( m 1 )} 2 = β ( vref − v data ) 2 equation 3 referring to equation 3 , the current flowing to the organic light emitting diode oled is determined by difference in voltage between the reference voltage vref and the data signal voltage vdata . since the reference voltage vref is a fixed voltage , any change in the current flowing to the organic light emitting diode oled , i oled , is determined by a change in the data signal voltage vdata . in addition , in an embodiment of the present invention , as shown in equation 3 , an image having uniform luminance can be displayed regardless of any variability among the threshold voltages of the first transistors m 1 , vth ( m 1 ), included in each of the plurality of pixels that make up the organic light emitting display device . fig5 is a diagram showing a pixel according to a second embodiment of the present invention . when fig5 is described , the same reference numerals refer to the same components as those of fig3 and a detailed description thereof will be omitted . referring to fig5 , a pixel 140 according to the second embodiment of the present invention includes a pixel circuit 142 ′ and an organic light emitting diode oled . herein , a first electrode of a fourth transistor m 4 included in the pixel circuit 142 ′ is connected to a first power elvdd and the rest of the components are established similarly as the pixel shown in fig3 . when the first electrode of the fourth transistor m 4 is connected to the first power elvdd , voltage levels of a first high power elvdd_h , a first low power elvdd_l , and a data signal voltage vdata are set as shown in equation 4 . referring to equation 4 , the data signal voltage vdata is set to a voltage equal to or lower than the first high power elvdd_h . that is , the pixel 140 according to a second embodiment of the present invention implements a gray level by a difference in voltage between the first high power elvdd_h and the data signal voltage vdata . the other detailed operation process is the same as that of the pixel 140 of fig3 and will thus not be provided again . fig6 is a diagram showing a pixel according to a third embodiment of the present invention . when fig6 is described , the same reference numerals refer to the same components as those of fig3 and a detailed description thereof will not be provided again . in addition , a pixel 140 connected to an n - th scan line sn and an m - th data line dm is shown for convenience of description . referring to fig6 , the pixel 140 according to the third embodiment of the present invention includes an organic light emitting diode oled and a pixel circuit 142 ″. the pixel circuit 142 ″ is connected between a third node n 3 and an initial voltage vint and includes a fifth transistor m 5 that is switched on when a scan signal is supplied to an n − 1 scan line sn − 1 . when the fifth transistor m 5 is switched on , initial voltage vint is supplied to the third node n 3 . in this case , the voltage of the first power elvdd maintains the voltage of the high level during a frame period . the voltage level including the initial voltage vint is set as shown in equation 5 . referring to equation 5 , the initial voltage vint is set to a voltage lower than the data signal voltage vdata . actually , the initial voltage vint is set to the voltage resulting from subtracting the threshold voltage of the first transistor m 1 , vth ( m 1 ), from the data signal voltage vdata . fig7 is a waveform diagram showing an embodiment of a driving method of a pixel shown in fig6 . referring to fig7 , during a compensation period cp , the scan signal is supplied to the scan lines s 1 to sn in sequence and a second control signal is supplied to a second control line cl 2 . in addition , the data signal is supplied to the data lines d 1 to dm . the data signal is synchronized with the scan signal . when the second control signal is supplied to the second control line cl 2 , a fourth transistor m 4 is switched on . when the fourth transistor m 4 is switched on , the reference voltage vref is supplied to the second node n 2 . in addition , when the scan signal is supplied to the n − 1 - th scan line sn − 1 , the fifth transistor m 5 is switched on . when the fifth transistor m 5 is switched on , the voltage at the third node n 3 is set to the initial voltage vint . thereafter , when the scan signal is supplied to the n - th scan line sn , the second transistor m 2 is switched on . when the second transistor m 2 is switched on , the data signal is supplied from the data line to the first node n 1 . at this time , the data signal voltage vdata is applied to the first node n 1 . when the data signal voltage vdata is applied to the first node n 1 , the voltage at the third node n 3 gradually increases up to a voltage resulting from subtracting the threshold voltage of the first transistor m 1 , vth ( m 1 ), from the data signal voltage vdata . herein , the compensation period cp is set to a sufficient time so that the voltage at the third node n 3 included in each of the pixels 140 increases up to the voltage resulting from subtracting the threshold voltage of the first transistor m 1 , vth ( m 1 ), from the data signal voltage vdata . meanwhile , during the compensation period cp , a voltage vref − vdata is charged in both ends of the second capacitor c 2 , and a voltage vref − vdata + vth ( m 1 ) is charged in both ends of the first capacitor c 1 . during the emission period ep , a first control signal cl 1 is supplied . when the first control signal cl 1 is supplied , the third transistor m 3 is switched on . when the third transistor m 3 is switched on , the first node n 1 and the second node n 2 are electrically connected to each other . in this case , the difference in voltage of both terminals of the first capacitor c 1 is set to 0 , and a voltage vgs ( m 1 ) between the gate electrode and the source electrode of the first transistor m 1 , also called the second electrode of the first transistor m 1 , is set to the voltage charged in the first capacitor c 1 . that is , the voltage between the gate electrode and the second electrode of the first transistor m 1 , vgs ( m 1 ), is set as shown in equation 2 . accordingly , the current flowing to the organic light emitting diode oled is determined by the difference in voltage between the reference voltage vref and the data signal voltage vdata as shown in equation 3 . fig8 is a diagram showing a pixel according to a fourth embodiment of the present invention . when fig8 is described , the same reference numerals refer to the same components as those of fig6 and a detailed description thereof will not be provided again . referring to fig8 , a pixel 140 according to the fourth embodiment of the present invention includes a pixel circuit 142 ′″ and an organic light emitting diode oled . a second electrode of a fifth transistor m 5 included in the pixel circuit 142 ′″ is connected to a first control line cl 1 . in this case , the fifth transistor m 5 is switched on when a scan signal is supplied to an n − 1 - th scan line sn − 1 to supply a voltage from the first control line cl 1 to a third node n 3 . when the first control signal is not supplied , the first control line cl 1 is set to a voltage that is lower than a voltage resulting from subtracting a threshold voltage of the first transistor m 1 , vth ( m 1 ) from a data signal voltage vdata . the other operation processes are the same as the fig6 and a detailed description will not be provided again . while the present invention has been described in connection with certain 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 , and equivalents thereof . | 6 |
referring to fig1 , a heat exchanger 10 in accordance with one embodiment of the present disclosure is illustrated . the heat exchanger in this example includes manifolds 12 and 14 that are arranged on opposite sides of a heat exchanger core 16 . in this example the manifolds 12 and 14 are identical in construction , but they need not be . it will be appreciated also that the dimensions and construction of the heat exchanger core 16 will dictate , at least in part , the outer dimensions of the manifolds 12 and 14 , as well as their dimensions . in fig1 manifold 12 has an inlet 18 and an outlet 20 . manifold 14 similarly has an inlet 22 and an outlet 23 . in this example the inlets and outlets have different diameters , but they could just as readily have the same diameter . in general operation , a fluid 19 may enter the inlet 18 of manifold 12 and circulate through the heat exchanger core 16 , where a major portion of heat transfer occurs to a cooling medium 21 , before the fluid exits outlet 23 . the cooling medium 21 may flow from inlet 22 to outlet 20 , and counter and parallel to the fluid 19 . the cooling medium 21 may be comprised of a liquid , a gas or any other fluid cooling medium that is flowable and capable of assisting in absorbing heat from the fluid entering inlet 18 . similarly , fluid 19 may be comprised of a liquid , a gas or any other flowable medium that requires cooling . referring to fig2 and 4 , a portion of the interior construction of the manifold 12 can be seen from a view looking straight into the inlet port 18 and outlet port 20 . since manifolds 12 and 14 are identical in construction , only the construction of manifold 12 will be described in detail . manifold 12 includes a plurality of vanes 24 that are arranged generally parallel to one another and spaced apart from one another . each of the vanes 24 forms two adjacent flow channels , first flow channel 26 a and second flow channel 26 b . each vane 24 further has a first end 24 a and a second end 24 b . first flow channel 26 a enables fluid 19 to flow therethrough , while the adjacent second flow channel 26 b enables the cooling medium 21 to flow therethrough counter to , but generally parallel to , the fluid 19 . each of channels 26 a has an input end 26 a 1 and an output end 26 a 2 , and each of channels 26 b has an input end 26 b 1 and an output end 26 b 2 . fig3 further schematically illustrates the counter flowing paths that the fluid 19 and the cooling medium 21 may take within the heat exchanger core 16 . it can also be seen from fig2 and 3 that the flow paths for the fluid 19 and the cooling medium 21 are arranged in alternating fashion to maximize heat transfer from the fluid 19 to the cooling medium 21 . opposing surface portions 30 a and 30 b ( fig2 and 5 ) of each vane 24 help to define the flow channels 26 a and 26 b . it is a benefit that the sum of cross sectional areas of all of the channels 26 a and 26 b defined by the vanes 24 approximately equals the cross sectional area of the inlet 18 . this is advantageous for maintaining a constant pressure in each manifold 12 and 14 , and avoiding a pressure drop across the heat exchanger 10 . however , it will be appreciated that if the needs of a particular application should dictate , that this ratio could be varied so that a greater or lesser cross sectional flow path area is provided for by the vanes 24 . additionally , the first and second fluids 19 and 21 could be flowed in the same direction if desired . referring to fig4 , when the fluid 19 enters the inlet 18 and begins to flow into the first flow channel 26 a , a ramp portion 28 of each vane 24 deflects the fluid vertically and also turns the fluid 19 about a twisting or spiral path as the fluid 19 begins to flow into the first flow channel 26 a . conversely , cooling fluid 21 returning to manifold 12 from the other manifold 14 will be deflected downwardly by each vane 24 as it enters the adjacent , second flow channel 26 b , and will flow along the second flow channel 26 b in a twisting or spiral path , but in the opposite sense as the fluid 19 flowing through the first flow channel 26 a . from fig5 - 13 , the cross - sectional shape and orientation of the two adjacent flow channels ( i . e ., paths ) 26 a and 26 b formed by each vane 24 can be seen to change along the length of the vane . in fig6 - 12 , the wall portion bridging vane 24 and wall portion 32 of the manifold 12 has been removed to reveal the interior area that forms the first flow channel 26 a . in particular , it will be noted that the aspect ratios ( i . e ., ratio of height - to - width ) of the two adjacent flow channels 26 a and 26 b defined by the vane 24 both change over the length of the vane in a similar but opposite ( i . e ., mirror image ) sense . this enables a counter - parallel - flow path configuration to be created . the adjacent flow channels 26 a and 26 b formed by each vane 24 also help to direct a greater portion of each the fluids 19 and 21 into contact with opposing wall surfaces of the vane 24 as each fluid flows through its respective flow channel 26 a or 26 b within the manifold 12 , thus ensuring more efficient cooling of the fluid 19 . the manifolds 12 and 14 , and particularly the vanes 24 , may be made from any suitable materials that enable excellent thermal conduction between the fluid 19 and the cooling medium 21 . suitable materials are aluminum , titanium , steel , etc ., but it will be appreciated that any suitable having reasonably good thermal conductivity may potentially be employed . the specific materials employed for the manifolds 12 and 14 may also depend in part on the specific types fluid that the manifolds will be used with . it will also be appreciated that the precise cross sectional shape and twisting orientation of the vanes 24 may be modified to suit the needs of a particular application . also , the total cross sectional area of the vanes 24 relative to the flow paths 26 may be varied to be suit the needs of a particular application . while various embodiments have been described , those skilled in the art will recognize modifications or variations which might be made without departing from the present disclosure . the examples illustrate the various embodiments and are not intended to limit the present disclosure . therefore , the description and claims should be interpreted liberally with only such limitation as is necessary in view of the pertinent prior art . | 1 |
the inventive method is preferably used to treat oil contaminated catalyst granulates , for example catalyst particles having an average diameter of about 5 mm . spent catalyst is contaminated with oil , hydrocarbons and other substances which are often pyrophoric . further , several toxic products are stuck to the surface of the catalyst which require a proper handling . the catalyst granulate is filled into a metal basket which is then enveloped by a plastic foil . since the catalyst material is contaminated with oil and other highly inflammable substances that filling process includes a certain risk of ignition . however , the loading of the catalyst granulate into the metal baskets is carried out at the refinery or petrochemical plant which is equipped with appropriate fire extinguishing means . then the enveloped catalyst granulate is transferred to a carbon dioxide cleaning installation . during the transport the plastic foil excludes any air from the inflammable catalyst material and thus there is no risk of ignition , fire or explosion . at the cleaning installation the plastic foil is removed from the metal basket . for safety reasons that removal is preferably carried out under inert gas atmosphere . the metal baskets filled with contaminated material are placed into the cleaning reactor of the carbon dioxide cleaning installation . again for safety reasons , the cleaning reactor is initially filled with gaseous carbon dioxide . thereby it is assured that the contaminated catalysts are handled in inert atmosphere all the time . then the cleaning reactor is closed and filled with liquid carbon dioxide . during filling surplus gaseous carbon dioxide is ventilated off the cleaning reactor . the liquid carbon dioxide is pressurized to 60 bar at a temperature of 15 ° c . and the cleaning operation in carbon dioxide is carried out for 75 minutes . the figure shows the result of a cleaning operation which has been repeated four times at the same conditions , that is at a pressure of 60 bar and a temperature of 15 ° c . after the first cleaning batch a weight reduction of about 8 % has been obtained . the reduction in weight of the metal basket filled with the initially contaminated catalyst is equivalent to the weight of oil removed from the catalyst . as shown in the figure , the weight reduction after four batches is already 16 %. between two cleaning batches , and / or alternatively continuously during the cleaning process , the dense phase carbon dioxide loaded with contaminants is withdrawn form the cleaning reactor and passed to a distillation vessel where the contaminants are separated from the carbon dioxide by distillation . the carbon dioxide is preferably filtered to collect insoluble small particles such as made of graphite , coke or ceramics . the carbon dioxide is condensed and passed to a storage tank for later use . the recovered oil contaminants are useful as refinery feedstock . after the cleaning step has been finished the metal basket is taken out of the cleaning reactor , and the cleaned catalyst material is unloaded from the metal basket and transferred to a metal recovery unit for further processing . it shall be pointed out that the speed and efficiency of cleaning can be further increased when one or more of the following measures are carried out : use of surfactants and additives , variations in pressure and / or temperature in order to force liquid and gas in and out of pores of the catalyst , enforced agitation of the dense phase gas by jet streams , propellers or by pumping dense phase gas through the cleaning reactor , mechanical agitation of the solids , for example by rotating the metal basket within the cleaning reactor . according to another embodiment of the present invention the oil contaminated catalyst granulate is loaded into bins or containers which are preferably inerted . at the cleaning installation the contaminated material is either transfilled into metal baskets or cassettes which comprises metal nets or other perforated material which allows gas and liquid to pass into the interior of the cassettes . the cleaning operation is then carried out as described above . if the cleaning reactor is provided with a rotating basket it is also possible to directly fill the contaminated granulate into that rotating basket . | 8 |
the present invention is carried out , for example , in such a manner that the herbicidal benzoylpyrazole compound is formulated by using various additives , and the formulation is diluted with e . g . water together with the activity - improving component and applied to undesired plants or to a place where they grow . further , the present invention is carried out in such a manner that the herbicidal benzoylpyrazole compound and the activity - improving component are formulated together by using various additives , and the formulation diluted with e . g . water or without being diluted is applied to undesired plants or to a place where they grow . in the above formula ( i ), the alkyl or the alkyl moiety has from about 1 to about 6 carbon atoms , may be either linear or branched , and may , for example , be specifically methyl , ethyl , propyl , butyl , tert - butyl , pentyl or hexyl . as the herbicidal benzoylpyrazole compound , for example , compounds as shown in table 1 may be mentioned . in table 1 , no . represents the compound number , me a methyl group , et an ethyl group and bu ( t ) a tertiary butyl group . these compounds are known compound disclosed in wo2007 / 069771 , wo2008 / 065907 , wo2008 / 078811 or wo2009 / 142318 . the salt contained in the herbicidal benzoylpyrazole compound may be any salt so long as it is agriculturally acceptable , and it may , for example , be specifically an alkali metal salt such as a sodium salt or a potassium salt ; an alkaline earth metal salt such as a magnesium salt or a calcium salt ; an amine salt such as a dimethylamine salt or a triethylamine salt ; an inorganic acid salt such as a hydrochloride , a perchlorate , a sulfate or a nitrate ; or an organic acid salt such as an acetate or a methanesulfonate . in a case where the herbicidal benzoylpyrazole compound has various structural isomers such as optical isomers or keto - enol tautomers , such isomers are , of course , included in the present invention . as at least one compound selected from the group consisting of a polyoxyalkylene sorbitan fatty acid ester , a polyoxyalkylene fatty acid ester , a polyoxyalkylene styryl aryl ether , a polyoxyalkylene styryl aryl ether condensate and a polyoxyalkylene alkyl ether sulfate , which is the activity - improving component , a commercially available surfactant containing the above compound may be used . in the above respective compounds as the activity - improving component , the number of addition of the oxyalkylene moiety is preferably from about 1 to about 100 , more preferably from about 1 to about 50 , further preferably from about 1 to about 30 , further preferably from about 4 to about 30 . further , the oxyalkylene moiety may be either linear or branched , and it preferably has , for example , from about 2 to about 3 carbon atoms . specific examples thereof include ethylene oxide , propylene oxide and — ch ( ch 3 ) ch 2 o —. hereinafter the polyoxyalkylene moiety may sometimes be referred to as poa and the polyoxyethylene moiety as poe . in the respective compounds as the activity - improving component , the oxyalkylene moiety may be a copolymer or a block copolymer , and the position of substitution of the oxyalkylene moiety is not particularly limited . now , the poa sorbitan fatty acid ester will be described below . the poa sorbitan fatty acid ester may be any of a mono - fatty acid ester , a di - fatty acid ester and a tri - fatty acid ester . the fatty acid moiety of the poa sorbitan fatty acid ester may be either a saturated fatty acid or an unsaturated fatty acid . the fatty acid moiety has preferably from about 4 to about 24 , more preferably from about 8 to about 20 carbon atoms . the fatty acid moiety may be linear , branched or cyclic , and may have a substituent . the number of the unsaturated bond ( s ) in the unsaturated fatty acid may be one or more , and the position is also optional . specific examples of the fatty acid moiety include butyric acid , valeric acid , caproic acid , enanthic acid , caprylic acid , pelargonic acid , capric acid , lauric acid , myristic acid , pentadecylic acid , palmitic acid , palmitoleic acid , margaric acid , stearic acid , oleic acid , vaccenic acid , linoleic acid , ( 9 , 12 , 15 )- linolenic acid , tuberculostearic acid , arachidic acid , arachidonic acid , behenic acid , erucic acid , lignoceric acid and nervonic acid . specific examples of the poa sorbitan fatty acid ester include the following compounds . further , tradenames for commercially available surfactants containing the compounds are exemplified . however , the activity - improving component of the present invention is not limited thereto . rheodol tw - l120 , tw - l106 , tw - p120 , tw - s120v , tw - s106v , tw - s320v , tw - o120v , tw - o106v and tw - o320v ( each manufactured by kao corporation ) sorbon t - 20 , t - 40 , t - 60 , t - 80 and t - 85 ( each manufactured by toho chemical industry co ., ltd .) agnique sml - 20 , sms - 20 , sts - 16 , sts - 20 , smo - 5 , smo - 20 , smo - 30 , sto - 20 , sto - 2095 and sto - 2299 ( each manufactured by basf ) nonion lt - 221 , lt - 20 , pt - 221 , ot - 206 , ot - 221 , ot - 80 , st - 206 , st - 221 , st - 60 , lt - 210 and ist - 221 ( each manufactured by nof corporation ) nikkol tl - 10 , tp - 10ex , ts - 10v , ts - 106v , ts - 30v , ti - 10 , to - 10 , to - 106v and to - 30v ( each manufactured by nikko chemicals co ., ltd .) the poa fatty acid ester may be either a mono - fatty acid ester or a di - fatty acid ester . the fatty acid moiety of the poa fatty acid ester is the same as that of the above - described poa sorbitan fatty acid ester . specific examples of the poa fatty acid ester include the following compounds . further , tradenames for commercially available surfactants containing the compounds are exemplified . however , the activity - improving component of the present invention is not limited thereto . pegnol 24 - o , 14 - o and eds ( s ) ( each manufactured by toho chemical industry co ., ltd .) agnique peg 200ml , 600ml , 200mo , 260mo , 300mo , 400mo , 600mo , 400ms , 660ms , 300do , 400do , 600do and 200dl ( each manufactured by basf ) cithrol 4ms , 10ms , 4ml , 6ml , 2do , 2de , 4dl and 4ds ( each manufactured by croda ) nikkol myl - 10 , mys - 10 , mys - 45 and myo - 10 ( each manufactured by nikko chemicals co ., ltd .) nonion l - 2 , l - 4 , o - 2 , o - 4 , o - 6 , s - 1 , s - 2 , s - 4 , s - 6 , s - 10 , s - 15 , mm - 4 , mm - 9 , is - 2 , is - 4 , is - 6 , dl - 4hn , dp - 1 . 5hn , do - 4hn , ds - 4hn , dis - 400 and dis - 600 ( each manufactured by nof corporation ) lionon mo - 60 , dt - 600m , dt - 600s and dbh - 40 ( each manufactured by lion corporation ) the poa styryl aryl ether may be any of a poa monostyryl aryl ether , a poa distyryl aryl ether and a poa tristyryl aryl ether . the aryl moiety of the poa styryl aryl ether may , for example , be phenyl . specific examples of the poa styryl aryl ether include the following compounds . further , tradenames for commercially available surfactants containing the compounds are exemplified . however , the activity - improving component of the present invention is not limited thereto . sorpol t - 10 , t - 15 , t - 20 , t - 26 , t - 30 , t - 32 and t - 18d ( each manufactured by toho chemical industry co ., ltd .) agnique tsp - 14 , tsp - 15 , tsp - 16 , tsp - 17 and tsp - 34 ( each manufactured by basf ) soprophor bsu , ts / 10 , ts / 16 , ts / 29 , ts / 54 , cy / 8 and s / 40 ( each manufactured by rhodia ) emulsogen ts100 , ts160 , ts200 , ts290 , ts400 , ts540 and ts600 ( each manufactured by clariant ) the poa styryl aryl ether condensate will be described below . the poa styryl aryl ether condensate is a condensate of a poa styryl aryl ether with formaldehyde . the poa styryl aryl ether condensate may be any of a poa monostyryl aryl ether condensate , a poa distyryl aryl ether condensate and a poa tristyryl aryl ether condensate , and optional ones among the poa monostyryl aryl ether , the poa distyryl aryl ether and the poa tristyryl aryl ether may be condensed . the aryl moiety of the poa styryl aryl ether may , for example , be phenyl . specific examples of the poa styryl aryl ether condensate include the following compounds . further , tradenames for commercially available surfactants containing the compounds are exemplified . however , the activity - improving component of the present invention is not limited thereto . sorpol f - 15 , f - 19 , f - 24 and f - 27 ( each manufactured by toho chemical industry co ., ltd .) the alkyl moiety of the poa alkyl ether sulfate preferably has from about 12 to about 14 carbon atoms . the alkyl moiety may be linear , branched or cyclic , and may have a substituent . specific examples of the alkyl moiety include dodecyl , tridecyl and tetradecyl . as the salt of the poa alkyl ether sulfate , various salts may be mentioned , such as a sodium salt , a potassium salt , a calcium salt , an ammonium salt and a triethanolamine salt . specific examples of the poa alkyl ether sulfate include the following compounds . further , tradenames for commercially available surfactants containing the compounds are exemplified . however , the activity - improving component of the present invention is not limited thereto . hitenol lal2 and la14 ( each manufactured by dai - ichi kogyo seiyaku co ., ltd .) nikkol nes - 203 - 27 , nes - 303 - 36 , sbl - 2a - 27 , sbl - 2n - 27 , sbl - 2t - 36 and sbl - 3n - 27 ( each manufactured by nikko chemicals co ., ltd .) emal 20c , e - 27c , 270j , 20cm , d - 3 - d , d - 4 - d , 20t , 125hp , 170j and 327 ( each manufactured by kao corporation ) persoft el , ek , ef , efk and ef - t ( each manufactured by nof corporation ) alscoap th - 330 , th - 330k , ns - 230 , th - 370n , da - 330s , n - 355t and a - 225b ( each manufactured by toho chemical industry co ., ltd .) in the present invention , the mixing ratio of the herbicidal benzoylpyrazole compound to the activity - improving component cannot generally be defined , as it varies depending upon various conditions such as the types of the herbicidal benzoylpyrazole compound and the activity - improving component , the type of the formulation , the weather conditions , and the type and the growth stage of plants to be controlled , and is preferably from 1 : 0 . 015 to 1 : 600 , more preferably from 1 : 0 . 03 to 1 : 600 , further preferably from 1 : 0 . 75 to 1 : 150 , particularly preferably from 1 : 0 . 75 to 1 : 100 by the weight ratio . the herbicidal composition of the present invention are capable of controlling a wide range of undesired weeds , such as gramineae such as barnyardgrass ( echinochloa crus - galli l ., echinochloa oryzicola vasing . ), crabgrass ( digitaria sanguinalis l ., digitaria ischaemum muhl ., digitaria adscendens henr ., digitaria microbachne henr ., digitaria horizontalis willd . ), green foxtail ( setaria viridis l . ), giant foxtail ( setaria faberi herrm . ), yellow foxtail ( setaria lutescens hubb . ), goosegrass ( eleusine indica l . ), wild oat ( avena fatua l . ), johnsongrass ( sorghum halepense l . ), quackgrass ( agropyron repens l . ), alexandergrass ( brachiaria plantaginea ), guineagrass ( panicum maximum jacq . ), paragrass ( panicum purpurascens ), sprangletop ( leptochloa chinensis ), red sprangletop ( leptochloa panicea ), annual bluegrass ( poa annua l . ), black grass ( alopecurus myosuroides huds . ), cholorado bluestem ( agropyron tsukushiense ( honda ) ohwi ), broadleaf signalgrass ( brachiaria platyphylla nash ), southern sandbur ( cenchrus echinatus l . ), italian ryegrass ( lolium multiflorum lam . ), and bermudagrass ( cynodon dactylon pers . ); cyperaceae such as rice flatsedge ( cyperus iria l . ), purple nutsedge ( cyperus rotundus l . ), yellow nutsedge ( cyperus esculentus l . ), japanese bulrush ( scirpus juncoides ), flatsedge ( cyperus serotinus ), small - flower umbrellaplant ( cyperus difformis ), slender spikerush ( eleocharis acicularis ), and water chestnut ( eleocharis kuroquwai ); alismataceae such as japanese ribbon waparo ( saqittaria pyqmaea ), arrow - head ( sagittaria trifolia ), and narrowleaf waterplantain ( alisma canaliculatum ); pontederiaceae such as monochoria ( monochoria vaginalis ), and monochoria species ( monochoria korsakowii ); scrophulariaceae such as false pimpernel ( lindernia pyxidaria ), and abunome ( dopatrium junceum ); lythraceae such as toothcup ( rotala india ), and red stem ( ammannia multiflora ); elatinaceae such as long stem waterwort ( elatine triandra schk . ); malvaceae such as velvetleaf ( abutilon theophrasti medic . ), and prickly sida ( sida spinosa l . ); compositae such as common cocklebur ( xanthium strumarium l . ), common ragweed ( ambrosia elatior l . ), thistle ( breea setosa ( bieb .) kitam . ), hairy galinsoga ( galinsoga ciliata blake ), wild chamomile ( matricaria chamomilla l . ); solanaceae such as black nightshade ( solanum nigrum l . ), and jimsonweed ( datura stramonium ); amaranthaceae such as slender amaranth ( amaranthus viridis l . ), and redroot pigweed ( amaranthus retroflexus l . ); polygonaceeae such as pale smartweed ( polygonum lapathifolium l . ), ladysthumb ( polygonum persicaria l . ), wild buckwheat ( polygonum convolvulus l . ), and knotweed ( polygonum aviculare l . ); cruciferae such as flexuous bittercress ( cardamine flexuosa with . ), shepherd &# 39 ; s - purse ( capsella bursa - pastoris medik . ), and indian mustard ( brassica juncea czern . ); convolvulaceae such as tall morningglory ( ipomoea purpurea l . ), field bindweed ( convolvulus arvensis l . ), and ivyleaf morningglory ( ipomoea hederacea jacq . ); chenopodiaceae such as common lambsquarters ( chenopodium album l . ), and mexican burningbush ( kochia scoparia schrad . ); portulacaceae such as common purslane ( portulaca oleracea l . ); leguminosae such as sicklepod ( cassia obtusifolia l . ); caryophyllaceae such as common chickweed ( stellaria media l . ); labiatae such as henbit ( lamium amplexicaule l . ); rubiaceae such as catchweed ( galium spurium l . ); euphorbiaceae such as threeseeded copperleaf ( acalypha australis l . ); and commelinaceae such as common dayflower ( commelina communis l .). therefore , they can be effectively used for selectively controlling noxious weeds in cultivation of useful crops such as corn ( zea mays l . ), soybean ( glycine max merr . ), cotton ( gossypium spp . ), wheat ( triticum spp . ), rice ( oryza sativa l . ), barley ( hordeum vulgare l . ), rye ( secale cereale l . ), oat ( avena sativa l . ), sorgo ( sorghum bicolor moench ), rape ( brassica napus l . ), sunflower ( helianthus annuus l . ), sugar beet ( beta vulgaris l . ), sugar cane ( saccharum officinarum l . ), japanese lawnqrass ( zoysia japonica stend ), peanut ( arachis hypogaea l . ), flax ( linum usitatissimum l . ), tobacco ( nicotiana tabacum l . ), and coffee ( coffea spp .). particularly , the herbicidal composition of the present invention is effectively used for selectively controlling noxious weeds in cultivation of corn , wheat , sugar cane , and the like . its application range extends to crop plant fields , orchards and plantations . and the herbicidal composition of the present invention can be effectively used for nonselectively controlling noxious weeds . the herbicidal composition of the present invention can effectively be used to selectively control noxious weeds in cultivation of various transgenic plants . examples of the transgenic plants include insect resistant transgenic plants , plant disease - resistant transgenic plants , transgenic plants regarding the plant constituents , and herbicide - resistant transgenic plants . the herbicidal benzoylpyrazole compound may be applied in an amount of preferably from 5 to 1 , 000 g / ha , more preferably from 10 to 100 g / ha . it is particularly very useful as a herbicidal composition for corn fields , since it can control noxious weeds or inhibit their growth without impairing corn . in the present invention , a herbicidal compound other than the herbicidal benzoylpyrazole compound may be mixed if desired , whereby more excellent effects or activity may be exhibited in some cases . for example , it may sometimes be possible to improve e . g . the range of the weeds to be controlled , the timing for the application of the herbicide or the herbicidal activities . the herbicidal benzoylpyrazole compound and another herbicidal compound may be individually prepared and mixed at the time of application , or they may be formulated together and applied . such another herbicidal compound may suitably be selected from the following compound groups ( 1 ) to ( 11 ) ( common names or test codes ). even when not specifically mentioned here , in a case where such compounds have salts , alkyl esters , structural isomers such as optical isomers etc ., they are , of course , all included . ( 1 ) those which are believed to exhibit herbicidal effects by disturbing hormone activities of plants , such as a phenoxy type such as 2 , 4 - d , 2 , 4 - d - butotyl , 2 , 4 - d - butyl , 2 , 4 - d - dimethylammonium , 2 , 4 - d - diolamine , 2 , 4 - d - ethyl , 2 , 4 - d - 2 - ethylhexyl , 2 , 4 - d - isobutyl , 2 , 4 - d - isoctyl , 2 , 4 - d - isopropyl , 2 , 4 - d - isopropylammonium , 2 , 4 - d - sodium , 2 , 4 - d - isopropanolammonium , 2 , 4 - d - trolamine , 2 , 4 - db , 2 , 4 - db - butyl , 2 , 4 - db - dimethylammonium , 2 , 4 - db - isoctyl , 2 , 4 - db - potassium , 2 , 4 - db - sodium , dichlorprop , dichlorprop - butotyl , dichlorprop - dimethylammonium , dichlorprop - isoctyl , dichlorprop - potassium , dichlorprop - p , dichlorprop - p - dimethylammonium , dichlorprop - p - potassium , dichlorprop - p - sodium , mcpa , mcpa - butotyl , mcpa - dimethylammonium , mcpa - 2 - ethylhexyl , mcpa - potassium , mcpa - sodium , mcpa - thioethyl , mcpb , mcpb - ethyl , mcpb - sodium , mecoprop , mecoprop - butotyl , mecoprop - sodium , mecoprop - p , mecoprop - p - butotyl , mecoprop - p - dimethylammonium , mecoprop - p - 2 - ethylhexyl , mecoprop - p - potassium , naproanilide or clomeprop ; an aromatic carboxylic acid type such as 2 , 3 , 6 - tba , dicamba , dicamba - butotyl , dicamba - diglycolamine , dicamba - dimethylammonium , dicamba - diolamine , dicamba - isopropylammonium , dicamba - potassium , dicamba - sodium , dichlobenil , picloram , picloram - dimethylammonium , picloram - isoctyl , picloram - potassium , picloram - triisopropanolammonium , picloram - triisopropylammonium , picloram - trolamine , triclopyr , triclopyr - butotyl , triclopyr - triethylammonium , clopyralid , clopyralid - olamine , clopyralid - potassium , clopyralid - triisopropanolammonium or aminopyralid ; and others such as naptalam , naptalam - sodium , benazolin , benazolin - ethyl , quinclorac , quinmerac , diflufenzopyr , diflufenzopyr - sodium , fluroxypyr , fluroxypyr - 2 - butoxy - 1 - methylethyl , fluroxypyr - meptyl , chlorflurenol , chlorflurenol - methyl , aminocyclopyrachlor , aminocyclopyrachlor - methyl or aminocyclopyrachlor - potassium . ( 2 ) those which are believed to exhibit herbicidal effects by inhibiting photosynthesis of plants , such as a urea type such as chlorotoluron , diuron , fluometuron , linuron , isoproturon , metobenzuron , tebuthiuron , dimefuron , isouron , karbutilate , methabenzthiazuron , metoxuron , monolinuron , neburon , siduron , terbumeton , trietazine or metobromuron ; a triazine type such as simazine , atrazine , atratone , simetryn , prometryn , dimethametryn , hexazinone , metribuzin , terbuthylazine , cyanazine , ametryn , cybutryne , triaziflam , indaziflam , terbutryn , propazine , metamitron or prometon ; a uracil type such as bromacil , bromacyl - lithium , lenacil or terbacil ; an anilide type such as propanil or cypromid ; a carbamate type such as swep , desmedipham or phenmedipham ; a hydroxybenzonitrile type such as bromoxynil , bromoxynil - octanoate , bromoxynil - heptanoate , ioxynil , ioxynil - octanoate , ioxynil - potassium or ioxynil - sodium ; and others such as pyridate , bentazone , bentazone - sodium , amicarbazone , methazole or pentanochlor . ( 3 ) quaternary ammonium salt type such as paraquat or diquat , which is believed to be converted to free radicals by itself to form active oxygen in the plant body and shows rapid herbicidal efficacy . ( 4 ) those which are believed to exhibit herbicidal effects by inhibiting chlorophyll biosynthesis of plants and abnormally accumulating a photosensitizing peroxide substance in the plant body , such as a diphenylether type such as nitrofen , chiomethoxyfen , bifenox , acifluorfen , acifluorfen - sodium , fomesafen , fomesafen - sodium , oxyfluorfen , lactofen , aclonifen , ethoxyfen - ethyl , fluoroglycofen - ethyl or fluoroglycofen ; a cyclic imide type such as chlorphthalim , flumioxazin , flumiclorac , flumiclorac - pentyl , cinidon - ethyl , fluthiacet or fluthiacet - methyl ; and others such as oxadiargyl , oxadiazon , sulfentrazone , carfentrazone - ethyl , thidiazimin , pentoxazone , azafenidin , isopropazole , pyraflufen - ethyl , benzfendizone , butafenacil , saflufenacil , flupoxam , fluazolate , profluazol , pyraclonil , flufenpyr - ethyl , bencarbazone , halauxifen , tiafenacil or ethyl [ 3 -( 2 - chloro - 4 - fluoro - 5 -( 3 - methyl - 2 , 6 - dioxo - 4 - trifluoromethyl - 3 , 6 - dihydro - 2h - pyrimidin - 1 - yl ) phenoxy ) pyridin - 2 - yloxy ] acetate . ( 5 ) those which are believed to exhibit herbicidal effects characterized by bleaching activities by inhibiting chromogenesis of plants such as carotenoids , such as a pyridazinone type such as norflurazon , chloridazon or metflurazon ; a pyrazole type such as pyrazolynate , pyrazoxyfen , benzofenap , topramezone or pyrasulfotole ; and others such as amitrole , fluridone , flurtamone , diflufenican , methoxyphenone , clomazone , sulcotrione , mesotrione , tembotrione , tefuryltrione , bicyclopyrone , isoxaflutole , difenzoquat , difenzoquat - metilsulfate , isoxachlortole , benzobicyclon , picolinafen , beflubutamid , cyclopyrimorate , kuh - 110 or a compound disclosed in the claim of wo2005118530 . ( 6 ) those which exhibit strong herbicidal effects specifically to gramineous plants , such as an aryloxyphenoxypropionic acid type such as diclofop - methyl , diclofop , pyriphenop - sodium , fluazifop - butyl , fluazifop , fluazifop - p , fluazifop - p - butyl , haloxyfop - methyl , haloxyfop , haloxyfop - etotyl , haloxyfop - p , haloxyfop - p - methyl , quizalofop - ethyl , quizalofop - p , quizalofop - p - ethyl , quizalofop - p - tefuryl , cyhalofop - butyl , fenoxaprop - ethyl , fenoxaprop - p , fenoxaprop - p - ethyl , metamifop - propyl , metamifop , clodinafop - propargyl , clodinafop or propaquizafop ; a cyclohexanedione type such as alloxydim - sodium , alloxydim , clethodim , sethoxydim , tralkoxydim , butroxydim , tepraloxydim , profoxydim or cycloxydim ; and others such as flamprop - m - methyl , flamprop - m or flamprop - m - isopropyl . ( 7 ) those which are believed to exhibit herbicidal effects by inhibiting an amino acid biosynthesis of plants , such as a sulfonylurea type such as chlorimuron - ethyl , chlorimuron , sulfometuron - methyl , sulfometuron , primisulfuron - methyl , primisulfuron , bensulfuron - methyl , bensulfuron , chlorsulfuron , metsulfuron - methyl , metsulfuron , cinosulfuron , pyrazosulfuron - ethyl , pyrazosulfuron , azimsulfuron , rimsulfuron , nicosulfuron , flazasulfuron , imazosulfuron , cyclosulfamuron , prosulfuron , flupyrsulfuron - methyl - sodium , flupyrsulfuron , triflusulfuron - methyl , triflusulfuron , halosulfuron - methyl , halosulfuron , thifensulfuron - methyl , thifensulfuron , ethoxysulfuron , oxasulfuron , ethametsulfuron , ethametsulfuron - methyl , iodosulfuron , iodosulfuron - methyl - sodium , sulfosulfuron , triasulfuron , tribenuron - methyl , tribenuron , tritosulfuron , foramsulfuron , trifloxysulfuron , trifloxysulfuron - sodium , mesosulfuron - methyl , mesosulfuron , orthosulfamuron , flucetosulfuron , amidosulfuron , propyrisulfuron , metazosulfuron , iofensulfuron or a compound disclosed in the claim of ep0645386 ; a triazolopyrimidinesulfonamide type such as flumetsulam , metosulam , diclosulam , cloransulam - methyl , florasulam , penoxsulam or pyroxsulam ; an imidazolinone type such as imazapyr , imazapyr - isopropylammonium , imazethapyr , imazethapyr - ammonium , imazaquin , imazaquin - ammonium , imazamox , imazamox - ammonium , imazamethabenz , imazamethabenz - methyl or imazapic ; a pyrimidinylsalicylic acid type such as pyrithiobac - sodium , bispyribac - sodium , pyriminobac - methyl , pyribenzoxim , pyriftalid or pyrimisulfan ; a sulfonylaminocarbonyltriazolinone type such as flucarbazone , flucarbazone - sodium , propoxycarbazone - sodium , propoxycarbazone or thiencarbazone ; and others such as glyphosate , glyphosate - sodium , glyphosate - potassium , glyphosate - ammonium , glyphosate - diammonium , glyphosate - isopropylammonium , glyphosate - trimesium , glyphosate - sesquisodium , glufosinate , glufosinate - ammonium , glufosinate - p , glufosinate - p - ammonium , glufosinate - p - sodium , bilanafos , bilanafos - sodium , cinmethylin or triafamone . ( 8 ) those which are believed to exhibit herbicidal effects by inhibiting cell mitoses of plants , such as a dinitroaniline type such as trifluralin , oryzalin , nitralin , pendimethalin , ethalfluralin , benfluralin , prodiamine , butralin or dinitramine ; an amide type such as bensulide , napropamide , propyzamide or pronamide ; an organic phosphorus type such as amiprofos - methyl , butamifos , anilofos or piperophos ; a phenyl carbamate type such as propham , chlorpropham , barban or carbetamide ; a cumylamine type such as daimuron , cumyluron , bromobutide or methyldymron ; and others such as asulam , asulam - sodium , dithiopyr , thiazopyr , chlorthal - dimethyl , chlorthal or diphenamid . ( 9 ) those which are believed to exhibit herbicidal effects by inhibiting protein biosynthesis or lipid biosynthesis of plants , such as a chloroacetamide type such as alachlor , metazachlor , butachlor , pretilachlor , metolachlor , s - metolachlor , thenylchlor , pethoxamid , acetochlor , propachlor , dimethenamid , dimethenamid - p , propisochlor or dimethachlor ; a thiocarbamate type such as molinate , dimepiperate , pyributicarb , eptc , butylate , vernolate , pebulate , cycloate , prosulfocarb , esprocarb , thiobencarb , diallate , tri - allate or orbencarb ; and others such as etobenzanid , mefenacet , flufenacet , tridiphane , cafenstrole , fentrazamide , oxaziclomefone , indanofan , benfuresate , pyroxasulfone , fenoxasulfone , dalapon , dalapon - sodium , tca - sodium or trichloroacetic acid . ( 10 ) msma , dsma , cma , endothall , endothall - dipotassium , endothall - sodium , endothall - mono ( n , n - dimethylalkylammonium ), ethofumesate , sodium chlorate , pelargonic acid , nonanoic acid , fosamine , fosamine - ammonium , pinoxaden , ipfencarbazone , aclolein , ammonium sulfamate , borax , chloroacetic acid , sodium chloroacete , cyanamide , methylarsonic acid , dimethylarsinic acid , sodium dimethylarsinate , dinoterb , dinoterb - ammonium , dinoterb - diolamine , dinoterb - acetate , dnoc , ferrous sulfate , flupropanate , flupropanate - sodium , isoxaben , mefluidide , mefluidide - diolamine , metam , metam - ammonium , metam - potassium , metam - sodium , methyl isothiocyanate , pentachlorophenol , sodium pentachlorophenoxide , pentachlorophenol laurate , quinoclamine , sulfuric acid , urea sulfate , methiozolin , etc . ( 11 ) those which are believed to exhibit herbicidal effects by being parasitic on plants , such as xanthomonas campestris , epicoccosirus nematosorus , epicoccosirus nematosperus , exserohilurn monoseras or drechsrela monoceras . in the present invention , in a case where the herbicidal benzoylpyrazole compound is formulated with various additives , or in a case where the herbicidal benzoylpyrazole compound and the activity - improving component are formulated together with various additives , it may be formulated into various formulations such as wettable powders , water dispersible granules , water - based suspensions , oil - based suspensions , gel formulation , emulsifiable concentrates , soluble concentrates , liquid formulation , emulsions , microemulsions , suspoemulsions and composite emulsions . the additives which can be used may be any additives so long as they are used in this technical field , and they may , for example , be a surfactant , a carrier , a solvent , a vegetable oil , a mineral oil , an anti - settling agent , a thickener , an anti - foaming agent , an anti - freezing agent , an antioxidant agent , an oil absorb agent , a gelling agent , a filler , a dispersion stabilizer , a safener , an anti - mold agent , a binder , a stabilizer , a disintegrator , a preservative agent and an inorganic ammonium salt . specific examples of the additives include the following compounds . the herbicidal benzolypyrazole compound can be formulated in accordance with a conventional method in this technical field . the surfactant may , for example , be an anionic surfactant such as a salt of fatty acid , a benzoate , an alkylsulfosuccinate , a dialkylsulfosuccinate , a polycarboxylate , a salt of alkyl sulfuric acid ester , an alkyl sulfate , an alkyl aryl sulfate , an alkyl diglycol ether sulfate , a salt of alcohol sulfuric acid ester , an alkyl sulfonate , an alkyl aryl sulfonate , an aryl sulfonate , a lignin sulfonate , an alkyl diphenyl ether disulfonate , a polystyrene sulfonate , a salt of alkyl phosphoric acid ester , an alkyl aryl phosphate , a styryl aryl phosphate , a salt of poe alkyl ether sulfuric acid ester , a poe alkyl aryl ether sulfate , a poe styryl aryl ether sulfate , a poe styryl aryl ether sulfonate , an ammonium salt of poe styryl aryl ether sulfate , a salt of poe alkyl aryl ether sulfuric acid ester , a poe alkyl ether phosphate , a salt of poe alkyl aryl phosphoric acid ester , a poe styryl aryl ether phosphoric acid ester or its salt , a salt of naphthalene suifonic acid condensed with formaldehyde , or a salt of alkylnaphthalene sulfonic acid condensed with formaldehyde ; a nonionic surfactant such as a sorbitan fatty acid ester , a glycerin fatty acid ester , a fatty acid polyglyceride , a fatty acid alcohol polyglycol ether , acetylene glycol , acetylene alcohol , an oxyalkylene block polymer , a poe alkyl ether , a poe aryl ether , a poe alkyl aryl ether , a poe styryl aryl ether , a poe glycol alkyl ether , a poe alkyl ester , a poe sorbitan alkyl ester , a poe sorbitol alkyl ester , a poe fatty acid ester , a poe sorbitan fatty acid ester , a poe sorbitol fatty acid ester , a poe glycerin fatty acid ester , poe hydrogenated castor oil , poe castor oil or a polyoxypropylene fatty acid ester ; or a cationic surfactant such as an alkoxylated fatty amine , and they may be used as a mixture of two or more if desired . the carrier or the filler may , for example , be diatomaceous earth , slaked lime , calcium carbonate , talc , white carbon , kaolin , bentonite , a mixture of kaolinite and sericite , clay , sodium carbonate , sodium bicarbonate , mirabilite , zeolite , starch , sodium chloride , ammonium phosphate , ammonium sulfate , ammonium chloride , sugar , urea , lactose or glucose , and they may be used as a mixture of two or more if desired . the solvent may , for example , be water , solvent naphtha , paraffin , dioxane , acetone , isophorone , methyl isobutyl ketone , cyclohexane , dimethyl sulfoxide , dimethyl formamide , n - methyl - 2 - pyrolidone , an alcohol , acetic acid , butyric acid , isopropyl acetate , butyl acetate , alkylbenzene , alkylnaphthalene or a glycol . they may be used as a mixture of two or more if desired . the vegetable oil may , for example , be olive oil , kapok oil , castor oil , papaya oil , camelia oil , coconut oil , sesame oil , corn oil , rice bran oil , peanut oil , cottonseed oil , soybean oil , rapeseed oil , linseed oil , tung oil , sunflower oil , safflower oil , a fatty acid derived from the above - described respective oils , or an alkyl ester of the fatty acid , and the mineral oil may , for example , be an aliphatic hydrocarbon such as liquid paraffin or paraffin petroleum , or an aromatic hydrocarbon such as an alkylbenzene or an alkylnaphthalene , and they may be used as a mixture of two or more if desired . the above - described fatty acid may , for example , be a c 12 - 22 saturated or unsaturated fatty acid such as lauric acid , palmitic acid , stearic acid , oleic acid , linoleic acid , linolenic acid , erucic acid or brassidic acid , and the alkyl ester thereof may be a c 1 - 18 linear or branched alkyl ester such as a methyl ester , a butyl ester , an isobutyl ester or an oleyl ester . the anti - settling agent may , for example , be silica , organic bentonite ( bentonite - alkylamino complex ), bentonite , white carbon or aluminum magnesium silicate , and they may be used as a mixture of two or more if desired . the thickener may , for example , be a heteropolysaccharide such as xanthan gum or guar gum , a water - soluble polymer such as polyvinyl alcohol , carboxymethylcellulose sodium salt or sodium alginate , or bentonite or white carbon , and they may be used as a mixture of two or more if desired . the anti - foaming agent may , for example , be polydimethylsiloxane or acetylene alcohol , and they may be used as a mixture of two or more if desired . the anti - freezing agent may , for example , be ethylene glycol , propylene glycol , glycerin or urea , and they may be used as a mixture of two or more if desired . the oil absorb agent may , for example , be silicon dioxide , starch hydrolysate , kaolin , clay , talc , diatomaceous earth , artificial diatomaceous earth / lime , asbestos , a mixture of kaolinite and sericite , calcium silicate , precipitated calcium carbonate light , silicificated precipitated calcium carbonate light , acid clay , carbon black , natural earthy graphite , pearlite product , ultrafine aluminum oxide anhydrous particles , ultrafine titanium oxide particles , basic magnesium carbonate , magnesium aluminosilicate , a silica / alumina synthetic filler or magnesium silicate hydrate , and they may be used as a mixture of two or more if desired . the gelling agent may , for example , be silica , organic attapulgite , clay , hydrogenated castor oil , a higher fatty acid ester , a higher alcohol , a salt of dialkylsulfosuccinic acid ester , a salt of benzoic acid , an alkyl sulfate , a mixture of a polyacrylic polymer or a polyacrylic copolymer and water , or 12 - hydroxystearic acid , and they may be used as a mixture of two or more if desired . the binder may , for example , be lignin sulfonate , xanthan gum , carboxymethylcellulose or starch , and they may be used as a mixture of two or more if desired . the disintegrator may , for example , be an inorganic salt such as carboxymethyl cellulose calcium salt , ammonium sulfate , potassium chloride or magnesium chloride , or one having disintegrating effect among the above - mentioned surfactants , such as sodium lauryl sulfate , sodium dodecylbenzene sulfonate or ammonium polyacrylate , and they may be used as a mixture of two or more if desired . the preservative agent may , for example , be formaldehyde , parachlorometaxylenol or 1 , 2 - benzoisothiazolin - 3 - one , and they may be used as a mixture of two or more if desired . in the above various formulations , the blend ratio of the respective components cannot be generally be defined , as it varies depending upon various conditions such as the type of the components , the type of the formulation , and the application site . for example , the herbicidal benzoylpyrazole compound is blended in a ratio of preferably from 0 . 1 to 95 parts by weight , more preferably from 2 to 85 parts by weight , and as the rest , the additives are blended in a ratio of preferably from 5 to 99 . 9 parts by weight , more preferably from 15 to 98 parts by weight . further , in a case where the activity - improving component is blended in a ratio of preferably from 0 . 1 to 94 . 9 parts by weight , more preferably from 5 to 60 parts by weight if desired , and another herbicidal compound is blended in a ratio of preferably from 0 . 1 to 94 . 9 parts by weight , more preferably from 0 . 5 to 75 parts by weight if desired , the additives are blended as the rest , so that the total amount is 100 parts by weight . the blend ratios of the respective components in several formulations are mentioned below , however , the present invention is not limited to such specific formulations . in the case of a water - based suspension , the herbicidal benzoylpyrazole compound is blended in a ratio of preferably from 0 . 1 to 60 parts by weight , more preferably from 2 to 50 parts by weight , the surfactant is blended in a ratio of preferably from 0 . 5 to 20 parts by weight , more preferably from 1 to 15 parts by weight , and as the rest , water is blended in a ratio of preferably from 25 to 99 . 4 parts by weight , more preferably from 30 to 97 parts by weight to prepare a water - based suspension . further , in a case where the activity - improving component is blended in a ratio of preferably from 0 . 1 to 60 parts by weight , more preferably from 5 to 40 parts by weight if desired , another herbicidal compound is blended in a ratio of preferably from 0 . 1 to 60 parts by weight , more preferably from 0 . 5 to 30 parts by weight if desired , an anti - foaming agent is blended in a ratio of preferably from 0 . 05 to 3 parts by weight , more preferably from 0 . 1 to 1 part by weight if desired , an anti - freezing agent is blended in a ratio of preferably from 0 . 5 to 10 parts by weight , more preferably from 2 to 10 parts by weight if desired , an anti - settling agent is blended in a ratio of preferably from 0 . 1 to 5 parts by weight , more preferably from 0 . 5 to 3 parts by weight if desired , a thickener is blended in a ratio of preferably from 0 . 1 to 5 parts by weight , more preferably from 0 . 1 to 2 parts by weight if desired , and a preservative agent is blended in a ratio of preferably from 0 . 01 to 1 part by weight , more preferably from 0 . 05 to 0 . 2 part by weight if desired , water is blended as the rest so that the total amount is 100 parts by weight to prepare a water - based suspension . in the case of an oil - based suspension , the herbicidal benzoylpyrazole compound is blended in a ratio of preferably from 0 . 1 to 40 parts by weight , more preferably from 2 to 35 parts by weight , the surfactant is blended in a ratio of preferably from 1 to 30 parts by weight , more preferably from 1 to 25 parts by weight , and as the rest , an oil , preferably a vegetable oil or a mineral oil is blended in a ratio of preferably from 10 to 98 . 9 parts by weight , more preferably from 20 to 97 parts by weight to prepare an oil - based suspension . further , in a case where the activity - improving component is blended in a ratio of preferably from 0 . 1 to 80 parts by weight , more preferably from 5 to 60 parts by weight if desired , another herbicidal compound is blended in a ratio of preferably from 0 . 1 to 40 parts by weight , more preferably from 0 . 5 to 30 parts by weight if desired , and an anti - settling agent is blended in a ratio of preferably from 0 . 1 to 5 parts by weight , more preferably from 0 . 5 to 3 parts by weight if desired , a vegetable oil or a mineral oil is blended as the rest so that the total amount is 100 parts by weight to prepare an oil - based suspension . in the case of a wettable powder , the herbicidal benzoylpyrazole compound is blended in a ratio of preferably from 0 . 1 to 95 parts by weight , more preferably from 5 to 85 parts by weight , the surfactant is blended in a ratio of preferably from 0 . 5 to 40 parts by weight , more preferably from 5 to 30 parts by weight , and as the rest , a carrier or a filler is blended in a ratio of preferably from 4 . 5 to 99 . 4 parts by weight , more preferably from 10 to 90 parts by weight to prepare a wettable powder . further , in a case where the activity - improving component is blended in a ratio of preferably from 0 . 1 to 94 . 9 parts by weight , more preferably from 10 to 60 parts by weight if desired , another herbicidal compound is blended in a ratio of preferably from 0 . 1 to 94 . 9 parts by weight , more preferably from 0 . 5 to 75 parts by weight if desired , and an oil absorb agent is blended in a ratio of preferably from 1 to 90 parts by weight , more preferably from 1 to 50 parts by weight if desired , a carrier or a filler is blended as the rest so that the total amount is 100 parts by weight to prepare a wettable powder . preferred embodiments of the present invention will be described below , but the present invention is by no means restricted thereto . 1 . a herbicidal composition comprising ( 1 ) 1 -( 1 - ethyl - 4 -( 3 -( 2 - methoxyethoxy )- 2 - methyl - 4 -( methylsulfonyl ) benzoyl )- 1h - pyrazol - 5 - yloxy ) ethyl methyl carbonate ( the above compound no . 6 ) or its salt and ( 2 ) at least one compound selected from the group consisting of a poa sorbitan fatty acid ester , a poa fatty acid ester , a poa styryl aryl ether , a poa styryl aryl ether condensate and a poa alkyl ether sulfate ( hereinafter referred to as an activity - improving component ). 2 . the herbicidal composition according to the above 1 , wherein the activity - improving component is at least one compound selected from the group consisting of a poa sorbitan fatty acid ester and a poa fatty acid ester . 3 . the herbicidal composition according to the above 1 , wherein the activity - improving component is a poa sorbitan fatty acid ester . 4 . the herbicidal composition according to the above 1 , wherein the activity - improving component is a poa fatty acid ester . 5 . a method for controlling undesired plants , which comprises applying ( 1 ) the above compound no . 6 or its salt and ( 2 ) the activity - improving component to the undesired plants or to a place where they grow . 6 . the method according to the above 5 , wherein the activity - improving component is at least one compound selected from the group consisting of a poa sorbitan fatty acid ester and a poa fatty acid ester . 7 . the method according to the above 5 , wherein the activity - improving component is a poa sorbitan fatty acid ester . 8 . the method according to the above 5 , wherein the activity - improving component is a poa fatty acid ester . 9 . a method for improving the herbicidal activity of the compound no . 6 or its salt by using the activity - improving component . 10 . the method according to the above 9 , wherein the activity - improving component is at least one compound selected from the group consisting of a poa sorbitan fatty acid ester and a poa fatty acid ester . 11 . the method according to the above 9 , wherein the activity - improving component is a poa sorbitan fatty acid ester . 12 . the method according to the above 9 , wherein the activity - improving component is a poa fatty acid ester . 13 . the herbicidal composition according to the above 3 , the method according to the above 7 , or the method according to the above 11 , wherein the poa sorbitan fatty acid ester is at least one compound selected from the group consisting of poe sorbitan monolaurate , poe sorbitan dilaurate , poe sorbitan trilaurate , poe sorbitan monopalmitate , poe sorbitan dipalmitate , poe sorbitan tripalmitate , poe sorbitan monomyristate , poe sorbitan dimyristate , poe sorbitan trimyristate , poe sorbitan monostearate , poe sorbitan distearate , poe sorbitan tristearate , poe sorbitan monoisostearate , poe sorbitan diisostearate , poe sorbitan triisostearate , poe sorbitan monooleate , poe sorbitan dioleate and poe sorbitan trioleate . 14 . the herbicidal composition according to the above 4 , the method according to the above 8 or the method according to the above 12 , wherein the poa fatty acid ester is at least one compound selected from the group consisting of poe monolaurate , poe dilaurate , poe monooleate , poe dioleate , poe monostearate , poe distearate , poe monoisostearate , poe diisostearate , poe monopalmitate , poe dipalmitate , poe monomyristate , poe dimyristate , poe di - 2 - ethylhexoate and poe dierucate . 15 . the herbicidal composition according to the above 4 , the method according to the above 8 or the method according to the above 12 , wherein the poa fatty acid ester is poa di - fatty acid ester . 16 . an oil - based suspension comprising ( 1 ) the above compound no . 6 or its salt , ( 2 ) the activity - improving component , ( 3 ) a surfactant and ( 4 ) a vegetable oil or a mineral oil . 17 . the oil - based suspension according to the above 16 , wherein the activity - improving component is at least one compound selected from the group consisting of a poa sorbitan fatty acid ester and a poa fatty acid ester . 18 . the oil - based suspension according to the above 16 , wherein the activity - improving component is a poa sorbitan fatty acid ester . 19 . the oil - based suspension according to the above 16 , wherein the activity - improving component is a poa fatty acid ester . 20 . the oil - based suspension according to any one of the above 16 to 19 , wherein ( 3 ) the surfactant is at least one surfactant selected from the group consisting of poe hydrogenated castor oil , poe styryl phenyl ether , a poe sorbitol fatty acid ester and a sorbitan fatty acid ester . 21 . the oil - based suspension according to any one of the above 16 to 20 , wherein ( 4 ) the vegetable oil or the mineral oil is a vegetable oil , a fatty acid derived from the vegetable oil or an alkyl ester of the fatty acid . 22 . the oil - based suspension according to any one of the above 16 to 21 , which contains ( 1 ) from 0 . 1 to 40 parts by weight of the above compound no . 6 or its salt , ( 2 ) from 0 . 1 to 80 parts by weight of the activity - improving component , ( 3 ) from 1 to 30 parts by weight of the surfactant , and ( 4 ) from 10 to 98 . 8 parts by weight of the vegetable oil or the mineral oil . 23 . an oil - based suspension , which contains ( 1 ) from 0 . 1 to 40 parts by weight of the above compound no . 6 or its salt , ( 2 ) from 0 . 1 to 80 parts by weight of the activity - improving component , ( 3 ) from 1 to 30 parts by weight of a surfactant , ( 4 ) from 0 . 1 to 5 parts by weight of an anti - settling agent and ( 5 ) from 10 to 98 . 7 parts by weight of a vegetable oil or a mineral oil . now , the present invention will be described in further detail with reference to examples . however , the present invention is by no means restricted to such specific examples . compound nos . in examples are compound nos . in the above table 1 . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity 99 . 6 %): 36 . 26 parts by weight ( 2 ) alkylnaphthalene sulfonate condensed with formaldehyde ( tradename : morwet d425 manufactured by akzonobel ): 2 . 21 parts by weight ( 3 ) poe styryl phenyl ether phosphate potassium salt ( tradename : soprophor flk / 70 manufactured by rhodia ): 2 . 21 parts by weight ( 4 ) aluminum magnesium silicate ( tradename : veegum r manufactured by sanyo chemical industries , ltd . ): 0 . 88 part by weight ( 6 ) dimethylpolysiloxane ( tradename : silcolapse 432 manufactured by bluestar silicones ): 0 . 35 part by weight ( 7 ) xanthan gum ( tradename : rhodopol 23 manufactured by rhodia ): 0 . 09 part by weight ( 8 ) 1 , 2 - benzisothiazolin - 3 - one ( tradename : proxel gxl manufactured by arch chemicals , inc . ): 0 . 04 part by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare a water - based suspension . this is diluted with water together with the activity - improving component and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 36 . 26 parts by weight ( 2 ) morwet d425 ( tradename ): 2 . 65 parts by weight ( 3 ) ammonium poe styryl phenyl ether sulfonate ( tradename : soprophor 4d384 manufactured by rhodia ): 2 . 21 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare a water - based suspension . this is diluted with water together with the activity - improving component and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 36 . 26 parts by weight ( 3 ) poe / polyoxypropylene block copolymer ( tradename : pluronic pe10300 manufactured by basf ): 2 . 21 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare a water - based suspension . this is diluted with water together with the activity - improving component and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 10 . 67 parts by weight ( 2 ) mixture containing poe hydrogenated castor oil ( tradename : sorpol 3815a manufactured by toho chemical industry co ., ltd . ): 10 . 42 parts by weight ( 3 ) organic bentonite ( bentonite - alkylamino complex ) ( tradename : new d orben manufactured by shiraishi kogyo kaisha , ltd . ): 1 . 04 parts by weight ( 4 ) poe sorbitan fatty acid ester ( tradename : sorbon t - 85 manufactured by toho chemical industry co ., ltd . ): 20 . 83 parts by weight ( 5 ) methylated seed oil ( tradename : agnique me 18rd - f manufactured by basf ): 57 . 04 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 10 . 67 parts by weight ( 4 ) isoparaffin ( tradename : ip solvent 1016 manufactured by idemitsu kosan co ., ltd . ): 57 . 04 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 31 . 25 parts by weight ( 3 ) silica ( tradename : aerosil r972 manufactured by nippon aerosil co ., ltd . ): 0 . 63 part by weight ( 4 ) poe styryl phenyl ether ( tradename : sorpol - 19 manufactured by toho chemical industry co ., ltd . ): 10 . 42 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 10 . 67 parts by weight ( 2 ) mixture containing poe sorbitol fatty acid ester ( tradename : sorpol 4300 manufactured by toho chemical industry co ., ltd . ): 10 . 42 parts by weight ( 4 ) poe fatty acid ester ( tradename : pegnol 24 - 0 manufactured by toho chemical industry co ., ltd . ): 52 . 08 parts by weight ( 5 ) methylated seed oil ( tradename : agnique me 18rd - f manufactured by basf ): 25 . 79 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 10 . 67 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 1 ) compound no . 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 or 9 ( purity : 99 . 6 %): 10 . 67 parts by weight ( 2 ) polycarboxylate ( tradename : geropon t / 36 manufactured by rhodia ): 3 parts by weight ( 3 ) alkylnaphthalene sulfonate ( tradename : supragil wp manufactured by rhodia ): 2 parts by weight ( 4 ) alkyl naphthalene sulfonate condensed with formaldehyde ( tradename : supragil mns / 90 manufactured by rhodia ): 5 parts by weight ( 5 ) poe alkyl ether sulfate ( tradename : hitenol lal2 manufactured by dai - ichi kogyo seiyaku co ., ltd . ): 40 parts by weight ( 6 ) white carbon ( tradename : carplex # 80 manufactured by evonik degussa japan co ., ltd . ): 39 . 33 parts by weight hitenol lal2 is adsorbed on carplex # 80 , and mixed with the other components to prepare a wettable powder . this is diluted with water and applied . the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 3 ) poe sorbitan fatty acid ester ( tradename : sorbon t - 60 manufactured by ( 4 ) sorbitan fatty acid ester ( tradename : sorbon s - 80 manufactured by toho chemical industry co ., ltd . ): 10 . 0 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . ( 3 ) poe fatty acid ester ( tradename : cithrol 4ml manufactured by croda ): 30 . 0 parts by weight the above components are mixed and pulverized by a wet pulverizer for 5 minutes to prepare an oil - based suspension . this is diluted with water and applied . now , test examples will be described . the activity - improving components used in test examples are as follows . upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of barnyardgrass ( echinochloa crus - galli l .) and seeds of velvetleaf ( abutilon theophrasti l .) were respectively sown and grown in a greenhouse . when the barnyardgrass reached 4 . 0 to 4 . 7 - leaf stage and the velvetleaf reached 3 . 0 to 4 . 0 - leaf stage , a prescribed amount ( 15 g a . i ./ ha ) of a composition comprising compound no . 6 as an active ingredient prepared in accordance with example 1 was diluted with water ( containing 0 . 05 vol % of the activity - improving component ) in an amount corresponding to 300 l / ha , and applied for foliar treatment . for comparison , a behenic acid monoethanolamide surfactant ( tradename : incromide manufactured by croda ) was used at a concentration of 0 . 05 vol % instead of the activity - improving component of the present invention , and the composition was applied for foliar treatment similarly . on the 25th day after treatment , the state of growth of the plants was visually observed to determine the growth inhibition rate (%)= 0 ( equivalent to the non - treated area ) to 100 ( complete kill ), and the results as shown in table 2 were obtained . in accordance with the above test example 1 , the effect on velvetleaf ( abutilon theophrasti l .) at 2 . 0 to 3 . 0 - leaf stage was confirmed . for comparison , a methylated seed oil activity - strengthening agent ( tradename : destiny ho manufactured by agriliance ) was used at a concentration of 0 . 5 vol %. on the 21st day after treatment , the growth inhibition rate (%) was determined in the same manner as in test example 1 and the results are shown in table 3 . in accordance with the above test example 1 , the effect on velvetleaf ( abutilon theophrasti l .) at 3 . 3 to 3 . 8 - leaf stage was confirmed . for comparison , methyl oleate ( a mixture of methyl oleate : commercially available emulsifying agent = 88 : 12 ) was used at a concentration of 0 . 05 vol %. the commercially available emulsifying agent used was a mixture of poe alkyl aryl ether , poe hydrogenated castor oil ether , a fatty acid derivative and sodium dialkylsulfosuccinate ( tradename : sorpol 3815k , manufactured by toho chemical industry co ., ltd .). on the 21st day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 4 . in accordance with the above test example 1 , the effect on barnyardgrass ( echinochloa crus - galli l .) at 3 . 5 to 4 . 3 - leaf stage was confirmed . for comparison , methyl oleate ( the same as in test example 3 ) was used at a concentration of 0 . 05 vol %. on the 23rd day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 5 . here , when no activity - improving component was added , the growth inhibition rate of barnyardgrass was 0 %. upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of crabgrass ( digitaria ciliaris ( retz .) koel .) were sown and grown in a greenhouse . when the crabgrass reached 3 . 6 to 4 . 2 - leaf stage , a prescribed amount ( 30 g a . i ./ ha ) of a composition comprising compound no . 6 as an active ingredient prepared in accordance with example 1 was diluted with water ( containing 0 . 05 vol % of the activity - improving component ) in an amount corresponding to 300 l / ha , and applied for foliar treatment . for comparison , a polyoxyethylene octyl phenyl ether surfactant ( tradename : kusarino manufactured by nihon noyaku co ., ltd .) or methyl oleate ( the same as in test example 3 ) were used at a concentration of 0 . 05 vol % instead of the activity - improving component of the present invention , and each composition was applied similarly . on the 25th day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 6 . upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of barnyardgrass ( echinochloa crus - galli l .) were sown and grown in a greenhouse . when the barnyardgrass reached 4 . 0 to 5 . 0 - leaf stage , a prescribed amount ( 100 g a . i ./ ha ) of a composition comprising compound no . 6 as an active ingredient prepared in accordance with example 1 was diluted with water ( containing 0 . 025 vol % of the activity - improving component ) in an amount corresponding to 300 l / ha , and applied for foliar treatment . for comparison , kusarino ( the same as in test example 5 ) was used at a concentration of 0 . 025 vol % instead of the activity - improving component of the present invention , and the composition was applied similarly . on the 21st day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 7 . upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of velvetleaf ( abutilon theophrasti l .) were sown and grown in a greenhouse . when the velvetleaf reached 4 . 4 to 5 . 4 - leaf stage , a prescribed amount ( 10 g a . i ./ ha ) of a composition comprising compound no . 6 as an active ingredient prepared in accordance with example 1 was diluted with water ( containing 0 . 5 vol % of the activity - improving component ) in an amount corresponding to 300 l / ha , and applied for foliar treatment . for comparison , kusarino ( the same as in test example 5 ) was used at a concentration of 0 . 5 vol % instead of the activity - improving component of the present invention , and the composition was applied similarly . on the 22nd day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 8 . upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of barnyardgrass ( echinochloa crus - galli l .) and velvetleaf ( abutilon theophrasti l .) were sown and grown in a greenhouse . when the barnyardgrass reached 4 . 0 to 4 . 5 - leaf stage and the velvetleaf reached 2 . 7 to 3 . 5 - leaf stage , a prescribed amount ( 30 g a . i ./ ha ) of an oil - based suspension comprising compound no . 6 as an active ingredient prepared in accordance with example 10 was diluted with water in an amount corresponding to 300 l / ha , and applied for foliar treatment . on the 26th day after treatment , the state of growth of the barnyardgrass was visually observed , and on the 24th day after treatment , the state of growth of the velvetleaf was visually observed , to determine the growth inhibition rates in the same manner as in test example 1 and the results are shown in table 9 . upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of corn ( zea mays l .) were sown and grown in a greenhouse . when the corn reached 3 . 8 to 4 . 5 - leaf stage , a prescribed amount ( 30 , 60 or 90 g a . i ./ ha ) of an oil - based suspension comprising compound no . 6 as an active ingredient prepared in accordance with example 10 was diluted with water in an amount corresponding to 300 l / ha , and applied for foliar treatment . on the 6th day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 10 . upland field soil was put into a 1 / 1 , 000 , 000 ha pot , and seeds of crabgrass { p47051 02264045 . 000 } ( digitaria ciliaris ( retz .) koel .) and barnyardgrass ( echinochloa crus - galli l .) were sown and grown in a greenhouse . when the crabgrass reached 4 . 4 to 5 . 4 - leaf stage and the barnyardgrass reached 4 . 0 to 5 . 1 - leaf stage , prescribed amounts ( 30 + 30 g a . i ./ ha ) of oil - based suspensions each comprising compound no . 6 and nicosulfuron as active ingredients , prepared in accordance with examples 11 and 12 , were diluted with water in an amount corresponding to 300 l / ha and applied for foliar treatment . on the 21st day after treatment , the growth inhibition rate was determined in the same manner as in test example 1 and the results are shown in table 11 . | 0 |
the system of the present invention is based on the proposal for the system b access control system the practical implementation for which is described on page 435 etc . of ebu document spb 284 , on page 206 etc . of ebu document spb 352 and page 221 etc . of ebu doc . jiwp 10 - 11 / 3 - 1 mentioned above . a detailed description to system b is not given herein and the reader is directed to the above mentioned documents for an understanding of system b . in the following description the references used in relation to packets and blocks of data and their format are assumed to be as disclosed in the above documents and detailed explanations will only be entered into where these differ from the disclosures . with the system b proposal the shared customer address ( sca ) provides either the subscriber validation or authorisation in the subscription mode or loads tokens into the subscriber &# 39 ; s controlled access sub - system in the pay - per - view mode . for a given programme it is not possible for different subscribers to gain entitlement to receive that programme in an intelligible manner by the two different modes nor for a subscriber not pre - authorised to receive that programme to gain access to it via the pay - per - view mode . with the present system both possibilities exist . fig1 shows the shared - key over - air addressing system for system b which is based on fig3 of the mentioned parts of the above documents . the figure is divided into three portions where reference 1 denotes the parts contained on the transmission side , reference 2 a transmission path and 3 the parts contained on the receiver side which includes the controlled access sub - system . on the transmission side control words cw ( which includes the control words cw1 and cw2 ) are applied via a connection 4 to a scrambling sequence generator ( not shown ) to control the scrambling of programme material , both sound and vision . the control word cw is also applied to a first encrypter 5 together with any programme data p and which is encrypted using a supplementary key s to produce at the output of encrypter 5 the cryptogram s ( p , cw ). the supplementary key s together with customer messages m are applied to a second encrypter 6 and which are encrypted using a shared distribution key d to produce at the output of encrypter 6 the cryptogram d ( m , s ). in the transmission path 2 the cryptogram s ( p , cw ) is conveyed in an entitlement checking message ( ecm ) whilst the cryptogram d ( m , s ) is conveyed in an entitlement management message ( emm ). at the receiver side 3 a first decrypter 7 present in a security device 8 ( receives the cryptogram d ( m , s ) from the emm together with the shared distribution key d , the decrypter 7 producing the supplementary key s and any customer messages m at separate outputs . a second decrypter 9 receives the cryptogram s ( p , cw ) from the ecm together with the supplementary key s from decrypter 7 to produce at separate outputs the control word cw and any programme data p . the control word cw ( which again includes the control words cw1 and cw2 ) is applied via a connection 10 to a descrambling sequence generator ( not shown ) to control the descrambling of the programme material . the customer message m and the programme data p from the respective outputs of decrypters 7 and 9 are applied to a store 11 for example , for charging purposes . with the present system two overall encryption channels can be defined , these being a primary encryption channel and a subscription encryption channel . the primary encryption channel is the data path used by the controlled access sub - system to obtain programmes in the pay - per - view mode and it can also be used during switch - on to gain quick access to a service and hence quickly receive a programme in an intelligible manner . this channel in operation is similar to that of system b in the pay - per - view mode except that in the present system token updates are sent using the unique customer packets . the primary encryption channel consists of a number of components in packet form . in the following description of various packets each packet contains a packet header ( ph ) block of 23 bits and a packet type ( pt ) block of 8 bits which have been omitted from the descriptions although shown in the corresponding figures . in these figures the plain text messages are assembled least significant bit first , encrypted , and then transmitted least significant bit first . where a number is shown in brackets this indicates the number of bits used for each function , before encryption and error protection ( which is not shown ). the primary encryption channel comprises a primary emm and primary ecm &# 39 ; s ( one for each separately scrambled service ). the primary emm comprises unique customer and shared customer packets . the unique customer packet is shown in fig2 and comprises : ______________________________________uca unique customer address as system b - ( 36 ) bits . ucbmd mode as system b - ( 4 ) bits . u unique key as system b - ( 64 ) bits . sdkup shared distribution key update as system b - ( 64 ) bits . saup shared address update as system b - ( 48 ) bits . cpup customer word position update . the function definition remains the same as system b . the available customer bits have been reallocated to indicate one of 276 customers - ( 10 ) bits . ctup customer token update . the definition is identical to that given in system b under shared customer packet data format - ( 12 ) bits . unused - ( 118 ) bits . unallocated - ( 4 ) bits . ______________________________________ the blocks ucbmd upto and including the unused block of ( 118 ) bits are encrypted with the unique key u . the shared customer packet is shown in fig3 and comprises : ______________________________________sca shared customer address - ( 24 ) bits . valmd mode . if all bits are set to zero the operation is as described in this proposal . other combinations are reserved for future use - ( 4 ) bits . spn next pay - per - view view supplementary key . its use and operation are identical to that in system b except it is only employed with the primary pay - per - view emc - ( 56 ) bits . unallocated - ( 276 ) bits . ______________________________________ the blocks valmd and spn together with the unallocated block of ( 276 ) bits are encrypted with the shared distributed key d . the construction of each primary ecm is shown in fig4 and comprises : ______________________________________ci command identifier as system b - ( 8 ) bits . li length indicator as system b - ( 8 ) bits . pi parameter identifier whose function is the same as for system b - ( 8 ) bits . code 00 signifies ` pay - per - view ` plain text message . li length indicator as system b - ( 8 ) bits . skl supplementary key link as system b - ( 12 ) bits . pasemm packet address for the subscription shared customer emm . this is sent in plain text and allows the controlled access sub - system to gain access to the subscription emm packets . the two most significant bits are set to zero . if the packet address given is all zeroes the programme being transmitted is solely pay - per - view and no subscription emm packets are being trans - mitted - ( 12 ) bits . pasecm packet address for the subscription ecm . this again is sent in plain text and allows the controlled access sub - system to gain access to the subscription ecm packets . the two most significant bits are set to zero . if the packet address given is all zeros the programme being transmitted is solely pay - per - view and no subscription ecm packets are being trans - mitted - ( 12 ) bits . spn ( spc ) current pay - per - view supplementary key encrypted by the next pay - per - view supplementary key and has an identical function to sn ( sc ) in system b - ( 64 ) bits . pi parameter identifier whose function is the same as that in system b - ( 8 ) bits . code 02 signifies pay - per - view per unit time as system b whilst code 03 sig - nifies pay - per - view per programme as system b . li length indicator as system b - ( 8 ) bits . spc current primary supplementary key which has an identical function to sc in system b - ( 56 ) bits . cw control word ( 64 ) bits . this function transports even and odd controls words which can have suffixes from 0 to 7 . the even / odd identification signifies the parity of the conditional access frame count thus linking a control word with an ` odd ` or ` even ` 256 t . v . frame period . fig5 shows the format of the cw commmand with the least significant bit first . in the enlarged section of the first four bits of byte 1 b0 , b1 and b2 are the cw identifier whilst b3 is the least significant bit of the controlled access frame count to which the control word corresponds . pcat programme category as system b - ( 8 ) bits . chid channel identification as system b - ( 169 ) bits . pnum programme number as system b - ( 24 ) bits . pi parameter identifier - ( 8 ) bits . the block replicates that following spn ( spc ). ppvpr pay - per - view price - ( 24 ) bits . as system b except pi = 02 , 03 , respectively for the two modes of pay - per - view . that is per unit time or per programme . 5 bytes unallocated - 40 bits . ______________________________________ the blocks spc up to and including ppvpr are encrypted with spc . as far as subscriber authorisation is concerned a ` central computer ` at the transmission end will have continous record of the entitlements of each viewer with respect to the programmes he is allowed to watch . this should be the only place where that data is stored and only that data which tells the receiver that it is ( or is not ) entitled to receive a particular programme in an intelligible manner should be transmitted over - air . this means that the entitlement authorisations have to be sent out with each programme and that the subscription supplementary key will only have a current value ( ssc ) changing with every programme . to transport the subscription entitlements and the current subscription supplementary key ( ssc ) a shared customer emm employing 276 by 1 bit authorisations is used . this emm can enable ( or disable ) 20 million or more viewers in less than 3 minutes using an effective data capacity of one nicam parity mono sound channel whereas with the system b proposal it would take about 30 minutes to authorise the same number of viewers . the subscription encryption channel contains a shared customer emm and the subscription ecm . the subscription shared customer emm is shown in fig6 and contains ______________________________________sca shared customer address - ( 24 ) bits . common to 276 subscribers . valmd mode - ( 4 ) bits . all bits set to zero represents the operation as described in this proposal . other values are reserved for future use . ssc current subscription supplementary key - ( 56 ) bits . definition is similar to that in system b except it is employed in conjunction with the subscription ecm ( see below ), and is changed at the start of each pro - gramme . ca customer authorisations . 276 × 1 bit customer authorisations used to enable a customer and allow the contrblled access sub - system to gain access to the subscription ecm and hence the control words . a binary ` 1 ` corresponds to being enabled . ______________________________________ the blocks valmd , ssc and ca are encrypted with the shared distribution key d . this method of customer authorisation is dealt with in greater detail in published european patent application no . 0 132 007 a1 . as proposed here it allows 20 × 10 6 or more viewers to be authorised in less than 3 minutes . the current subscription supplementary key ssc is changed at the end of each programme to avoid piracy as it could be envisaged that a subscriber could take out a minimum subscription and be validated quite legally and still get access to the ssc if this were long term . the subscriber could then instruct his receiver to ignore all further subscription shared customer emm &# 39 ; s and although his location ( authorisation ) bit may be switched to disable the receiver will continue to receive valid programmes until the ssc is changed . thus , if for a sequence of programmes a new ssc is required for each programme and re - validation required for each programme . ______________________________________ci command identifier as system b - ( 8 ) bits . li length indicator as system b - ( 8 ) bits . pi parameter identifier whose function is the same as for system b - ( 8 ) bits . code 01 signifies ` subscription ` plain text message . li length indicator as system b - ( 8 ) bits . pl programme link - ( 16 ) bits . this give advanced indication of a change in ssc , i . e . at the end of programme . the 16 bits correspond to the 16 least significant bits of the controlled access frame count . pi parameter identifier whose function is the same as for system b - ( 8 ) bits . code 04 ` subscription ` cipher text message . li length indicator as system b - ( 8 ) bits . ssc current subscription supplementary key - ( 56 ) bits . definition is similar to that in system b and is used here as a security check . cw , pcat , chid , pnum , pias defined in the primary ecm ( fig4 ). 30 bytes unallocated - 240 bits . ______________________________________ the blocks ssc up to and including pi are encrypted with ssc . whilst by using a system of packets as described above to achieve the ability of receiving a programme either in the subscription or pay - per - view modes , it also offers a high degree of security . the security aspects are based on the following : i . the security of the system is based on the unique address , the unique key and if these are tied to a specific brand and serial number of receiver the security is further enhanced . ii . cloning of the system must be one approach of a pirate to avoid payments . however , if the checks set out in ( i ) above are strictly applied then programme purchase would have to be by a single person and the unit a major item . cloning is only of advantage in the subscription mode , it does not give free pay - per - view . further the system allows for a unique address to be disabled from the system by giving a new shared address to the other 275 valid occupants of that address . the old shared address is no longer transmitted and up - dated with the new keys . no legally purchased systems are disabled . iii . another level of attack has to be at the shared address packet and its contents . in particular the next supplementary key spn . if in some way access could be achieved to this key then it could be envisaged that the pay - per - view mechanism could be by - passed . to reduce the risk of this occurring important keys such as spn which have to be stored in the control access unit for significant periods could be stored encrypted with the unit &# 39 ; s unique key . in this way the plain text version of these keys only exist transiently in the control access sub - system central processor unit . considerable care should be given to the security of the unique address key . iv . in the subscription mode the keys are of short duration . however , a possible method of attack is to arrange that all the customer bits are set to enable . it seems extremely unlikely that this could be done on the received signal and would have to be tackled within the controlled access sub - system software . v . a controlled access sub - system designed to by - pass the above with a unique address and key from a legitimately purchased unit could be envisaged . such an item would be more difficult to detect since it would only be necessary to apply for a shared address once . however , if the legitimate industry does not provide an interface for such a unit then the pirate is still faced with the marketing problems identified under ( ii ) above . a receiver using the present system is shown in fig8 for receiving signals from a c - mac transmission and where the reference indicates a dish aerial suitable for receiving satellite television signals in the 12 ghz band , the aerial having a down converter 13 attached to it which frequency converts the incoming television signal to a frequency within the 1 to 2 ghz band depending of course on the frequency of the incoming signal . the down converted signal is applied over a co - axial cable 14 to a terminal 15 forming the input for the television receiver , this terminal 15 being connected to an r . f . amplifier and frequency changer stage 16 which amplifies and transforms the incoming signal to a suitable i . f . frequency of about 480 mhz which is further amplified by an i . f . amplifier 17 . the output of the amplifier 17 is applied to a frequency demodulator 18 as the vision components of the broadcast satellite television signal are frequency modulated , the demodulated output of the demodulator 18 being applied to an input of a mac signal analogue processor unit 19 which separates the analogue vision components from the mac signal . the output of the i . f . amplifier 17 is also applied to a digital demodulator stage 20 where the incoming digital signals which are 2 - 4 psk modulated are converted to normal binary form and from which synchronising information and various clock frequencies are derived together with the sound / data and control signals and applied to the analogue processor unit 19 . the vision components from the analogue processor unit 19 are applied to an analog to digital converter 21 for conversion to digital form and thence applied to a vision decoder 22 where the luminance and chrominance vision components , subjected to line cut rotation scrambling at the transmission source , are descrambled and re - assembled for application to a digital to analog converter 23 to produce simultaneous analogue y , u and v components for application to a matrix ( not shown ) prior to being prepared for display . the data and clock signals from the digital portion of the mac signal are applied from the analogue processor unit 19 over a connection 24 to a sync . control unit 25 where various data and synchronising information are processed under the control of a microprocessor 26 . such data are contained in certain areas of the multiplex such as the service information ( si ) packets and data in line 625 and are applied to the microprocessor 26 over a connection 27 . control data for the sync . control unit 25 is applied from the microprocessor 26 over a connection 28 . the sync . control unit 25 applies control data over a connection 29 to the analogue processor unit 19 to control the timing of the digital data to unit 25 and the analogue signals to converter 21 whilst a connection 30 applies control data to the vision decoder 22 to control the descrambling and assembly of the y , u and v components of the vision signal . the latter control data will include the control word cw2 for application to a descrambling sequence generator controlling the descrambling of the vision components . data and control signals , including the control word cw1 for application to a descrambling of the sound / data components , are applied over a connection 31 to a sound decoder 32 where the appropriate sound / data services are selected and descrambled , the sound / data signals having been subjected to scrambling at the transmission source by the addition of a pseudo random sequence using an exclusive or - gate . the appropriate descrambled sound / data services are applied from the sound decoder 32 to a second digital to analog converter 33 to produce ( say ) two such services s1 , s2 for reproduction . the microprocessor 26 is additionally connected over a two way connection 34 to an interface 35 conveying the data needed for communication with a controlled access sub - system 36 which is connected by input ( 37 ) and output ( 38 ) connections . the components of the sub - system 36 may be contained within the receiver or may be present on a smartcard or other such similar device as already proposed and connected to the receiver as required . the sub - system 36 contains an interface 39 between the input and output connections 37 , 38 and a bus 40 . the bus 40 interconnects a central processor unit 41 with a read only - memory ( rom ) 42 which provides the program for running the sub - system , a random access memory ( ram ) 43 which stores data , and a non - volatile memory ( nvm ) 44 which provides long time storage for long term keys such as the unique key and the supplementary keys . it is the controlled access sub - system 36 in combination with the other parts of the receiver which controls which services may be received in an intelligible manner and the control software of the sub - system 36 is organised to that end . the flow chart of fig9 a , 9b and 9c provides an illustration of such control software . in the flow chart of fig9 a , 9b and 9c the various boxes and the legends contained therein specify the control software steps as follows : at this point the user selects the channel he wishes to receive . this is an instruction to determine whether a next pay - per - view supplementary key ( spn ) value is present in the non - volatile memory 44 . at this point the user selects the service in the channel he wishes to receive . the access related message ( accm ) in packet ` 0 ` supplies the decoder with the appropriate ecm packet address . this is an instruction to wait for the primary ecm packet . this is an instruction to attempt to decrypt the primary ecm assuming that the stored spn equals the actual spn by first deciphering spn ( spc ). this is an instruction to determine whether spc from spn ( spc ) equals spc from the ciphertext block . this step is entered into when step f3 does not find an spn value in non - volatile memory 44 and is an instruction to wait for a primary emm having a packet address given by list x in packet ` 0 `, with either a unique customer address ( uca ) or shared customer address ( sca ) ( if known ). this step is also entered into on two other conditions ( below ). this is an instruction to determine whether an uca or an sca is present . this is an instruction , if an uca is present at step f9 to update the sca and the shared distribution key ( sd ) ( and tokens ). once this instruction is completed the program reverts to step f8 . this step is entered into if an sca is present at step f9 and is an instruction to decipher the emm to get the next pay - per - view supplementary key ( spn ) and to store it in the nvm 44 . this step is entered into if spc from spn ( spc ) does not equal spc from ciphertext block at step f7 and is an instruction to attempt to decrypt assuming that the stored spn is equal to the actual spc . this is an instruction to determine whether the stored spn ( used for decrypting ) equals spc from the ciphertext block . if these are not equal the program reverts to step f8 . this is an instruction to determine whether the programme category ( pcat ) permits access to this service . this is an instruction to display an explanatory message if pcat at step f14 does not permit access . this is an instruction to determine whether the user is entitled to free instant access to the service ( user may have done this within the last ( say ) 15 minutes ). this is an instruction to the decoder to be supplied with control words cw . this step is entered into if at step f16 the user is not entitled to free instant access and is an instruction to commence charging at the normal pay - per - view rate . this is an instruction to determine whether the subscription emm and ecm addresses in the primary ecm packet are both zero . this step is entered into if step f19 determines that the subscription emm and ecm addresses in the primary ecm packet are both zero and is an instruction to wait for the primary ecm packet . the status quo has now been achieved with user charged as pay - per - view . this is an instruction to monitor the primary ecm &# 39 ; s for a change in programme number ( pnum ) and on a change of pnum to go to step f14 . this step is entered into if step f19 determines that the subscription emm and ecm addreses in the primary ecm packet are not both zero and is an instruction for the decoder to search for subscription emm packets with addresses from primary emm packets . this is an instruction to the decoder to decipher the subscription emm to determine whether the user is authorised . this step is entered into if step f24 determines the user is not authorised and is an instruction to the decoder to search for primary emm packets again instead of subscription emm packets . when found goes to step f20 . this step is entered into if step f24 determines that the user is authorised and is an instruction to obtain the current subscription supplementary key ssc . this is an instruction for the decoder to search for primary emm packets again instead of subscription emm packets . this is an instruction for the decoder to search for subscription ecm packets rather than primary ecm packets . this is an instruction to the decoder to decipher the subscription ecm packet to determine whether the programme link ( pl ) in subscription ecm packets indicates an imminient change of ssc . if no such change is indicated the program cycles through steps f29 and f30 . the status quo has been achieved with the user receiving a service to which he has subscribed , but pl continued to be monitored to anticipate a change of ssc and hence the end of the programme . this step is entered into if step f30 determines that pl does indicate an imminent change of ssc meaning that the end of the programme is imminient and is an instruction to the decoder to search for primary ecm packets again rather than subscription ecm packets . this is an instruction to decrypt the primary ecm by first using the stored spn to obtain spc from spn ( spc ) and then return to step f14 . the strategy of the above software is to always engage the primary mode ( pay - per - view ) before establishing the subscription mode . this ensures that normal viewing will always be obtained with mininal delay , due to the longer term pay - per - view supplementary key ( spc ). the cover - time of this key may be 2 - 3 weeks which means that the controlled access sub - system will usually have the key stored in its memory from a previous viewing session either in its ` next ` or ` current ` form . in this way ` free viewing ` can be given during a switch on phase whilst the controlled access sub - system searches for the subscription authorisation . this free viewing period works in the following way . although other methods could be used , it is believed that the one described is adequate to deter most forms of piracy . each programme has a unique identification given to it by the channel identification ( chid ) and programme number ( pnum ) sent in the ecm data streams . thus every programme that has been accessed by the controlled access sub - system can be recorded in its memory ( this information could also be used for market research , etc .) to prevent a viewer from obtaining successive free viewing periods , by either turning his ` set ` on and off , or changing channel and returning , the controlled access sub - system compares the current identification with those stored over say the last 15 minutes and if any match the controlled access sub - system starts to charge at the pay - per - view rate . if after the search for subscription authorisation the controlled access sub - system has been enabled by the subscription shared customer emm , the sub - system then operates in subscription mode mode monitoring the subscription ecms for changes in programme using the programme link ( pl ). however , if authorisation is not received the user is offered the possibility of staying in pay - per - view mode charged either on a programme or unit time basis . the switching from one encryption channel to another is achieved by commands send by the controlled access sub - system to the decoder hardware by means of the conditional access interface . the relevant packet addresses are obtained from the si ( though the above ebu documents do not , at present , allow the signalling of emm channels linked to a particular service ), or internally derived from the primary ecm packets . in the flow chart the programme category ( pcat ) is used as a ` parental key ` further restricting programme access on a local basis , e . g . to prevent young children from watching ` adult material `. unless authorisation is denied , the access process is totally transparent to the user ; only in the pay - per - view mode is the user involved in making a decision . | 7 |
during a teeth - whitening treatment in a dental office , a whitening gel is applied to the teeth and a protective barrier is placed on the gums , the mucosa and lips to prevent burning of the tissues by the high concentration of hydrogen peroxide in the whitening gel . a leading edge of the whitening gel is placed on a tooth surface . an led - based white light is placed a few inches from a tooth surface to help activate free radical oxygen , most of which becomes lost into the air . in this invention , the mouthpiece seals or encloses a photosensitive agent , such as carbamide or hydrogen peroxide gel , to prevent the loss of the active electrons of the photosensitive agent ( carbamide or hydrogen peroxide ) into the air . the mouthpiece holds led - based white light sources and alternating heat resistors . a power source , which may be remote from the mouthpiece , is in electrical connection with the led - based white light sources and heat resistors via a wire . the power source energizes the led - based white light sources and heat resistors which generate light rays and a warming heat . the light rays strike the tooth surface on the front and the edge and the back of the edge , i . e ., in all directions , while the mouthpiece is in its intended position relative to the tooth surface . further , a “ closed system ” created by the mouthpiece or guard that seals or encloses ( against exposure to the atmosphere ) is efficient for keeping the active free radical oxygen in close proximity to the teeth to enable their movement onto the tooth surface to breakdown the color pigments inside the tooth . a much lower concentration of the carbamide or hydrogen peroxide gel may be used in comparison to what would be needed to achieve like results in an “ open system ” that did not seal or enclose the photosensitive agent ( carbamide or hydrogen peroxide ) from exposure to atmosphere . indeed , the whitening device ( mouthpiece ) of the present invention may be used for seven to ten consecutive days with little to no sensitivity to the teeth and gums . this seven to ten consecutive day use constitutes a higher frequency of use than is available in conventional professional whitening techniques and helps avoid a regression phenomenon that has been observed in the professional whitening technique . the mouthpiece 10 adjusts to a broad range of user dental arch sizes ( curvature attributed to lower or upper sets of teeth ). it also distributes light and heat in a controlled and focused fashion and provides a means of sealing an area being treated from exposure to oxygen . the heat generated from the alternating heat resistors molds the thermoplastic material of the mouthpiece , i . e ., tpr rubber or medical grade silicone , to the user &# 39 ; s anatomy and creates the closed system around the formulations , preventing oxygen escape , and thus lower wear time , and thus lower sensitivity for the user . referring to fig1 and 2 , the mouthpiece 10 includes upper and lower edges 11 , 13 ( fig2 ) and a bite surface 12 formed of segments . the bite surface 12 is perpendicular to the main body 14 . the bite surface is also central with respect to the main body 14 , with substantially equal portions of the main body 14 above and below the bite surface 12 as seen in fig2 and 4 . referring to fig2 , the mouthpiece 10 is formed of a clear , elastomeric , molded outer shape 14 that encases a flexible circuit board 22 , light emitting diodes 24 and heat generating resistors 26 . there is a deformable frame 28 that holds the circuit board 22 during fabrication and may be bent by the user to adjust the orientation of the mouthpiece 10 to set the arch for comfort in the user &# 39 ; s mouth . the bite surface 12 is preferably segmented as shown in fig1 to help facilitate the adjustability of the mouthpiece 10 to mouths of differing dimensions . additionally , adjustability of the mouthpiece 10 to the shape of the arch of the user is facilitated when the heat generating resistors 26 are activated . this is because the heat so generated softens the mouthpiece 10 and increases its malleability , thereby allowing it to be bent and flexed to conform to the particular configuration of the user &# 39 ; s arch . a series of super bright light emitting diodes ( leds ) 24 and heat generating resistors 26 are arrayed on an inner , lingual side of the flexible circuit board 22 . the power cord 20 is centrally attached to the outer surface . looking at fig2 , there are 3 rows of elements , with the top and bottom rows preferably entirely including heat generating resistors 26 and with the middle row preferably entirely consisting of leds 24 . as shown in fig4 and 5 , the leds 24 are preferably coplanar with the bite surface 12 . a parallel series of textured bands 16 , whose surface texture resembles elongated convex surfaces configured to channel led light , are formed on the lingual side of the outer shape 14 for the purposes of led light diffusion over the surface of the tooth being treated . referring to fig3 a , areas between the segmented bite surfaces 12 allow the device to open as in fig3 b or close as in fig3 c . referring to fig4 , an inner surface 30 of the mouthpiece 10 tilts inward at an angle of 5 to 15 degrees as noted by b to seal the seal bead 18 and borders the edge of the mouthpiece 10 . referring to fig5 , the inward tilt of the inner surface 30 allows the seal bead 18 to contact the gum above the tooth . this contact provides a barrier seal to both retain the whitening gel and to prevent oxygen from entering the treatment area of the tooth ( that is to be treated with the whitening gel ). the light 32 emitted by the leds 24 is guided and directed to more evenly illuminate the surface of the teeth 34 by the textured bands 16 . the texture of the textured bands 16 provides surfaces that are closer to perpendicular to the light path and less reflective than the generally polished surface of the mouthpiece . the light 32 emitted by the leds 24 is directed through the clear material of the main body 14 into both the spaces above and below the bite surface 12 as shown in fig5 . while the foregoing description and drawings represent the preferred embodiments of the present invention , it will be understood that various changes and modifications may be made without departing from the spirit and scope of the present invention . | 0 |
in attaining the objects , features and advantages of this invention , it has now been found , that difficult to deliver drugs can be delivered according to the mode and the manner of the invention . the method of the invention uses an osmotic device for delivering the drug . the osmotic device comprises a wall that surrounds and defines a compartment . the compartment houses a drug , a basic compound having a carbon dioxide generating moiety , and optionally other ingredients . there is a passageway through the wall for dispensing the drug , the compound and the other ingredients from the device . the wall of the osmotic system is formed of a material that does not adversely affect the drug , the compound , a host , or the environment of use . the wall is formed of a polymeric material that is permeable to the passage of an exterior fluid , such as water and biological fluids , and it is essentially impermeable to the passage of drugs , solutes and the like . the selectively permeable polymers useful for manufacturing the devices are represented by a member selected from the group consisting of cellulose acylate , cellulose diacylate , cellulose triacylate , cellulose acetate , cellulose diacetate , cellulose triacetate , polyamides , polyurethanes , and the like . suitable semipermeable polymers for manufacturing osmotic devices are disclosed in u . s . pat . nos . 3 , 845 , 770 ; 3 , 916 , 899 ; 4 , 008 , 719 ; 4 , 036 , 228 ; and 4 , 111 , 210 . these patents are assigned to the alza corporation of palo alto , calif ., the assignee of this patent application . in an embodiment , the wall can be a laminate comprising a semipermeable lamina in laminar arrangement with a microporous lamina . the semipermeable lamina is formed of the above described polymers . the microporous lamina has a plurality of micropores and interconnected micropaths for admitting fluid into the device . the microporous lamina can comprise the above polymers housing a pore former that is dissolved , or leached from the lamina , when the device is in operation in the environment of use . the pore formers are non - toxic and they do not react with the materials forming the wall . on their removal from the lamina , the paths formed therein fill with fluid , and these paths become a means for fluid to enter the device . typical pore formers are represented by sodium chloride , potassium chloride , sorbitol , mannitol , polyethylene glycol , hydroxypropyl methylcellulose , hydroxypropyl butylcellulose , and the like . osmotic devices having a laminated wall comprising a semipermeable lamina and a microporous lamina are disclosed in u . s . pat . no . 4 , 160 , 452 , assigned to the alza corporation . the expression passageway as used herein , includes an aperture , orifice , bore , hole and the like through the wall . the expression also includes an erodible element in the wall , such as a gelatin plug that erodes and forms a passageway in the environment of use . a detailed description of osmotic passageways , and the maximum and minimum dimensions for passageways are disclosed in u . s . pat . nos . 3 , 845 , 770 and 3 , 916 , 899 . these patents are assigned to the alza corporation . the expression drug as used herein broadly includes any compound , composition of matter , or mixture thereof , that can be delivered from the device to produce a beneficial and useful result . the term drug more specifically includes any substance that produces a local or a systemic effect in animals , avians , pisces , and reptiles . the term animals includes primates , humans , household , sport and farm animals , such as goats , cattle , horses , dogs , cats , and the like . the term animal also includes laboratory animals such as mice , rats , and guinea pigs . the drugs that can be delivered by the method of the invention include inorgainic and organic drugs , such as central nervous system acting drugs , hypnotics , sedative , psychic energizers , tranquilizers , antidepressants , anticonvulsants , muscle relaxants , antiparkinson , anesthetics , antiinflammatory , local anesthetics , antimalarials , hormones , sympathomimetics , diuretics , antiparasitics , neoplastics , hypoglycemics , ophthalmics , cardiacs , nutritionals , and the like . the term , in a more preferred embodiment , embraces drugs that are practically insoluble , or have a limited solubility in neutral and acidic environments . that is , these drugs precipitable in such environments . the expression neutral includes water and like biological environments , and the expression acid includes the stomach and the hydrochloric acid produced therein , the vagina and the lactic acid produced therein , and the like . the phrase acidic body fluid as used herein denotes gastric fluid , vaginal fluid and like acid environments in an animal body . a specific groups of drugs suitable for delivery to the above environments by the method of the invention are the acidic antiinflammatory drugs . the antiinflammatory drugs are represented by arylcarboxylic acid drugs , and enolic acid drugs . examples of arylcarboxylic acid drugs include alclofenac or 4 - allyloxy - 3 - chloro - phenylacetic acid ; aspirin or acetylsalicyclic acid ; fenoprofen or dl - 2 -( 3 - phenoxyphenyl ) propionic acid ; flufenamic acid or 2 -( 3 - trifluoromethylanilino ) benzoic acid ; ibuprofen or 2 ( 4 - isobutylphenyl ) propionic acid ; indomethacin or 5 - methoxy - 2 - methyl - 1 -( 4 &# 39 ;- chlorobenzoyl )- 3 - indole - acetic acid ; ketoprofen or 2 -( 3 - benzoylphenyl ) propionic acid ; metiazinic acid or 10 - methyl - 2 - phenothiazinylacetic acid ; naproxen or d - 2 -( 6 &# 39 ;- methoxy - 2 &# 39 ;- naphthyl ) propionic acid ; niflumic acid or 3 - trifluoromethyl - 2 - phenyl - aminonicotinic acid ; tolmetin or 1 - methyl - 5 - p - toluoylpyrrole - 2 - acetic acid ; and sulindac or cis - 5 - fluoro - 2 - methyl - 1 -[ p -( methylsulfinyl )- benzylidene ] indene - 3 - acetic acid . examples of enolic acid drugs include azapropazone or 3 - dimethylamino - 7 - methyl - 1 , 2 -( n - propylmalonyl )- 1 - 2 , dihydro - 1 , 2 , 4 - benzotriazone ; phenylbutazone or 3 , 5 - dioxo - 4 - n - butyl - 1 , 2 - diphenylpyrazolidine ; prenazone or 4 - prenyl - 1 , 2 - diphenyl - 3 , 5 - pyrazolidinedione ; sudoxicam or 4 - hydroxy - 2 - methyl - n -( 2 - thiazolyl )- 2h - 1 , 2 - benzothiazine - 3 - carboxamide - 1 , 1 - dioxide ; and the like . other antiinflammatory drugs include diclofenac or 2 -[ 2 , 6 - dichlorophenyl ) amino ] benzeneacetic acid ; and peroxicam or 2h - 1 , 2 - benzothiazine - 3 - carboxamide . examples of other drugs that are practically insoluble or very slightly soluble in water that can be delivered by the method of the invention include diphenidol , meclizine hydrochloride , prochlorperazine maleate , anisindone , diphenadione , erythrityl tetranitrate , dizoxin , resperpine , acetazolamide , methazolamide , bendroflumethiazide , chloropropamide , tolazamide , allopurinol , aluminum aspirin , salicylic acid , sodium salicylate , salicylamide , acetaminophen , acetophenetidin , colchicine , mefenamic acid , oxphenbutazone , zomepirac , methotrexate , acetyl sulfisoxazole , hydrocortisone , desoxycorticosterone acetate , cortisone acetate , triaminolone , 17 - estradiol , 17 - hydroxyprogesterone , 19 - norprogesterone , prednisolone , progesterone , norethindrone acetate , norethynodrel , and the like . the amount of drug present in a device will vary depending on the activity and the amount of drug to be administered to the host . generally , the device will house from 0 . 5 mg to 3 g or more , with individual devices containing for example 25 mg , 50 , 125 mg , 250 mg , 1 . 5 g and the like . the drug can be in the device in various forms such as dispersion , granule , powder , pressed mass , film , and the like . also , the drug can be mixed with a binder , diluent , dispersant , stabilizer , dye and the like . the beneficial drugs , their solubilities , their present doses are known to the art in pharaceutical sciences , by remington , 15th ed ., 1975 , published by the mack publishing co ., easton , pa . ; the drug , the nurse , the patient , including current drug handbook , 1974 - 1976 , by falconer , et al , published by saunder company , philadelphia , pa . ; in physician desk reference , 33rd ed ., 1979 , published by medical economics co ., oradell , n . j . ; in ann . of allergy , vol . 41 , pages 75 to 77 , 1979 ; in arzenim . forsch ., vol . 25 , pages 1629 to 1635 , 1975 ; and in j . inter . med . res ., vol . 7 , page 335 to 338 , 1979 . the gas generating compound suitable for the purpose of the invention is preferably a solid , basic compound that is pharmaceutically acceptable , and ( a ) exhibits a concentration gradient across the semipermeable wall and imbibes fluid into the device , ( b ) acts as a buffer and dissolves in fluid that enters the device forming a solution containing drug , ( c ) raises outside of the device , the ph of the immediate surrounding area of the passageway high enough to lessen the rate of precipitation of the drug , and ( d ) reacts , outside the device at the passageway environment interface , with the acid of the environment to produce carbon dioxide effervescence that directs drug away from the device in a finely , dispersed form . the basic compounds include non - toxic metal carbonate and bicarbonate salts , such as alkali metal carbonates and bicarbonates , the alkaline earth carbonates and bicarbonates , and mixtures thereof . the preferred compounds are those soluble in water and produce rapid effervescence on contact with the acid of the environment . a mixture of compounds with different degrees of solubility in water can be use with at least one compound being very soluble in water . exemplary compounds include lithium carbonate , sodium carbonate , potassium carbonate , lithium bicarbonate , sodium bicarbonate , potassium bicarbonate , magnesium carbonate , calcium carbonate , magnesium bicarbonate and the like . also useful gas generating compounds are ammonium carbonate , ammonium bicarbonate , ammonium sesquecarbonate , sodium sesquecarbonate and the like . these compounds , when dissolved in water , show a ph greater than 7 , usually between 8 and 12 . optionally , it is often desirable to select the drug and the compound free of a common ion effect , so their respective solubilities in a fluid that enters the device are at their maximum . the amount of basic compound , or mixture thereof housed in the compartment generally is about 0 . 5 mg to 3 g , or more , and more preferrably 25 mg to 750 mg . the compounds and their solubilities in water are disclosed in the handbook of chemistry and physics , 48th ed ., 1968 , published by the chemical rubber co ., cleveland , ohio . the drug and the basic compound also can be used mixed with a binder and a lubricant . the drug and the compound are mixed in a water soluble binder , or in a water insoluble binder that releases the drug and compound on contact with water . typical water soluble binders include poly ( ethylene glycol ), gelatin , agar , carboxycellulose , ethylmethyl - cellulose , poly ( vinyl alcohol ), poly ( vinylpyrrolidone ), water soluble starch derivatives , and the like . typical lubricants include stearic acid , magnesium stearate , zinc stearate and the like . the amount of binder or lubricant used generally is about 0 . 1 mg to 150 mg , or more . the osmotic devices of the invention are manufactured by standard techniques . for example , in one embodiment , the drug is mixed with the basic compound and other ingredients by ballmilling , calendering , stirring and pressing into a preselected shape . the material forming the wall of the device can be applied by dipping , molding or spraying the pressed mixture . one procedure for applying the wall is the air suspension technique . the air suspension technique can be used for manufacturing a wall formed of a single layer , or formed of a multiplicity of layers . the air suspension procedure is described in u . s . pat . no . 2 , 799 , 241 ; in j . am . pharm . assoc ., vol . 48 , pages 451 to 459 , 1959 ; and in ibid , vol . 49 , pages 82 to 84 , 1960 . an osmotic passageway or aperture through the wall is made by mechanical drilling , laser drilling , punching or cutting with die . a procedure for forming the passageway using a laser is described in u . s . pat . nos . 3 , 916 , 899 and 4 , 088 , 864 , both assigned to the alza corporation . other standard manufacturing procedures are described in modern plastic encyclopedia , vol . 46 , pages 62 to 70 , 1969 ; in remington &# 39 ; s pharmaceutical sciences , 14th ed ., pages 1649 to 1698 , 1970 , published by mack publishing co ., easton , pa ., and in the therapy and practice of industrial pharmacy , by lachman , et al , pages 197 to 225 , 1970 , published by lea & amp ; febiger co ., philadelphia , pa . the following examples are merely illustrative of the present invention and they should not be considered a limiting the scope of the invention in any way , as these examples and other equivalents thereof will become more apparent to those versed in the art in the light of the present disclosure , and the accompanying claims . an oral osmotic device for the delivery of a nonsteroid antiinflammatory drug sodium indomethacin was manufactured as follows : a drug composition was prepared for housing in the compartment of the device by thoroughly blending 105 . 2 mg of sodium indomethacin trihydrate , 142 mg of potassium bicarbonate , 5 . 0 mg of polyvinyl pyrrolidone , and 7 . 1 mg of stearic acid , and then compressing the homogenous blend into a pre - compartment forming drug formulation . next , the compressed drug formulation was placed in an air suspension machine and coated with a microporous lamina forming composition . the microporous lamina composition comprised 45 % by weight of cellulose acetate having an acetyl content of 39 . 8 %, 27 . 5 % by weight of hydroxypropyl methylcellulose , and 27 . 5 % by weight of polyethylene glycol 4000 . the lamina was formed from a methylene chloride -- 95 % ethanol solvent ( 80 : 20 wt : wt ). the microporous lamina was 5 mil thick . next , an exterior semipermeable lamina was laminated onto the microporous lamina , in the air suspension machine . the semipermeable lamina forming composition comprised 50 % by weight of cellulose acetate having an acetyl content of 39 . 8 % and 50 % by weight of cellulose acetate having an acetyl content of 32 %. the semipermeable lamina was applied from a solvent mixture comprising methylene chloride and 95 % ethanol , 80 : 20 wt : wt . the systems were dried , and a 10 mil passageway was laser drilled through the laminated wall . the system releases indomethacin at the rate of 8 mg per hour . the device in operation , releases a solution that effervesces on contact with the acidic gastric fluid at the exit end of the passageway , producing carbon dioxide bubbles that disperse the drug in a fluffy state due to the entrapped gas bubbles . an oral osmotic device for the controlled and continuous delivery of indomethacin was made by following the general procedure described above . in the present device , the compartment housed a drug formulation comprising 56 . 4 % potassium carbonate , 37 . 6 % sodium indomethacin trihydrate , 3 % providone ® and 3 % stearic acid . the formulation after compressing had a diameter of 7 . 93 mm , an area of 1 . 6 cm 2 and a density of 1 . 65 g / ml . the device had a laminated wall comprising an interior microporus lamina consisting essentially of 45 % by weight of cellulose acetate having an acetyl content of 39 . 8 %, 45 % by weight of sorbitol , and 10 % by weight of polyethylene glycol 400 . the lamina was applied from a solvent comprising methylene chloride - methanol - water , 62 : 35 : 3 by wt . a semipermeable lamina was laminated onto the microporous lamina , which semipermeable lamina consists of 50 % by weight of cellulose acetate having an acetyl content of 39 . 8 %, and 50 % by weight of cellulose acetate having an acetyl content of 32 %. the lamina was applied from a solvent consisting of methylene chloride and methanol , 80 : 20 by wt . the microporous forming lamina was 5 ml thick , and the semipermeable lamina 2 . 4 mil thick . the device had a 9 mil passageway and delivered indomethacin at the rate of 8 mg / hr . the device delivers the drug substantially free of rapid precipitation at the passageway environment interface , and on the wall of the device in the vicinity of the passageway . the procedure of example 2 was repeated with the conditions as described except that the microporous forming lamina was 1 mil thick , the semipermeable lamina 2 . 7 mil thick , and the rate of release was 8 mg / hr . the osmotic device of examples 1 and 2 was manufactured in this example , wherein , ( a ) the microporous lamina was 5 mil thick , the semipermeable lamina was 3 . 4 mil thick , and the device had a release rate of 6 mg / hr , and ( b ) a device wherein the microporous lamina was 5 mil thick , the semipermeable lamina was 1 . 7 mil thick , and the system had a release rate of 12 mg / hr . a series of oral osmotic devices for releasing an arylcarboxylic acid antiinflammatory drug in the gastrointestional tract are prepared according to the invention , wherein the device houses from 40 to 250 mg of sodium indomethacin and more preferably from 85 to 125 mg of sodium indomethacin trihydrate the equivalent of 70 to 100 mg of indomethacin , from 50 to 300 mg of potassium bicarbonate and more preferably from 130 to 190 mg of potassium bicarbonate , 2 to 20 mg of binder , and more preferably 5 to 10 mg of binder , and 2 to 20 mg of lubricant , and more preferably 5 to 10 mgs . the device has an inner microporous forming lamina weighing 18 to 25 mg with a thickness of 0 . 10 to 0 . 16 mm , and an exterior semipermeable lamina weighing 6 to 20 mg with a thickness of 0 . 035 to 0 . 100 mm . the device has a passageway of 0 . 18 mm to 0 . 38 mm , and releases drug at the rate of 5 to 15 mg / hr . the unexpected benefits produced by the invention are seen in fig1 and fig2 . fig1 shows the release of indomethacin from an osmotic device manufactured without a basic gas generating compound . the device releases the drug in the presence of an artifical gastric fluid containing hydrochloric acid , however , the drug precipitates onto the wall of the device and the exit port of the passageway , and it is therefore not observed in the fluid of the environment , which is analyzed on an hourly basis , as displayed in fig1 . fig2 shows the release of indomethacin from an osmotic device manufactured with a basic gas generating compound . this device in operation releases drug in both an artificial intestional fluid according to the spirit of the invention . the method of this invention provides an unique means for delivering numerous drugs that evidence properties that do not easily lend themselves to delivery in an environment having a ph of neutral or lower . while there has been described and pointed out novel features for delivering hard to deliver drugs at controlled and continuous rates , it is to be understood , those versed in the art will appreciate that various modifications , changes and omissions in the method can be made without departing from the spirit of the invention . | 0 |
fig1 shows a starter device that is identified by the reference symbol 100 . the starter device 100 comprises a handle 2 that enables the user to introduce a pulling force into a starter pulling means 3 . the starter pulling means 3 are realized in the form of a rope and wound up on a pulling means spool 4 in the form of a rope spool . if the user pulls on the starter pulling means 3 , the pulling means spool 4 is set in rotation due to the unwinding of the starter pulling means 3 from the pulling means spool 4 such that a starter torque is introduced . the rotation of the pulling means spool 4 is transmitted to a coupling member 15 , wherein the transmission is realized by means of a double crank mechanism 5 . the double crank mechanism 5 comprises a coupling rod 6 that is arranged between a hinge pin 7 situated on the plane side of the pulling means spool 4 and a lever arm 9 . the rotational movement of the pulling means spool 4 causes the hinge pin 7 to rotate about a spool axis 8 , wherein the lever arm 9 is supported such that it is rotatable about an output axis 11 that is offset relative to the spool axis 8 . the rotational movement of the pulling means spool 4 is transmitted into the lever arm 9 by means of the coupling rod 6 such that the lever arm carries out a non - uniform movement relative to the rotational movement of the pulling means spool 4 . if the pulling means spool 4 carries out a uniform rotational movement , the lever arm 9 rotates slowly over one segment of a circle and rapidly over another segment of a circle during one full revolution of the pulling means spool 4 . this makes it possible to realize a conversion of the torque that is adapted to the torque demand for starting the internal combustion engine . the pulling means spool 4 is rotatably supported on a receptacle plate 12 while the lever arm 9 comprises a bearing section 14 that extends through a receptacle bridge 10 in order to be supported . the receptacle bridge 10 is mounted on the receptacle plate 12 by means of spacer elements 13 , wherein the receptacle bridge 10 extends similar to a beam and features a screw connection with one respective spacer element 13 on its ends . a coupling member 15 is arranged on the end of the lever arm 9 that extends through the receptacle bridge 10 such that the rotational movement of the lever arm 9 about the output axis 11 is transmitted into the coupling member 15 . all in all , the starter device 100 thusly makes it possible to generate a periodically changing rotational movement in the coupling member 15 when the starter pulling means 3 are subjected to a uniform pulling motion . fig2 shows another embodiment of the inventive double crank mechanism 5 in the starter device 100 . an end of the coupling member 15 is moulded onto a disk element 16 , wherein the disk element 16 is rotatably accommodated on a bearing journal 17 and the bearing journal 17 is arranged in the receptacle plate 12 . a pulling means spool section 19 , on which the pulling means spool 4 is rotatably supported , extends between the bearing journal 17 and the receptacle plate 12 . the bearing journal 17 extends along a coupling member axis 18 that is offset relative to the spool axis 8 . consequently , the bearing journal 17 is arranged eccentrically on the pulling means spool section 19 in order to realize the offset of the crank elements required for the double crank mechanism 5 . the first crank element of the double crank mechanism 5 is formed by the pulling means spool 4 with a hinge pin 7 arranged on its plane side and rotates about the spool axis 8 , wherein the second crank element is formed by the disk element 16 and the coupling rod 6 extends between the hinge pin 7 and another hinge pin 20 arranged on the disk element 16 . this simplifies the arrangement because the lever arm 9 ( see fig1 ) and the coupling member 15 are realized in the form of a one - piece disk element 16 . fig3 shows an advantageous additional development of the double crank mechanism 5 of the starter device 100 . this double crank mechanism comprises a coupling rod 6 that is realized in the form of an elastically bendable coupling element 21 . the elastically bendable coupling element 21 is rotatably inserted between the hinge pin 7 and the lever arm 9 and able to change its effective length due to the bending elasticity . if a torque is applied to the double crank mechanism 5 by means of the pulling means spool 4 and the hinge pin 7 , the elastically bendable coupling element 21 bends such that its defective length is shortened and the torque transmitted to the lever arm 9 increases . if the load on the elastically bendable coupling element 21 is alleviated , its effective length once again increases such that the rotational speed of the lever arm 9 increases once again as the torque decreases . fig4 shows a perspective representation of the elastically bendable coupling element 21 that takes over the function of the coupling rod 6 . the elastically bendable coupling element 21 has a horseshoe - shaped structure and comprises two hinge pin bores 23 , through which the hinge pins ( hinge pins 7 , 20 ; see fig2 ) extend and respectively form a sliding bearing . the elastically bendable region 22 is realized between the ends of the horseshoe - shaped coupling element 21 such that the distance between the hinge pin bores 23 can be increased and decreased . a limit stop geometry 24 is provided for limiting the bending within the elastically bendable region 22 . if the bending load becomes excessively high , the surfaces of the limit stop geometries 24 respectively contact one another such that the additional bending of the elastically bendable region 22 is limited . fig5 shows a perspective representation of the crankshaft flange 25 . this flange features a plane side 27 that forms the side that points away from the internal combustion engine and toward the starter device 100 . blade elements are integrally moulded onto the circumference of the crankshaft flange 25 in order to ventilate the complete system consisting of the internal combustion engine and the starter device 100 . ratchet elements 26 with a different height referred to the plane side 27 are arranged on the plane side 27 of the crankshaft flange 25 . the ratchet elements 26 are rotatably supported on cylinder members 38 , wherein the cylinder members respectively have a different length . the cylinder members 38 are arranged on the plane side opposite of one another referred to the rotational axis of the crankshaft flange 25 , wherein the first cylinder member 38 is shorter than the second cylinder member 38 . the coupling member 15 features engagement windows 28 , into which the ratchet elements 26 can engage . in order to assign one respective ratchet element 26 to a defined engagement window 28 , the engagement windows 28 also have a different axial position in the direction of the rotational axis of the crankshaft flange 25 . this ensures that the starter device 100 with the assigned torque characteristic corresponds to the correct compression or expansion phase of the internal combustion engine . fig6 and 7 show another embodiment of the starter device 100 . a centrifugal clutch with a centrifugal element 29 is arranged between the pulling means spool 4 and the crankshaft flange 25 in such a way that the centrifugal element 29 acts as a coupling rod 6 and forms a double crank mechanism 5 together with the crankshaft flange 25 and the pulling means spool 4 . one can ascertain that a joint socket geometry 31 is integrally moulded onto the pulling means spool 4 such that the centrifugal element 29 is driven by the joint socket geometry 31 . if the crankshaft flange 25 rotates faster than the starter device 100 when the internal combustion engine starts , the centrifugal element 29 separates from the joint socket geometry 31 and turns radially outward due to the centrifugal force . the internal combustion engine or the crankshaft flange 25 therefore can rotate freely without the starter device 100 participating in this rotational movement . therefore , the function of the double crank mechanism 5 is combined with the function of an overrunning clutch . a crankshaft 1 that is illustrated centrally in the crankshaft flange 25 points in the direction of the ( not - shown ) internal combustion engine in the form of a shaft end . fig8 shows another perspective representation of the starter device 100 that extends between the receptacle plate 12 and the crankshaft flange 25 . a friction ring 33 and a roll element 34 arranged between the engaging element 30 and the crankshaft flange 25 cooperate in such a way that a torque transmission takes place when the starter device 100 is actuated and this torque transmission is not interrupted until the internal combustion starts . the engaging element 30 comprises roll tracks 35 that are realized in the direction of the crankshaft flange 25 , wherein 3 roll tracks are arranged on the circumference in a star - shaped configuration and angularly spaced apart by 120 °. the roll tracks 35 serve for the rolling motion of a roll element 34 , with the roll tracks 35 extending with a radial curvature . the engaging element 30 and the pulling means spool 4 furthermore comprise a quick - acting screw thread 32 that connects both components such that they can be screwed relative to one another . the axial position of the engaging element 30 relative to the pulling means spool 4 is related to a defined rotatory position due to the quick - acting screw thread 32 such that the roll element 34 rolls on the roll track 35 in dependence on the rotatory position of the engaging element 30 . this results in a different torque characteristic between the pulling means spool 4 and the crankshaft flange 25 in order to create a functional connection according to the present invention , in which the crankshaft torque introduced into the crankshaft 1 is variable in dependence on the rotational angle of the crankshaft at a constant torque in the pulling means spool 4 . the design of the invention is not limited to the above - described embodiments . on the contrary , it would be conceivable to realize a multitude of variations that also utilize the described solution in fundamentally different types of designs . fig9 to 22 show another embodiment of the starter device 100 . a centrifugal clutch with a centrifugal element 39 is arranged between the pulling means spool 4 and the crankshaft flange 25 in such a way that the centrifugal element 39 acts as a roll track and forms a cam roller gear together with the crankshaft flange 24 and the pulling means spool 4 . in this case , the roll track lever 39 is supported on the hinge pin 7 in a rotatable and pivoted fashion and held in the idle position shown in one of fig1 ( top view ) and 12 ( perspective representation ), in which the first contact section 41 of the roll track lever 39 is still supported on the limit stop 42 of the coupling flange 25 , by means of the pull - back spring 40 . after the internal combustion engine starts , the disengaging weight 43 of the roll track lever 39 displaces the roll track lever 39 into the operating position “ engine running ” shown in fig1 ( top view ) and 14 ( perspective representation ) and the second contact section 44 of the roll track lever 39 contacts the limit stop bolt 45 on the crankshaft flange 25 . during the starting process , the roll track section 44 of the roll track lever 39 contacts one of the two stopping bolts 47 arranged on the pulling means spool 4 such that the roll 48 arranged on each stopping bolt 47 rolls on the roll track section 44 and thusly transmits the starter torque . the roll track lever 39 has a contour referred to the roll track section 46 that corresponds to the optimal change in the transmission ratio of the double crank mechanism 5 in dependence on the rotational angle of the crankshaft . the roll track lever 39 also has a width that corresponds to the respective moments and forces to be transmitted . the contour of the roll track lever 39 preferably is continuously tapered referred to its width from the hinge pin 7 up to the second contact section 44 . in order to ensure an early engagement or an early contact between the stopping bolt 47 and the roll track lever 39 with respect to the rope path , two stopping bolts 47 are provided , wherein the limit stop bolt 45 respectively makes contact in the roll track section 46 of the roll track lever 39 and the other stopping bolt 47 pivots the roll track lever 39 inward once again when the engine is running and the crankshaft flange 25 “ passes ” the pulling means spool 4 . fig1 and 12 show the operating situation in the “ idle position ,” and fig1 and 14 show the operating situation “ engine running .” during the course of one respective revolution of the pulling means spool 4 on one hand and the crankshaft flange 25 on the other hand , the coupling gear 5 causes a relative movement that results in different distances a between the contact point b of the limit stop bolt 45 on the roll track section 46 of the roll track lever 39 and the spool axis 8 such that a transmission ratio is achieved that varies over 360 ° with respect to the torque to be transmitted and the resulting speed . the individual prominent operating points during one revolution are illustrated in fig1 to 22 , fig1 indicates in an exemplary fashion that the transmission ratio i results from the ratio between i output and i input and according to the formula fig2 and 24 show another embodiment of the starter device 100 that largely corresponds to the embodiment shown in fig6 and 7 . identical components are also identified by the same reference symbols . the difference between these embodiments can be seen in that the joint socket is not moulded onto the pulling means spool 4 , but rather onto the centrifugal element ( coupling rod ) 6 . consequently , the joint ball and the joint socket are merely interchanged . this provides the option of using one ( or more ) bolt ( s ) inserted into the pulling means spool as the joint ball . fig2 shows a diagram with the transmission ratios u and the torque demand in dependence on the crankshaft angle k . the round drawings of the gear illustrated in this figure do not correspond to the drawings according to fig9 - 22 , but merely serve as schematic representations . in this case , a step - down transmission ratio ( il ) is illustrated above the line l ( torque equal to zero ) and a step - up transmission ratio ( is ) is illustrated below said line . the torque demand characteristic ( dbv ) was qualitatively calculated from the gas forces . although several embodiments have been described in detail for purposes of illustration , various modifications may be made to each without departing from the scope and spirit of the invention . accordingly , the invention is not to be limited , except as by the appended claims . | 8 |
it has been reported that profound adaptive responses involving alterations in metabolic properties occur in the skeletal muscles of horses undergoing various forms of physical training . dramatic increases in the concentration of mitochondria and concomitant increases in the concentration of oxidative enzymes involved in atp production have been frequently documented . in contrast , the anaerobic potential of equine skeletal muscle is intrinsically high and is not greatly influenced by altered patterns of physical activity or nutrition . accordingly , horses already involved in training programs , provide a particularly appropriate model for evaluating a composition designed to increase intracellular synthesis of atp . to establish the efficacy of the present invention , seven standard - bred horses already involved in training programs were selected . each of the horses had hematological and blood chemistry studies performed prior to or at the outset of atp baseline determinations . blood samples were collected from each subject two to three times a week for a period of twenty - five days while the horses continued to receive their normal training ration of feed . blood samples were drawn into acd blood tubes ( 8 . 5 ml blood , 1 . 5 ml anti - coagulent ); samples were held on ice until refrigerated at 4 ° c . whole blood was analyzed for levels of atp within twenty - four hours after bleeding using the sigma test kit procedure , sigma diagnostics , p . o . box 14508 , st . louis , mo . 63178 . in plasma , atp is present in trace amounts at best . for this reason , atp assay procedures require that blood cells be ruptured . hence , the atp level found in such an assay is directly related to the intracellular level of atp . the procedure for atp determination is based on the action of the enzyme phosphoglycerate phosphatase to form 1 , 3 diphosphoglycerate from atp and 3 - phosphoglycerate . the enzyme glyceraldehyde phosphate dehydrogenase catalyzes the reation to form glyceraldehyde - 3 - p and nad + p , thus causing a reduction in the absorbance at 340 nm wavelength . the reaction , then , is limited by the amount of atp present , and the reduction in absorbance is proportional to the atp present . after the initial twenty - five day period , four of the subjects received eight ounces daily ( 4 oz . in a . m . feed , 4 oz . in p . m . feed ) of a mixture containing the composition of the present invention and a group of nutritional elements . the remaining three subjects received four ounces daily ( 2 oz . in a . m . feed ,- 2 oz . in p . m . feed ) of the same mixture . the nutritional elements were combined with the present invention primarily to make it more palatable to the horses and to provide additional vitamins and minerals . the most preferred composition of the present invention is set out in table i along with the acceptable weight ranges of the individual components . table ii sets out the nutritional elements combined with the present invention in their preferred weight ratios . table i______________________________________component preferred acceptable______________________________________l - glycine 0 . 6 kg 0 . 5 kg - 0 . 7 kgl - arginine 2 . 4 kg 2 . 2 kg - 2 . 6 kgd / l methionine 12 . 0 kg 10 . 8 kg - 13 . 2 kgcholine chloride 10 . 1 kg 9 . 1 kg - 11 . 1 kginositol 8 . 9 kg 8 . 0 kg - 9 . 8 kgl - aspartic acid 8 . 9 kg 8 . 0 kg - 9 . 8 kgl - tryptophan 2 . 6 kg 2 . 3 kg - 2 . 9 kgl - phenylalanine 2 . 1 kg 1 . 9 kg - 2 . 3 kgl - histidine 2 . 0 kg 1 . 8 kg - 2 . 2 kgl - proline 1 . 5 kg 1 . 4 kg - 1 . 7 kgd - ribose 8 . 9 kg 8 . 0 kg - 9 . 8 kgmagnesium phosphate 7 . 7 kg 6 . 9 kg - 8 . 5 kgtotal 67 . 7 kg 60 . 9 kg - 74 . 6 kg______________________________________ table ii______________________________________component______________________________________lactalbumin 300 . 00 kgyeast culture ( saccharomyces cerevisiae ) 340 . 90 kgdried beet molasses 181 . 80 kgdicalcium phosphate 90 . 90 kgsodium bicarbonate 22 . 70 kgmulti - vitamin mixture ( vitamin a , vitamin d3 , 45 . 45 kgvitamin e , vitamin b12 , riboflavin , niacin , pantothenic acid , menadione , folic acid , thiamine , pyridoxine , ascorbic acid and biotin ) lignan sulphate 13 . 07 kgflavoring agents 1 . 36 kgtotal 996 . 18 kg______________________________________ background information for each horse was collected regarding training performance , stamina , race times and results , and general history . a daily journal was maintained by the trainer for each horse during the study period . dietary supplementation with the present invention had a marked effect on the level of atp in the subjects &# 39 ; blood . as noted above , the blood level of atp is directly related to the level of atp inside the cell . fig1 illustrates atp blood levels for all seven subjects before and after dietary supplementation . as a group , after supplementation , subjects had a mean increase ( percentage increase ) of atp blood levels of 23 . 54 %. fig2 - 8 illustrate that each individual subject showed marked increase in atp blood levels ranging from a high of 38 . 4 % ( fig2 ) to a low of 11 . 8 % ( fig8 ). fig9 - 12 illustrate the correlation between increased blood levels of atp and improved performance levels for four of the seven subjects . fig9 - 12 correspond to subjects 1 , 3 , 4 and 7 respectively . since these four subjects continue to race competitively and train accordingly , they generated sufficient data to form the basis for an atp blood level / performance level correlation . the solid line on each of the figures illustrates , in alternate form , the data expressed in the bar graphs of fig1 ∝ 8 . that is , dietary supplementation with the present invention produces a marked increase in atp blood levels over the levels found in the period immediately preceding the start of supplementation . the broken line on each of fig9 - 12 illustrates the mean atp blood level for the period immediately preceding supplementation and the period of supplementation . the solid double line in each of the fig9 - 12 illustrates the correlation between increased blood levels of atp and increased performance levels . as noted above , background information for each subject was collected regarding training performance , stamina , race times and results , and general history . the background information was compiled over a period of approximately one year , the period coinciding with the racing season completed prior to the initiation of dietary supplementation with the present invention . the background information consists of quantitative data such as race times , split times and race results . in addition , the background information includes subjective evaluations of the horses by their trainers . the background information collected on each subject was used to establish an average expected behavior or zero rating for each horse . the zero rating was established by evaluating each subject on the basis of four criteria : speed , stamina , aggressiveness and vitality . each subject was given a rating for each of the four criteria based on a scale of - 5 to + 5 . once the zero rating for each subject was established , the horses were again evaluated according to the four criteria during the twenty - five day period preceding dietary supplementation and for the period of dietary supplementation . the second and third sets of evaluations resulted in a performance rating relative to the previously determined zero rating for each of the periods just mentioned . as fig9 - 12 clearly illustrate , each of the subjects had a performance level very near to or below their zero rating for the twenty - five day period preceding the initiation of supplementation . however , fig9 - 12 also clearly indicate that as atp blood levels increased during the period of dietary supplementation , performance levels increased to the point where , by the end of the supplementation period , each of the subjects had a performance rating well above the subject &# 39 ; s zero rating . in fact , two of the subjects , number 4 , a four - year - old , and number 7 , a seven - year - old , established new life - time race marks . it is important to note that at no time during the study were trainers informed of any blood test results . to demonstrate that the composition of the present invention increases the rate of wound repair , another series of experiments were conducted wherein the composition was applied to excised wounds on the dorsum of laboratory rats . this was performed as follows : male sprague - dawley rats ( 250 - 300 g , charles river breeding laboratories , willmington , me .) were anesthetized with an intraperitoneal injection of ketamine / rompun ( 90 mg / ketamine and 10 mg / rompun ). each rat was given a single full - thickness excized wound 2 . 5 cm in diameter over the dorsal midline . while the rats were anesthetized , photographs were taken to represent zero time ( initial size [ area ]) compared to a second photograph taken ten days later . for forty - eight hours post - surgery , all animals were maintained on analgesic levels of acepromazine ( 0 . 015 %) in their water supply , which eliminated signs of discomfort from the wounds . after the experimental period , the rat were euthanized and skin sections prepared for sub - stage illumination and photographic measurement of final wound area . at this time , the wounded areas were dissected free from surrounding tissue , weighed and frozen in dry ice / acetone for future atp determination . the process required 45 seconds from the removal of the skin section to freezing in a weighing boat for atp analysis . the procedures used for atp determination were the same as those outlined above using the sigma diagnostic test kit . the experimental design consisted of eight ( 8 ) groups containing six ( 6 ) rats each with treatment summarized as follows : group 1 -- composition of the present invention ( 1 % composition in sterile isotonic saline ). the most preferred composition is set out in table iii along with the acceptable weight ranges of the individual components . group 2 -- atp solution ( 33 mg per ml in sterile isotonic saline ). group 3 -- a solution containing both the composition and atp combined to give the same concentrations above . group 4 -- the composition in a gel ( 10 % avalon gel containing 1 % of the compostion ). group 5 -- atp in a gel ( 10 % avalon gel containing 33 mg per ml added in sterile saline ). group 6 -- the composition and atp combined in 10 % avalon gel to provide the same concentrations as above . table iii______________________________________composition of atp - e preferred acceptablecomponent grams grams______________________________________l - glycine 8 . 9 8 . 0 - 9 . 8l - arginine 35 . 4 31 . 9 - 38 . 9d / l methionine 177 . 2 159 . 5 - 194 . 9choline chloride 149 . 2 134 . 3 - 164 . 1inositol 131 . 5 118 . 3 - 144 . 7l - aspartic acid 131 . 5 118 . 3 - 144 . 7l - tryptophan 38 . 4 34 . 6 - 42 . 2l - phenylalanine 31 . 0 27 . 9 - 34 . 1l - histidine 29 . 5 26 . 5 - 32 . 4l - proline 22 . 2 20 . 0 - 24 . 4d - ribose 131 . 5 118 . 4 - 144 . 7magnesium phosphate 113 . 7 102 . 3 - 125 . 1 1000 . 0 900 . 0 - 1100 . 0______________________________________ treatments with the above solutions and gels were administered once daily in the first trial reported here . in the second trial , solutions and gels were applied three times daily for the first three days , then once daily for seven days . each application consisted of either 0 . 5 ml of solution or 0 . 5 g of gel . at the end of the ten day period in both trials , the rats were euthanized and wound tissues taken for study . the procedure for wound size measurements was as follows : wound size measurements were made from standardized photographs , and area was determined with a planimeter . the sections were photgraphed with standardized magnification , and planimetric measurement was made of the wound outline . a metric scale in the plane of the wound assured reproducable determinations . wound weights were determined by making an excision of the entire wound down to the panus . fig1 shows the correlation between wound area surface and wound weight , thus providing a basis for determinations on either weight or area . after each wound was removed it was immediately frozen at - 80 ° c . for wound weight and atp determinations . the concentration of atp was determined in wound tissue by mincing the entire section containing granulation tissue . the atp levels were expressed as atp milligram / 10 g of tissue . the data set out in table iv below demonstrates that a single daily application of the composition as a solution produced a rate of closure which was 17 . 8 % faster than wounds treated with sterile isotonic saline ( control ). when the composition was applied as a gel , the rate was 1 . 2 % faster . the composition applied three times a day as a solution produced a marked improvement over treatments applied once each day . the data shown in table v demonstrates these improvements , wherein composition treated wounds had a mean reduction of 37 . 1 %, atp 31 . 2 % and the mixture composition / atp 37 . 3 %. the values for percent reduction are based on a decrease in wound weight compared to the mean wound weight of 1 . 153 for the isotonic saline treated control wounds . table iv______________________________________percent increase in contraction rate overcontrol when applied once each day for 10 days % increase differ - overgroup initial final ence control * ______________________________________i composition soln . 59 . 3 (+ 12 . 3 ) 77 . 3 17 . 8 136 . 6 (+ 7 . 30 ) ii atp soln . 61 . 1 (+ 94 ) 69 . 4 5 . 8 130 . 5 (+ 12 . 8 ) iii composition gel 61 . 5 (+ 13 . 2 ) 66 . 4 1 . 2 127 . 9 (+ 6 . 7 ) iv atp gel 71 . 9 (+ 7 . 4 ) 61 . 6 ( 6 ) 133 . 5 (+ 5 . 8 ) v saline gel control 64 . 3 (+ 11 . 5 ) 71 . 3 -- 135 . 6 (+ 5 . 5 ) vi isotonic saline conrol 72 . 3 (+ 14 . 4 ) 65 . 6 -- ______________________________________ * value for difference ( initial minus final ) for treated minus that difference for control divided by control times 100 equals percent increase in contraction rate .? table v______________________________________percent reduction in wound weightwound weight percent reduction * ______________________________________group i composition1 -- -- 2 0 . 832 27 . 93 -- -- 37 . 1 ± 7 . 34 0 . 627 45 . 65 0 . 706 38 . 76 0 . 736 36 . 2group ii atp1 0 . 765 33 . 72 0 . 855 25 . 93 1 . 053 8 . 7 31 . 2 ± 13 . 94 0 . 614 46 . 85 0 . 838 27 . 46 0 . 642 44 . 4group iii mixture composition / atp1 0 . 887 23 . 12 0 . 708 38 . 63 0 . 700 39 . 3 37 . 3 ± 8 . 24 0 . 734 36 . 45 0 . 589 48 . 96 0 . 721 37 . 5group viii isosaline control , valued used for above calculationscalculations was 1 . 153 ± 0 . 1311 1 . 2702 1 . 1313 0 . 9764 1 . 2345 1 . 0266 1 . 284______________________________________ * the control value minus treated value and that difference divided by the control times 100 yields percent reduction . fig1 shows the relationship between wound surface area and wound weight . the linear relationship between weight and area suggests that weight measurements may be a useful means for determining wound contraction . the bar graph shown in fig . 14 depicts the increased rate of contraction for composition / atp mixture gels compared to control gels . although the gel treated wounds contracted faster than controls , they did not contract as fast as the solution treated wounds . however , in each group wounds treated with the composition or the composition / atp mixture had greater rates of contraction than their counterparts . both solution and gel treatments , in addition to producing a marked reduction in wound weight , also reduced the amount of atp found in the wound . this is evident in tables vi and vii and in fig1 and 16 . while it is apparent both in gel and solution treated wounds that atp levels are reduced by the composition , the reduced level of atp at the wound site is not unexpected , since protein metabolism for wound repair and the wound contraction produced by the myofibroblasts both require significant amounts of energy in the form of atp . that is , additional intracellular atp synthesized by the cells in response to the present invention is quickly utilized for contraction , glueoneogenisis and protein synthesis . table vi______________________________________solutions applied to excised woundswound initial finalwt . od od atp atp / g mean______________________________________group1 0 -- -- -- -- 2 0 . 832 0 . 645 0 . 616 7 . 4 8 . 89 atp3 1 . 668 0 . 654 0 . 638 6 . 2 3 . 72 8 . 78 ± 2 . 574 0 . 627 0 . 654 0 . 631 8 . 0 12 . 8 tissue wt . 5 0 . 706 0 . 671 0 . 638 12 . 9 18 . 3 0 . 725 ± . 086 0 . 736 0 . 639 0 . 615 9 . 4 12 . 8groupii1 0 . 765 0 . 454 0 . 420 13 . 3 17 . 42 0 . 855 0 . 454 0 . 451 1 . 2 1 . 40 atp3 1 . 053 0 . 454 0 . 468 -- 8 . 9 ± 5 . 374 0 . 614 0 . 418 0 . 427 -- tissue wt . 5 0 . 838 0 . 418 0 . 450 11 . 7 14 . 0 0 . 794 ± . 1606 0 . 642 0 . 469 0 . 450 7 . 4 14 . 6groupiii1 0 . 887 0 . 631 0 . 591 15 . 6 17 . 62 0 . 708 0 . 445 0 . 485 -- atp3 0 . 700 0 . 423 0 . 436 -- 6 . 9 ± 6 . 184 0 . 734 0 . 423 0 . 417 2 . 3 3 . 1 tissue wt . 5 0 . 589 0 . 423 0 . 405 7 . 0 11 . 9 0 . 723 ± . 0956 0 . 721 0 . 609 0 . 602 2 . 7 3 . 7groupviii1 1 . 270 0 . 515 0 . 500 5 . 9 4 . 72 1 . 131 0 . 474 0 . 468 2 . 3 2 . 0 atp3 0 . 976 0 . 495 0 . 478 6 . 6 6 . 8 7 . 64 ± 4 . 754 1 . 234 0 . 477 0 . 478 -- tissue wt . 5 1 . 026 0 . 477 0 . 456 8 . 2 8 . 0 1 . 153 ± 0 . 1316 1 . 284 0 . 670 0 . 631 15 . 2 11 . 8______________________________________ table vii______________________________________gels applied to excised rat wounds ( three applications per day ) wound initial finalwt . od od atp atp / g mean______________________________________groupiv composition gel1 1 . 218 0 . 553 0 . 549 1 . 6 1 . 32 0 . 805 0 . 579 0 . 565 5 . 5 6 . 8 atp3 0 . 882 0 . 565 0 . 548 6 . 6 7 . 5 5 . 2 ± 2 . 54 1 . 139 0 . 565 0 . 548 6 . 6 5 . 8 tissue wt . 5 1 . 376 0 . 580 0 . 570 3 . 9 2 . 8 1 . 082 ± 0 . 2126 1 . 076 0 . 956 0 . 938 7 . 2 6 . 7group1 1 . 100 0 . 774 0 . 717 22 . 2 20 . 22 . 954 0 . 815 0 . 777 14 . 8 15 . 5 atp3 1 . 236 0 . 906 0 . 588 124 . 0 100 . 3 17 . 7 ± 3 . 04 1 . 158 0 . 749 0 . 704 17 . 6 15 . 2 tissue wt . 5 1 . 157 0 . 929 0 . 881 18 . 7 16 . 2 1 . 196 ± 0 . 2076 1 . 574 0 . 608 0 . 569 15 . 2 9 . 7group mixture composition / atp gelvi1 1 . 336 0 . 580 0 . 458 47 . 6 35 . 62 1 . 111 0 . 598 0 . 498 39 . 0 35 . 1 atp3 1 . 480 0 . 592 0 . 479 44 . 1 29 . 8 32 . 6 ± 5 . 74 1 . 338 0 . 678 0 . 568 42 . 9 32 . 1 tissue wt . 5 1 . 390 0 . 595 0 . 453 55 . 4 39 . 9 1 . 425 ± 0 . 2606 1 . 896 0 . 595 0 . 482 44 . 1 23 . 3group isosaline gelvii control1 1 . 073 0 . 635 0 . 520 44 . 9 41 . 82 1 . 540 0 . 628 0 . 520 42 . 1 27 . 3 atp3 1 . 219 0 . 604 0 . 476 49 . 9 40 . 9 36 . 9 ± 6 . 54 1 . 127 0 . 604 0 . 476 49 . 9 44 . 3 tissue wt . 5 1 . 256 0 . 577 0 . 465 43 . 7 34 . 8 1 . 285 ± 0 . 1926 1 . 496 0 . 617 0 . 494 48 . 0 32 . 1______________________________________ in summary , solutions and gels containing the composition of the present invention caused an improvement in wound closure rate over that of controls consisting of sterile isotonic saline . the wound repair rate appeared dose dependent in reference to the number of applications made ; that is , one application daily produced a 17 . 8 % faster rate of wound closure and three applications per day produced a 37 . 2 % faster rate . as in any other bioassay , dose related responses are significant from the standpoint of data validity . composition containing solutions and gels caused an improved wound closure rate over that of controls by increasing the available components for gluconeogenesis and protein synthesis . in addition , increased intracellular atp synthesized by the cells in response to the present invention was quickly utilized as an energy source for these processes and for the wound contraction mechanism . finally , the stoichiometry of wound weight to wound size was consistent as was the inverse relationship between wound weight and atp levels . | 0 |
fig1 illustrates a diagram outlining an example of the operation ( s ) of a communication system 1 used in the reporting of an emergency incident . in one embodiment of the invention , an audio ( or text ) message 1911 reporting selected details of the emergency ( i . e ., “ accident yyy at location xxx has already been reported ”) is broadcast to cellular telephones , “ blackberries ”® or other telecommunication devices 100 in the geographic area of the incident . devices which are to receive this notification can be determined by the tracking capabilities of local transmission facilit ( ies ) 10 ( indicating which device telephone number ( s ) are sending / receiving signals to / from that transmitter ) or by use of satellite navigation ( gps ) systems accessible by the devices , etc . however , broadcasting this information to all communicating phones / devices within the area requires all users to be targeted instead of only those reporting an emergency , and it requires a user to read ( or listen to ) the message for it to be effective . thus in another ( more preferred ) embodiment of the invention , only “ 911 ” calls received from locations close to the ( already - reported ) emergency yyy are directed to an audio message 1911 providing these details . in that case , the relevant incident information is provided to a caller 100 by the emergency communication system 1 when a “ 911 ” call is placed from within the surrounding area near the incident . the extent of the incident surrounding area can be algorithmically determined or initially configured for the emergency system or determined by manual entry ( per incident report ). as an example , the incident surrounding area may be set to one ( 1 ) mile in an urban area , whereas it may be set to five ( 5 ) miles in a rural or highway area to allow for more rapid transit of vehicles . this feature avoids the need to broadcast the message to all individuals moving past the emergency scene ( which can potentially disrupt driver concentration ) and it does not preclude receiving other calls from the same geographic area that might pertain to a different problem . note that it is desirable to allow emergency “ 911 ” calls to be connected in all cases ( since a subsequent call to an emergency system may contain new or additional information ). upon delivering the message 1911 to a subsequent caller 100 , the system 1 can allow the caller to make the determination as to whether to proceed with the call ( with knowledge that the incident has already been reported ). the “ 911 ” operator receiving the initial report ( s ) can determine whether an emergency is “ private ” or “ public ”. “ public ” incidents are defined as those which are likely to be reported by multiple individuals ( and are visible from public locations ). examples include car accidents , fires , and the like . incidents that are not “ public ” are classified as “ private ”. the system 1 determines the location of the emergency , which may be obtained from a user device 100 equipped with a gps system or by identifying the radio / cellular telecommunications site 10 involved ( or by analyzing signal strength from multiple locations , etc .). if the call is from a fixed ( landline ) telephone site 10 such as a public switched telephone network ( pstn ) line or a cable - connected voice over internet protocol ( voip ) line , then the system 1 may receive the location from the telecommunications carrier through calling line identification or media access control ( mac ) address identification . the location may also be identified through verbal or manual reporting of a street address from which the call is made and the system may itself identify the caller location ( or may receive such information from the user device or from the communications carrier as described above ). all of this information can be recorded automatically or through manual entry ( such as by pinpointing the accident site on a map or using a computer “ pull down ” menu to select from a list of locations and / or emergency types ). for example , the emergency operator can “ click on ” a computerized map ( e . g ., showing “ the intersection of route 9a and pleasantville road ” as the accident site ) and / or choose an accident description ( i . e ., “ jack knifed — tractor trailer ”) from a “ pull down ” menu . the emergency response system 1 can include a reporting call “ threshold ” ( to provide empirical proof of a bonafide “ public emergency ”) before triggering automatic notification of other potential callers ( since notification of an already - reported duplicate call can be potentially confusing to callers ). for example , if the notification threshold is set at “ 3 ” then three independent reports of the same emergency are required to allow verification of authenticity ( and the collection of incident details ) before automatic notification to callers in the geographic location of the emergency will take place ( using the methods described herein ). such a threshold may be automatically ( i . e ., algorithmically ) or manually set to any numerical value ( including one or zero ) to account for any type of disaster . when another caller reports the same emergency , details of the emergency will continue to be recorded until the threshold has been exceeded ( whereupon new callers will receive an automated message indicating the reported problems in the area as described above ). for example , a person calling from a location close to “ the intersection of route 9a and pleasantville road ” will read or hear an automated message ( such as “ the jackknifed tractor trailer near route 9a and pleasantville road has already been reported . unless you have additional information about that accident or are calling about another problem you may hang up . to speak to a “ 911 ” operator press # 1 ”). audio or text messages may be generated automatically by the emergency reporting system 1 using excerpts of synthetic or recorded speech to form the message ( in order to minimize the impact on “ 911 ” operators and on reporting callers ) if the incident type and location is known . a preferred embodiment of the invention can use tracking of uniquely identified callers ( such as through identification of individual calling telephone numbers ) for determining if the automatic emergency notification threshold has been exceeded , since counting only the number of reporting callers from the same geographic area may prevent a caller from completing an incident report if a connection is lost and then reestablished . for example , if a caller dials “ 911 ” and ( in mid - report ) loses the telephone connection ( through user error or loss of a cellular signal , etc .) then the feature requiring identification of unique callers will assure that such partial attempts do not trigger the informational 1911 message . while certain preferred features of the invention have been shown by way of illustration , many modifications and changes can be made that fall within the true spirit of the invention as embodied in the following claims , which are to be interpreted as broadly as the law permits to cover the full scope of the invention , including all equivalents thereto . | 7 |
fig2 illustrates one implementation of an on - chip capacitor 200 . on - chip capacitor 200 includes two layers 201 , 203 of conducting strips formed upon a substrate 202 . substrate 202 can be a p - type substrate or an n - type substrate . a first layer 201 is formed by two sets of conducting strips 204 a and 204 b . conducting strips 204 a and 204 b are arranged alternately and substantially in parallel to each other ( i . e ., a conducting strip 204 a is next to a conducting strip 204 b , which , in turn , is located next to a second conducting strip 204 a , and so on ). a second layer 203 is formed by two sets of conducting strips 206 a and 206 b . second layer 203 can be separated from first layer 201 by an insulating layer ( not shown ). the insulating layer can be a silicon dioxide layer . second layer 203 at least partially overlies first layer 201 — e . g ., at least one conducting strip of the second layer overlies at least a portion of a conducting strip in the first layer . conducting strips 206 a and 206 b are also arranged alternately and substantially in parallel to each other . in one implementation , conducting strips 206 a and 206 b overlie and are substantially perpendicular to conducting strips 204 a and 204 b . conducting strips 204 a of first layer 201 and conducting strips 206 a of second layer 203 are connected to form a first common node . in one implementation , conducting strips 204 a and conducting strips 206 a are connected by vertical vias . likewise , conducting strips 204 b of first layer 201 and conducting strips 206 b of second layer 203 are connected to form a second common node . the first common node and the second common node form opposing nodes of on - chip capacitor 200 . each conducting strip 204 a connected to the first common node has one or more overlying conducting strips 206 b and one or more overlying conducting strips 206 a . likewise , each conducting strip 204 b connected to the second common node has one or more overlying conducting strips 206 a and one or more overlying conducting strips 206 a . in one implementation , the number of “ a ” and “ b ” conducting strips are equal within each layer . fig3 . shows a cross - section of on - chip capacitor 200 ( fig2 ). a parallel plate capacitance ( cpp ) is present between each conducting strip 204 b and conducting strip 206 a . furthermore , a sidewall capacitance ( csw ) is present between each adjacent pair of conducting strips ( e . g ., conducting strips 204 a and 204 b ) within each layer . in addition , a substrate capacitance ( cb ) is formed between conducting strips in first layer 201 ( e . g ., conducting strips 204 a and 204 b ) and substrate 202 . as shown in fig3 , substrate 202 can be at ground ( or a low voltage potential ). fig4 illustrates a top view of how conducting strips 204 a and 204 b of first ( lower ) layer 201 and conducting strips 206 a and 206 b of second ( upper ) layer 203 are laid out in one implementation . conducting strips 204 a and 204 b of the lower layer are shown in solid lines . in one implementation , conducting strips 204 a are connected by a base strip 208 a and conducting strips 204 b are connected by a base strip 208 b . alternatively , each of conducting strips 204 a and conducting strips 204 b can be respectively connected by vertical vias ( not shown ). base strips 208 a and 208 b are located at opposing ends of conducting strips 204 a and 204 b so that conducting strips 204 a and 204 b are interdigitated . in one implementation , base strips 208 a and 208 b are sized to be narrow — e . g ., as wide as conducting strips 204 a and 204 b — to minimize space occupied by on - chip capacitor 200 . conducting strips 206 a and 206 b of the upper layer are shown by dotted lines and are displaced to distinguish the upper layer conducting strips 206 a and 206 b from the lower layer conducting strips 204 a and 204 b . in general , conducting strips 206 a and 206 b substantially lie perpendicularly directly over conducting strips 204 a and 2043 . in one implementation , conducting strips 206 a are connected by a base strip 210 a and conducting strips 206 b are connected by a base strip 210 b . alternatively , each of conducting strips 206 a and conducting strips 2063 can be respectively connected by vertical vias ( not shown ). as shown in fig4 , base strips 210 a and 210 b are at opposing ends of conducting strips 206 a and 206 b . in one implementation , the second layer pattern of interdigitated conducting strips 206 a and 206 b is substantially perpendicular to the first layer pattern . the interconnections between the “ a ” conducting strips — i . e ., conducting strips 204 a and 206 a , and the “ b ” conducting strips — i . e ., conducting strips 204 b and 206 b , are not shown . in one implementation , the interconnections are made by vertical vias ( not shown ) through the insulating layer between first layer 201 and second layer 203 of on - chip capacitor 200 . fig5 . shows a cross - section of one implementation of on - chip capacitor 200 ( fig2 ). as shown in fig5 , on - chip capacitor 200 includes a guardband 500 for attenuating coupling between on - chip capacitor 200 and external electromagnetic fields . guardband 500 can be formed from a conductive material , for example , polysilicon , aluminum , and copper . in one implementation , guardband 500 is provided on each of first layer 201 and second layer 203 and substantially encircles the first and second common nodes of on - chip capacitor 200 . guardband 500 can encircle less than all of first layer 201 and second layer 203 . guardband 500 can only run along one side of on - chip capacitor 200 . in addition , guardband 500 can be included on other layers either above or below first layer 201 and second layer 203 of on - chip capacitor 200 . in one implementation , guardband 500 is spaced from the conducting strips a distance ( dg ) that is approximately twice the distance ( dh ) between adjacent conducting strips . distance ( dg ) can be selected to minimize the parasitic fringing capacitance that is formed between guardband 500 and an adjacent conducting strip or base strip , while at the same time maintaining a volumetrically efficient on - chip capacitor 200 . in one implementation , to maintain a predetermined ratio between the capacitance of on - chip capacitor 200 and the parasitic capacitance formed from guardband 500 , distance ( dg ) is increased when there are fewer conducting layers or conducting strips , and distance ( dg ) is decreased when there are more conducting layers or conducting strips . in one implementation , a line width of guardband 500 is selected to be the same as a line width of a conducting strip — e . g ., conducting strip 206 a or 206 b . however , other line widths can be selected . in one implementation , guardband 500 is coupled through a low impedance ( not shown ) to a voltage potential such as ground . in one implementation , guardband 500 floats with respect to system voltage potentials . fig6 illustrates a top view of one implementation of a path configuration for an on - chip capacitor 600 . on - chip capacitor 600 contains conducting strips that are laid out a path configuration that is substantially spiral . in particular , on - chip capacitor 600 includes lower layer conducting strips 602 a and 602 b and upper layer conducting strips 604 a and 604 b . conducting strips 602 a and 602 b of the lower layer are shown in solid lines and conducting strips 604 a and 604 b of the upper layer are shown in dotted lines . conducting strips 604 a and 604 b of the upper layer are displaced to distinguish the upper layer conducting strips 604 a and 604 b from the lower layer conducting strips 602 a and 602 b . in one implementation , conducting strips 604 a and 604 b respectively lie substantially directly over conducting strips 602 b and 602 a . other path configurations can be implemented , e . g ., l - shaped paths and s - shaped paths . fig7 a . shows a cross - section b - b ( fig7 b ) of an on - chip capacitor 700 . on - chip capacitor 700 includes two layers 701 , 703 of conducting strips formed upon a substrate 702 . a first layer 701 is formed by two sets of conducting strips 704 a and 704 b . conducting strips 704 a and 704 b are arranged alternately and substantially in parallel to each other so that a conducting strip 704 a is located next to a conducting strip 704 b , as shown in fig7 b . referring to fig7 a and 7b , a second layer 703 is formed by two sets of conducting strips 706 a and 706 b . conducting strips 706 a and 706 b are also arranged alternately and substantially in parallel to each other so that a conducting strip 706 a is located next to a conducting strip 706 b . conducting strips 706 a and 706 b respectively overlie and are substantially parallel to conducting strips 704 a and 704 b , such that conducting strips of a same polarity overlie one another . for example , conducting strip 706 a — shown as having a “+” polarity — substantially overlies conducting strip 704 a — also shown as having a “+” polarity . on - chip capacitor 700 further includes vertical vias 708 a that interconnect conducting strips 706 a and 704 a , and vertical vias 708 b that interconnect conducting strips 706 b and 704 b . a parallel plate capacitance ( cpp ) is present between each adjacent pair of conducting strips ( e . g ., conducting strips 706 a and 706 b ) within each layer . furthermore , a via capacitance ( cv ) is present between each adjacent pair of vertical vias ( e . g ., vertical vias 708 a and 708 b ). fig7 c shows a top view of on - chip capacitor 700 . in one implementation , conducting strips 706 a are connected by a base strip 710 a and conducting strips 706 b are connected by a base strip 710 b . base strips 710 a and 710 b are located at opposing ends of conducting strips 706 a and 706 b so that conducting strips 706 a and 7063 are interdigitated . in one implementation , base strips 710 a and 710 b are sized as wide as conducting strips 706 a and 706 b . in one implementation , base strips 710 a and 710 b include vertical vias 712 a and 712 b , respectively . vertical vias 712 a and 712 b interconnect with corresponding base strips ( not shown ) underlying base strips 710 a and 710 b . vertical vias 712 a can be placed along base strip 710 a at locations substantially adjacent to one or more vertical vias 708 b that are located on conducting strips 706 b . likewise , vertical vias 712 b can be placed along base strip 710 b at locations substantially adjacent to one or more vertical vias 708 a that are located on conducting strips 706 a . in addition to the parallel plate capacitance ( cpp ) ( fig7 a ), and the via capacitance ( cv ) ( fig7 a ), a base strip via capacitance ( cvb ) is present between each adjacent pair of base strip vertical via and conducting strip vertical via ( e . g ., vertical vias 712 a and 708 b ). fig8 . shows a cross - section of one implementation of on - chip capacitor 700 ( fig7 a ). as shown in fig8 , on - chip capacitor 700 includes a guardband 800 for attenuating coupling between on - chip capacitor 700 and external electromagnetic fields . in one implementation , guardband 800 is provided on each of first layer 701 and second layer 703 and substantially encircles the first and second common nodes of on - chip capacitor 700 . guardband 700 can encircle less than all of first layer 701 and second layer 703 . guardband 800 can only run along one side of on - chip capacitor 700 . in addition , guardband 800 can be included on other layers either above or below first layer 701 and second layer 703 of on - chip capacitor 700 . a number of implementations have been described . nevertheless , various modifications to the implementations may be made . for example , an on - chip capacitor can be formed in a split - capacitor configuration 900 as shown in fig9 . split - capacitor configuration 900 includes a first on - chip capacitor 902 and a second on - chip capacitor 904 formed upon a substrate 906 . each of first on - chip capacitor 902 and second on - chip capacitor 904 can have any one of the capacitor structures described in the implementations above . in addition , each of the capacitor structures described above can have any number of conducting layers , e . g . more than two layers . accordingly , other implementations are within the scope of the following claims . | 7 |
fig1 shows an application in which the system of the present invention may be used to great advantage . for example , the integrated arrangement may be comprised of conveyors 11 for delivering signatures from a press to a plurality of signature stackers 12 for stacking the incoming signatures into signature bundles 13 which may be of the compensated or uncompensated type . each stacker 12 transfers a completed bundle to an outfeed conveyor 14 for delivery to a tying station 15 . each tied bundle is transferred from the tying station to a conveyor 16 for delivering each completed bundle to an overhead loader 17 which will be more fully described hereinbelow . each of the overhead loaders is controlled by a computer to precisely drop a completed bundle into the desired tray assembly 20 as it passes beneath the proper overhead loader . the loader conveyor may be used to bypass the overhead load and deliver a bundle to a bypass conveyor as an alternative delivery path to a truck , loading dock or other location . each of the tray assemblies 20 is pivotally linked to the adjacent upstream and downstream tray assembly to provide a closed loop product conveyor arrangement wherein each tray assembly serves as a &# 34 ; link &# 34 ; within an elongated , closed loop conveyor &# 34 ; chain &# 34 ; which is continuously recirculated about the loop by linear electric motors arranged at spaced intervals about the loop with the path of the loop being defined by a closed loop track 40 which is arranged to traverse a particular region and to substantially accommodate the contours and configuration of the region . for example , in the network 10 shown in fig1 the application provided therein is deliver predetermined bundles to a predetermined delivery truck 50 under control of a computer system . in order to provide a gravity feed arrangement , the track is provided with an inclined portion 40a to lift the trays and hence the bundles carried thereby to an elevation sufficient to feed a bundle to the desired truck by means of gravity . by computer control , a pneumatic ejector tilts the proper tray assembly , such as , for example , the tray assembly 20 &# 39 ; causing the bundle 13b to be dispensed from tray assembly 20 &# 39 ; and fall downwardly by gravity along an outfeed chute 60 and thereafter along an outfeed conveyor 62 for delivery directly to the desired truck 50 positioned at the loading dock in alignment with the outfeed conveyor 62 . as will be more fully described , a pair of straightening cams are utilized to return the tilt tray to the upright position preparatory to being returned to the bundle receiving portion of the conveyor &# 34 ; chain &# 34 ; whereby the tray may be loaded with a bundle from any of the overhead loaders , all under control of the computer system for controlling the loading and unloading operations . fig2 a - 2d show a typical tilt tray assembly 20 and the manner in which it is guided by the guide track 40 . as shown best in fig2 b and 2c , the guide track is comprised of track portions 41 and 42 which are joined to suitable supporting elements ( not shown for purposes of simplicity ) so that the flanges 41a , 42a cooperate to provide a guide for the vertical roller 27 of the tilt tray assembly which cooperates with the guide flanges 41a and 42a to limit the lateral movement of the tray assembly as it moves along the track . upper and lower portions 41b , 41c and 42b , 42c of track portions 41 and 42 form guides for the horizontal rollers of the tilt tray assembly to limit movement of the tilt tray assembly in a direction transverse to the horizontal . as can be appreciated from fig1 the track may be comprised of a plurality of straight portions , curved portions , inclined and downwardly sloping portions of both the straight and curved type , the design of the tilt tray assemblies enabling the conveyor to navigate around horizontal curves as small as six ( 6 ) feet in radius , vertical curves as small as ten ( 10 ) feet in radius , and inclination angles of up to 30 °. the track sections are preferably formed of a suitable metallic material to provide a rugged and highly serviceable track . each tilt tray assembly 20 is comprised of a one - piece frame 21 shown in detail in fig3 a - 3d and comprised of a base portion 21c provided with forward and rearward uprights 21b , 21a having openings whose centerlines are horizontally aligned for supporting a shaft 22 for swingably mounting the tilt tray 23 . tilt tray 23 is comprised of a substantially flat base portion 23a having integral forward and rearward sides 23b , 23c which form an angle slightly greater than 90 ° with base portion 23a . left and right - hand sides 23d , 23e form an angle of just slightly less than 180 ° with base portion 23a . forward and rearward sides 23b , 23c serve to retain a bundle therebetween to a much greater degree than sides 23d and 23e which are designed to facilitate the dispensing of a bundle when the tilt tray is tilted from the upright position shown in fig2 b to the tilted position shown in fig2 c , to facilitate the delivery of a bundle at an outfeed chute location 60 , shown for example , in fig1 . the forward end of frame 21 extends forwardly beyond upright 21b and is provided with a threaded opening 21d for receiving a ball and socket assembly comprised of threaded member 24 having a circular &# 34 ; socket &# 34 ; portion 24a for rotatably supporting the ball member 24b having an opening 24c adapted to receive a pin provided at the rearward end of the tilt tray assembly positioned immediately in front of tilt tray assembly 20 shown , for example , in fig2 a . this pin is shown , for example , as pin p arranged within the vertically aligned opening 21e provided in the portion of frame 21 extending rearwardly of rear upright 21a ( see fig2 b ). the central portion of opening 21e in the frame is enlarged as shown at 21f to receive the ball and socket assembly of the tilt tray assembly 20 shown in fig2 a , for example . the rearward end of frame 21 is further provided with horizontally aligned threaded openings 21g , 21h which receive and threadedly engage the threaded portions of a pair of axle pins 24 , 24 which serve to rotatably mount the wheels 25 , 25 which rotate about the wheel bearings 25a , 25a . the bottom surface 21i of frame 21 is provided with a cold rolled steel plate 26a and an aluminum plate 26b respectively laminated to the bottom surface thereof and cooperating with the linear motor ( to be more fully described ) to set up the proper eddy current paths for propelling the tilt tray assembly . as was mentioned hereinabove , vertical pin p , in addition to extending through the hollow opening 24c in ball member 24 , further rollingly supports vertical wheel 27 having bearings 27a for rotation about the pin p . the tilt assembly ta is comprised of a threaded locking pin 28 threadedly engaging tapped opening 21j in frame 21 . a tip frame 29 shown in fig4 a , 4b and 4c is a substantially rectangular - shaped frame having openings 29a , 29b for receiving and being swingably mounted upon shaft 22 which is rigidly secured to uprights 21b , 21a by fasteners f , f . tip frame 29 is provided with tapped openings 29c for threadedly receiving suitable fasteners to secure tray 23 thereto . frame 29 has a pair of projections 29d , 29e which extend rearwardly and are positioned on opposite sides of the frame upright 21a . a latch block 30 forming part of the tilt assembly and shown in detail in fig5 a and 5b is comprised of latch block lower and upper halves 30a , 30b secured to one another by means of fasteners f1 extending through openings 30b - 1 in upper block 30b and threadedly engaging one of the tapped openings 30a - 1 in lower block portion 30a . the blocks are machined or otherwise formed with semi - circular portions so that when they are joined together in the manner shown , for example , in fig2 a and 5a , they define openings o1 and o2 . opening o1 is coincident with the openings 29d - 1 , 29e - 1 in rearward projections 29d and 29e of tip frame 29 . the central axes of these openings serve as a pivot axis for the latch block 30 and latch plate 32 . larger opening o2 is substantially aligned with the elongated openings 29d - 2 , 29e - 2 provided in rearward projections 29d and 29e of tip frame 29 . elongated shaft 31 extends through openings o2 , 29d - 2 and 29e - 2 as shown best , for example , in fig2 a - 2e . cam follower rollers 31a , 31b are rotatably mounted at the opposite ends of shaft 31 . the intermediate portion of shaft 31 extends through opening o2 and is tightly clamped between the latch block halves 30a and 30b . resilient o - rings 31c prevent metal - to - metal contact between shaft 31 and the interior surfaces of the elongated openings 29d - 2 and 29e - 2 . a latch plate 32 having a substantially semi - circular - shaped slot 32a for embracing locking pin 28 , is provided with a pair of tapped openings 32b , 32c for threadedly engaging fasteners f2 for securing latch plate 32 to the lower half 30a of latch block 30 . a shaft 34 extends through opening o1 in latch block 30 and openings 29d - 1 and 29e - 1 in tip frame 29 . the latch block halves are clamped together to rigidly secure the latch block to shaft 34 which is free to rotate within the openings 29d - 1 , 29e - 1 by suitable bearings 34a , 34b . at least one torsion spring 35 is wrapped about shaft 34 near roller 31b . if desired , a second torsion spring may be provided adjacent the roller 31a . the spring is preferably wrapped about two ( 2 ) to four ( 4 ) turns about shaft 34 . one end of torsion spring 35 rests against the lower rear edge of tray 23 and the other end rests against an adjacent portion of shaft 31 , the torsion spring normally urging the tilt assembly in the counterclockwise direction about shaft 34 relative to fig2 a so as to normally urge and position latch plate 32 against the rearward surface of upright 21c in the manner shown in fig2 a in order to embrace locking pin 28 . the torsion spring 35 also further serves to normally orient the tip frame and tray in the upright position , especially when two such springs are provided . when one of the rollers , such as for example , the right - hand cam follower roller 31a is urged upwardly from the position shown in fig2 b toward the position shown in fig2 c by an opening cam surface c shown in dotted fashion in fig2 c , the initial upward movement of the cam follower roller 31a causes latch block 32 to rotate clockwise ( relative to fig2 a ) about pivot pin 34 , moving latch plate 32 away from latch pin 28 . as soon as the latch plate cup 32a clears latch pin 28 , the tip frame and tray are free to tilt about mounting shaft 30 , moving the tip frame 29 , tilting assembly 27 and tray 23 counterclockwise about shaft 30 ( relative to fig2 b ) to move the tip frame and tray from the position shown in fig2 b to the position shown in fig2 c . the angle of the tilt tray shown in fig2 c is sufficient to cause a bundle riding therein , such as a signature bundle , to be dispensed therefrom . the angle of the tray , together with the rapid movement of the tip frame and tray from the position shown in fig2 b to the position shown in fig2 c , cooperate to drop the signature bundle carried thereon to an outfeed chute , such as , for example , any of the chutes 60 shown in fig1 . as an alternative arrangement , there may be a reversal of parts whereby latch plate 32 may be provided with a pin , and upright frame 21a may be provided with an opening for receiving the pin , said reversal of parts providing substantially the same operation as the arrangement shown , for example , in fig2 a . as will be described more fully hereinbelow , a pair of restoring or straightening cams , arranged on opposite sides of the centerline of movement of the tilt tray assemblies engageable by the cam follower rollers 31a , 31b , cause the tilt tray to be moved to and retained in the upright position . the use of a pair of restoring cams , in addition to restoring the tilt tray to its upright position , prevents overshooting of the tilt tray from the tilted position to a position beyond the upright position . upon return to the upright position , the latch plate cup 32a moves into alignment with latch pin 28 causing the cup to embrace the latch pin under the force of torsion spring 35 and causing the latch plate to be urged against the rear surface of upright 21a to return the tipping assembly to the latched position . the tray assembly will remain in the upright position indefinitely and until tipped therefrom by a tipping cam . as shown in fig2 a , a linear electric motor having a length and width which is substantially equal to the length and width of the bottom surface of frame 21 , is secured to the guide track frame , in the region between flanges 41f and 42f as shown best in fig2 b and is spaced a very small distance away from the bottom surface of the laminated plates arranged upon the bottom surface of frame 21 . the linear electric motor , which may be of the single - sided type produced by northern magnetics , inc . of van nuys , ca , is preferably a three - phase linear motor spaced from the bottom surface of plate 27 to provide an air gap of the order of 0 . 09 inches . the three phase linear motor sets up electromagnetic fields which create eddy currents in the laminated plates secured to the bottom of frame 21 developing a thrust which causes the tray assembly to move in the forward direction as shown by arrow a in fig2 a . the thrust of the motor is sufficient to propel the tray assemblies by providing lims at regularly spaced intervals about the closed loop path . for example , employing the lims of the type described hereinabove , a plurality of such lims spaced at distances of the order of fifty foot intervals have been found to be more than adequate to provide the desired operating speed , which in one preferred embodiment is of the order of 3 . 7 miles per hour having the capability of delivering a 175 bundles per minute at the aforementioned operating speed . the actual spacing , however , is a function of the inclines , curves and other path shapes as well as the bundle weight and may vary dependent upon these factors . the linear motor is further provided with blower means b for maintaining the linear motor at a desired operating temperature , as is conventional . the tray assemblies are conveyed about the closed loop track without any direct mechanical connection whatsoever between the drive motors ( lims ) and the tray assemblies . fig9 shows a simplified view of the manner in which the operating speed is controlled , as will be more fully described . the fig7 a - 7c show the tip cam assembly referred to hereinabove , for tilting the tiltable tray assembly . the tip cam assembly 70 is comprised of an l bracket 71 for mounting the tip cam assembly to one of the guide tracks and , as shown in fig7 c , specifically guide track 41 . fasteners f3 secure the vertical arm of bracket 71 to one vertical side 41d of track 41 while the horizontal arm of l bracket 71 is secured to the horizontal surface 41b of track member 41 by fasteners f4 . the tip cam assembly is further comprised of a ramp member 72 secured to the horizontal arm or bracket 71 by fasteners f5 and having an inclined cam surface 72c . the pivot ramp is further provided with a pair of bifurcated arms 72a , 72b each provided with an opening for receiving a mounting pin 73a extending through an opening in elongated tip cam 73 whose opening is provided in a downwardly depending forward portion 73b . tip cam 73 is coupled to a pair of links 74 , 74 by means of pin 75 . the opposite ends of the links 74 , 74 are coupled to pin 76 which extends through a pair of slider yokes 77 , 77 . a pair of slider blocks 78 , 78 are slidably arranged within the elongated slots 77a , 77a of the associated slider yokes 77 , 77 . the tip cylinder 79 is secured to a mounting block 80 by means of pin 81 which is coupled to the clevis 79a provided at the right - hand end of cylinder 79 . mounting block 80 is secured to the horizontal portion of mounting bracket 71 by fasteners f7 . the cylinder piston 79b extends outwardly from the cylinder and to the left and is provided with a mounting eyelet 79c having an opening for receiving pin 76 . cylinder 79 is a pneumatic cylinder provided with control ports 79d , 79e . assuming the tip cam assembly to be in the off condition with tip cam 73 in the solid line position , and assuming that the next tilt tray assembly is to be tilted , pneumatic pressure is applied to port 79e driving piston 79b to the left . this movement is imparted to the links 74 , 74 which lift tip cam 73 from the solid line position to the phantom line position 73 &# 39 ;. phantom circles 31a , 31a &# 39 ;, 31a &# 34 ; show the progress of the tip cam follower roller 31a . the ramp surface 72c provided along ramp member 72 assures gradual movement of a roller onto the cam surface of the tip cam in the event that there is any misalignment of the cam follower rollers to prevent the cam follower rollers and hence the tip cam assembly from experiencing any sudden jolt or impact as a cam follower roller moves , approaches and engages the tip cam assembly . the tip cam assembly may be rapidly reset by applying pneumatic pressure to port 79d to thereby abruptly move the tip cam from the phantom line position 73 &# 39 ; to the solid line position 73 in order to prevent the tilting of a tilt tray assembly which is not intended to be unloaded at the output chute location . tip cam assemblies of the type shown as assembly 70 in fig7 a - 7c are provided at a location slightly upstream relative to each output chute 60 in order to selectively tilt the desired tilt tray assembly . it should be noted that each tilt tray assembly is capable of being tilted either in the clockwise direction or in the counterclockwise direction ( relative to fig7 c , for example ) and further that the output chutes may be placed on either side of the closed loop track enabling unloading of a signature bundle to an outfeed location on either side of the closed loop track . thus , by placing a tip cam assembly on the opposite side of the track assembly , i . e . by mounting a tip cam assembly to the track portion 42 shown in fig7 c , the tilt tray may be tilted in the clockwise direction relative to fig7 c , the side upon which the dispensing of bundles is to take place being dependent only upon the needs of the user . fig8 a - 8c show the tray straightener cam assemblies 90 , 90 , there being a tray straightener cam assembly mounted to each track half 41 , 42 as shown in fig8 c . since the tray straightener cam assemblies are substantially identical and are actually symmetrical to one another , these assemblies have been identified by like numerals . each assembly is comprised of an l - shaped mounting bracket 91 whose vertical arm is secured to an associated one of the track portions by fasteners f1 while the horizontal arm is coupled to one of the track sections by fasteners f2 . a straightener cam 92 is provided with a ramp portion 92a which slopes upwardly in the direction of movement of the tip cam follower roller 31a and , after reaching a peak at 92b , has a downward sloping portion 92c . a cam mount 93 cooperates with cam 92 for positioning a slidable cam 94 . cam mount 93 has a tapered portion 93a which can be seen to be coplanar with an upper portion of the sloping portion 92a of cam 92 . at a peak 93b which is in alignment with the peak 92b of cam 92 , cam mount 93 has a downwardly sloping portion 93c which is coplanar with the downwardly sloping portion 92c of cam 92 . adjustable cam member 94 is provided with a pair of elongated slots 94a , 94b through which the fasteners f2 and f3 extend , fasteners f2 and f3 being threaded at their free ends to threadedly engage tapped apertures 92d , 92e in cam member 92 . adjustable cam 94 has an upwardly sloping surface portion 94c and a downwardly sloping portion 94d , these portions being substantially coplanar with the upwardly sloping portions 92a , 93a , and the downwardly sloping portions 92c , 93c . adjustable cam 94 is slidable either downwardly and to the left or upwardly and to the right to extend the upward sloping portion in order to adjust the tray straightener assemblies to compensate for any deviations from the normal spacings between the cam follower rollers and the cam straightener assemblies . noting fig8 c , a pair of cam straightener assemblies are provided for cooperation with each cam follower roller 31a , 31b regardless of the direction in which the tray is tilted for the reason that the provision of two cam straighteners each cooperating with the associated cam follower rollers prevents the tilting assembly from overshooting the desired upright position , regardless of the direction in which the tray has been tilted . the tray straightener cam assemblies are mounted just downstream from each output chute in order to straighten each tilt tray assembly as it passes the tray straightener cam assembly . as was mentioned hereinabove , the linear motors are controlled to accurately regulate the speed of the tilt tray assemblies in order to accurately dispense bundles from each of the outlet chute locations , as well as being capable of operating the loader which loads bundles onto the tilt tray assemblies , the operation of the loaders also being dependent upon accurate control of the speed of the tilt tray assemblies . the manner in which the desired control is obtained is by way of a feedback arrangement shown in fig9 comprised of a controller 100 for controlling the current to each of the lims . a speed setting input 100a receives the desired speed . for example , a touch screen may be employed for inputting the desired speed and for displaying the desired speed which has been inputted . controller 100 is coupled to encoder 104 which provides a feedback signal of the conveyor speed which is continuously compared against the set speed for regulating the amplitude of the three - phase current applied to each of the linear motors 102 . encoder 104 is comprised of an encoder assembly shown best in fig9 a - 9f and includes a substantially u - shaped encoder support 106 coupled to the downwardly depending flange portions of the track sections 42 and 41 shown best in fig9 b . a pair of plates 108 , 110 are secured together in spaced parallel fashion by means of spacers 109 arranged between the plates and set within shallow circular recesses provided in the plates as shown in the vicinity of the uppermost spacer 109 &# 39 ; shown in fig9 a . the spacers are secured to plates 108 and 110 by fasteners f1 . three tires 111 , which are substantially identical to one another , are mounted to rotate upon shafts 112 journaled within bearings arranged within the plates 108 and 110 . each tire 111 has an integral gear member 111a while the uppermost tires 111 &# 39 ; are further provided with left - hand integral gear members 111b . an encoder 113 is fixedly secured to left - hand plate 108 by fasteners f2 . encoder 113 is provided with a similar gear or sprocket 113a extending to the right of the encoder housing . the shaft upon which the sprocket is mounted extends through a clearance opening 108a provided in plate 108 . encoder 113 is designed to provide an electrical signal representative of the rotational speed developed by the encoder shaft 113b which is coupled to the right - hand gears 111a by means of a common timing belt 114 shown in dotted fashion . the tire assemblies 111 &# 39 ; also have their left - hand gears coupled in common by a single timing belt 115 . three shafts 116a , 116b , 116c shown in dotted fashion in fig9 a and shown in solid line fashion in fig9 b through 9e , extend through cooperating openings , such as , for example , the openings 108b , 110b provided in plates 108 and 110 . clamp collars 117 orient plates 108 and 110 relative to the shafts 116a , 116c , each clamp collar further including a threaded fastener 117a as shown in fig9 b for rigidly securing each clamp collar to its associated shaft and for further clamping plates 108 and 110 between each associated pair of clamp collars . each of the shafts 116a - 116c have their left and right - hand ends extending through elongated slots 106a , 106b provided in the vertical sides of support 106 . clamp collars 117 &# 39 ; fixedly secure the shafts against movement in the direction of their longitudinal axis while at the same time permitting each of the shafts to move vertically up or down within the elongated slots . note , for example , slot 106b shown in fig9 e . a plurality of mounting pin assemblies 18 are secured to the right - hand vertical side of support 106 and each of said assemblies , at their free ends support the upper end 119a of a helical spring 119 whose lower end 119b embraces an associated one of said shafts 116a - 116c . a plurality of somewhat similar pin assemblies 120 are fixedly secured to the left - hand vertical side of support 106 and , in a similar fashion , each supports the upper end 121a of a helical spring 121 whose lower end 121b is wrapped about the left - hand end of an associated one of the shafts 116a - 116c . each of the shafts is preferably provided with an annular groove for receiving and retaining the lower ends 119b , 121b of the helical springs 119 , 121 respectively . the resiliently mounted tire assembly is adjusted so that the surfaces of the tires 111 and 111 &# 39 ; engage the bottom surfaces of the tilt tray assemblies as they pass over the sensor assembly 104 with the resiliency of the springs being adjusted so that the wheels are urged against the bottom surfaces of the frames with a force of the order two ( 2 ) to four ( 4 ) pounds . the spring supporting pins 118 and 120 are mounted within elongated slots in the vertical sidewalls of support 106 , such as , for example , elongated slot 106c provided in the right - hand vertical side of the support 106 and are adjustable to adjust the spring force . fig9 f shows the manner of operation of the encoder assembly . as was mentioned hereinabove , all three tires are tied together with at least one timing belt and in operation , the tires 111 and 111 &# 39 ; are positioned in such a manner that two of the three tires are always in rolling engagement with one of the tilt tray assemblies . the tires are further always maintained in rotation since even a tire moving into the gap g between adjacent tilt tray assemblies 20 will not be free wheeling due to the fact that it is rotated by the timing belt of the remaining two tires which make rolling engagement with the passing tilt tray assemblies 20 . thus , the encoder assembly provides an accurate indication of the operating speed enabling the controller to dynamically adjust for any changes in operating speed by altering the driving signal applied to the linear motors 102 . all of the linear motors are coupled in electrical parallel and the nature of the system is such that even the failure of one or two of the linear motors will not require shutdown of the system . fig1 a - 10f show the top loader 17 employed for purposes of loading bundles into the desired tilt tray assembly . each such top loader is comprised of four support frames 125 , each provided with a mounting plate 126 for securement to a support surface . the vertical support members 125 are secured at their top ends to form a substantially rectangular frame by means of cross pieces 127 , 128 , 129 and 130 forming a substantially rectangular - shaped frame , each of the cross pieces being of a substantially rectangular - shaped cross - section . additional cross pieces 131 and 132 are respectively secured to cross pieces 128 and 130 and are arranged in spaced parallel fashion to cross pieces 127 and 129 , respectively . a support plate 133 secured to cross pieces 129 and 132 by fasteners f1 supports a pair of bearing assemblies 134 , 134 whose lower ends are fastened by suitable fastening means to support plate 133 . the bearing assemblies 134 , 134 rotatably support a jack shaft 140 which is free - wheelingly rotatable within the bearing assembly and has a first end thereof secured to a timing belt pulley 135 which is driven by a timing belt 136 entrained about a timing belt pulley 137 mounted to the output shaft of a servo - motor 138 which is mounted upon a support bracket 139 which in turn forms an integral part of the support plate 133 . a timing belt pulley 141 is mounted to the opposite end of jack shaft 140 . an elongated timing belt 142 is entrained about timing belt pulley 141 and a driven timing belt pulley 143 rotatable about shaft 144 mounted upon support bracket assemblies 145 , 145 , each having a resilient member 145a , 145a for providing proper tension for timing belt 142 . the tensioning assemblies are each provided with threaded fasteners 145b , 145b which extend through and threadedly engage tapped openings in support shaft 144 which is thereby fixedly secured against rotation , timing belt pulley 143 being provided with suitable bearing means for free - wheelingly mounting the timing belt pulley upon shaft 144 . servo - motor 138 ultimately drives timing belt pulley 142 in a reciprocating fashion for unloading bundles from the top loader conveyor ( to be more fully described ) and for rapidly resetting the pusher member . the pusher assembly is comprised of a pair of elongated cylindrical rods 146 , 146 which are fixedly secured to cross pieces 131 , 132 as shown best in fig1 c . a mounting plate 147 is provided with guides 148 arranged along opposite sides of the mounting plate and provided with free - wheeling rollers 148a which rollingly move along the rods 146 , 146 to guide the movement of the mounting plate . a pair of vertical mounting brackets 149 , 149 are secured to support plate 147 and in turn have pusher plate 150 secured thereto . the vertical mounting brackets 149 have an l - shaped cross - section and are provided with a tapered portion 149a as shown best in fig9 a to enhance the inherent supporting strength of vertical brackets 149 . mounting plate 147 further includes a timing belt clamping member 151 secured to mounting plate 147 by fasteners f2 . the bottom surface of clamping member 151 is provided with a gear - like configuration conforming to the toothed configuration of the timing belt 142 and is adapted to interfit with the timing belt so to provide excellent clamping and securement therebetween . thus , movement of the lower run 142a of timing belt 142 is directly imparted to the pusher 150 through mounting plate 147 and vertical mounting brackets 149 . fig1 a and 10c show the position of the pusher preparatory to pushing a bundle from the conveyor assembly ( to be more fully described ). servo - motor 138 is rotated to move the lower run 142a of the timing belt in the direction shown by arrow a causing pusher 150 to move in the same direction . the pusher is moved through a distance sufficient to move a bundle to the position to be dispensed off the belt conveyor assembly ( to be more fully described ) and thereafter to rapidly return to the start position in readiness for dispensing the next bundle . the conveyor assembly 151 is comprised of a closed loop conveyor belt 152 entrained about a drive roller 153 and driven roller 156 mounted between a pair of support plates 154 . a plurality of spaced parallel rollers 155 are free - wheelingly mounted between the plates 154 , 154 in the space between rollers 153 and 156 and serve to rollingly support the conveyor belt 152 in the space between the drive roller 153 and the driven roller 156 . motor means 158 moves the drive roller 153 and hence the conveyor belt at the proper linear speed . tension adjusting assemblies 157 , 157 are arranged on the left and right - hand support plates 154 , 154 for adjusting the spacing between driven roller 156 and drive roller 153 to thereby adjust the tension of the conveyor belt 152 . the conveyor belt is preferably formed of a suitable low friction material or may be formed of a suitable fabric , for example , which is coated with a material to provide an extremely low friction outer surface to provide a low coefficient of sliding friction . bundles are introduced onto the conveyor which moves in the direction shown by arrow b in fig1 c at a speed commensurate with the mating delivery conveyor . a gate assembly is positioned to the downstream side of the pusher 150 and is comprised of a reciprocating gate 160 shown in fig1 a through 10c and shown in greater detail in fig1 d and 10e . gate 160 is slidably mounted between a pair of upper and lower tracks 161 , 162 . the tracks are secured to a gate mounting plate 163 by means of supports 164 arranged at both the upper and lower ends . a cylinder 165 is secured to mounting bracket 163 by supports 166 . the cylinder 167 is provided with ports 167a , 167b . conduits 167c , 167d are coupled to suitable pneumatic sources for applying pneumatic pressure to the cylinder whose piston 167 extends outwardly from cylinder 165 and is provided with a clevis 168 at its free end for receiving a fastener f3 for coupling the piston rod 167 to gate 160 which is provided with a mounting member 169 having a tapped opening for receiving fastener f3 and having a tapped opening for receiving a fastener f4 for securing mounting block 169 to gate 160 . the head of fastener f4 is flush with the lower surface of gate 160 as shown in fig1 d . the gate 160 is provided with a plurality of fasteners f5 which are threadedly secured to gate 160 and extend in opposite directions therefrom so as to be slidably engaged with the sidewalls of the guide tracks . noting , for example , fig1 d , gate 160 is provided with elongated strips 160a , 160b secured to gate 160 by fasteners f5 , said strips slidably engaging the sidewalls of the tracks , the heads of fasteners f5 being flush with the surfaces of the strips so as to provide a low friction surface for engaging the sidewalls of the track . a bundle is delivered from a mating conveyor positioned adjacent to the driven conveyor roller 156 ( see fig1 c ) and moves on to the conveyor which is operated so that its upper run moves in the direction shown by arrow b at a speed which may be the same speed as the mating conveyor if the mating conveyor is powered . however , any conveyor speed commensurate with the delivery rate of bundles may be employed . a motion sensor 178 ( see fig1 a ) senses the motion of gate 160 due to a bundle moving against the gate , whereupon the controller operates servo - motor 138 to move pusher plate 150 toward the right in a direction shown by arrow b in fig1 a to push a bundle off of the belt conveyor when the appropriate tiltable tray assembly is positioned beneath the conveyor assembly 151 . gate 160 limits the travel of a bundle on conveyor belt 152 and also aligns the bundle with the path of movement of the tray assemblies beneath the conveyor . pusher 150 sweeps the bundle on the conveyor belt 152 off of the right - hand end of the conveyor ( relative to fig1 a and 10c ) so as to fall upon the tiltable tray assembly moving beneath the top loader assembly . although the bundle being delivered is moved off of the conveyor 151 at a rather rapid rate , a portion of the bundle overhanging the right - hand end of the conveyor assembly 151 undergoes a tipping action wherein the right - hand end of the bundle is lowered relative to the left - hand end which is still supported by the conveyor belt . thus , when a bundle is totally clear of the conveyor belt , it will be tilted as it experiences free fall in dropping into the desired tilt tray assembly . thus , in order to correct for this , and thereby be assured that each bundle is oriented horizontally as it experiences free fall in dropping into the appropriate tilt tray assembly , the conveyor belt assembly is tilted so that its right - hand end 151a is higher than its left - hand end 151b ( note fig1 a ). similarly , the guide rods 146 , 146 and hence pusher plate 150 are tilted relative to the vertical so that its lower end 150a extends further to the right than its upper end 150b ( relative to fig1 a ) in order to provide a uniform pushing force against the left - hand end of the bundle engaged by pusher plate 150 . the tilt angle and path of movement of pusher plate 150 and the tilt angle of the conveyor are preferably equal . sensors 177a and 177b serve to positively identify the location of the gate piston rod 167 for assuring the proper positioning thereof and further for assuring the proper control . as was mentioned hereinabove , the pusher 150 is moved in such a manner that its full stroke occurs within a period of 0 . 7 seconds . fig1 g shows a plot of pusher plate velocity versus distance . the velocity increases from zero until it reaches a maximum at approximate the midpoint of a full stroke at which time the velocity decreases until it reaches the end point of a full stroke . the actual shape of the velocity / time curve is not critical so long as proper stroke interval is maintained and the bundle is properly dispensed . sensors 179 , 180 and 181 serve for sensing the extreme left - hand position , the home position and the forward stroke position respectively of the pusher plate . the sensors cooperate with a rod 147a extending from mounting plate 147 to provide a signal for identifying the position of the pusher plate 150 . the gate 160 may be retracted to enable a bundle or bundles to be delivered to a bypass conveyor 16a aligned with the conveyor 151 and adjacent the conveyor roller 153 ( see fig1 ) for delivery to a truck or any other outfeed location . for example , if all of the bundles from each stacker are the same and can be delivered to any trucks , there is no need to deliver bundles using the closed loop conveyor . thus , the gate 160 may be retracted and bundles delivered to a bypass conveyor to the loading dock , for example . a latitude of modification , change and substitution is intended in the foregoing disclosure , and in some instances , some features of the invention will be employed without a corresponding use of other features . accordingly , it is appropriate that the appended claims be construed broadly and in a manner consistent with the spirit and scope of the invention herein described . | 1 |
a schematic representation of the handheld electronic cryoprobe 10 is shown in fig1 . cryoprobe 10 is used in conjunction with a disposable application or probe tip 12 . probe tip 12 can be of varying sizes , shapes and lengths , and has a biocompatible treatment surface in thermal contact with the distal end 17 of heat pipe 16 . a handle 14 is provided to facilitate use of probe 10 by the physician . in general , cryoprobe 10 is reusable , since tip 12 is the only component which is disposable . in general , probe 10 may include a number of different handle and tip configurations to tailor the probe to a particular surgical procedure and / or the preference of a particular physician . for this reason , tip 12 and handle 14 are shown in schematic form . the disposable probe tip 12 can contain thermoelectric and / or heat pipe materials , and is used as a trim cooler / heater to give fine temperature or control during the surgical procedure . a sterile sleeve ( not shown ) can be attached in the configuration so that it will slide over the heat pipe extension when installed . a quick snap - on connection ( not shown ) automatically makes power and thermocouple leads . heat pipe extensions can also be quick - connected to the main power thermoelectrics in the handle ( not shown ), and contain power and thermocouple extension wiring for controlling the tip 12 . the proximal end 19 of heat pipe 16 is attached to peltier effect thermoelectric cooling modules 18 . proximal cooling modules 18 draw heat from tip 12 and rejects it into a heat exchanger system depicted at 20 . a liquid coolant such as tap or chilled water may be circulated through appropriate tubing 22 , 23 to transfer heat from cryoprobe 10 to the remote heat exchanger 20 which in turn rejects the heat into the environment . tubing 22 , 23 may be made , for instance , of any well known plastic material , and may be insulated . alternatively , to get the heat from the thermoelectrics in handle 14 to the remote heat exchanger 20 , it is possible to use a circulating liquid system where supply and return liquid channels and wiring are contained within one tube ( not shown ). this tube will have a closed cell insulation extruded over the channels , with an outer protective sheath , such as silicone . heat pipe 16 is of a typical heat pipe construction known in the industry , as described above , having a closed thin wall tube with its inner wall covered with a capillary wick composed of several layers of fine material such as mesh screen , sintered metal wool , or powdered metal . preferably , heat pipe 16 and thermoelectric modules 18 are vacuum insulated . heat pipe 16 is evacuated and a volatile fluid , such as ammonia , is metered into the tube to a proper vapor pressure . cryogenic heat pipe 16 has a condenser end 19 and an evaporator end 17 . the condenser end 19 is cooled , and the gas condenses . the condensed liquid is absorbed by the wick and flows via capillary action to the evaporator end 17 . as heat is applied to the evaporator end 17 , some of the liquid evaporates to a gaseous state . high efficiency is achieved through the phase change of the liquid to its gaseous state . this gas travels at near sonic speeds through the hollow center to the cooled condenser end 19 where it gives up its heat . the gas recondenses and starts the cycle again through the wick . thus , the heat pipe is a closed cycle refrigerator which has no moving mechanical parts , and is powered externally by the thermoelectric materials . thermoelectric cooling modules 18 are essentially a multi - stage thermoelectric heat pump assembly containing numerous cascaded n - type semiconductors and p - type semiconductors well known in the art . electrons in the n - type semiconductors and holes in the p - type semiconductors move heat from the cool body to a heat sink where the heat is removed . a control unit 24 is provided to manage the power requirements of the system . control unit 24 supplies power through a connection 26 to control the circulation of coolant in heat exchanger 20 . control unit 24 also provides electrical power to the proximal thermoelectric modules 18 through a connection 28 . control unit 24 may be programmed to cycle the power to the thermoelectric modules 18 . connection 26 and connection 28 can be any connection commonly used in the industry . in general , the amount of d . c . voltage supplied to thermoelectric modules 18 controls the heat transfer rate of the module because heat moves through the n and p - doped semiconductor relative to the current flow , which in turn varies with voltage application . in operation , feedback sensors may be located at the tissue treatment site to provide temperature information to control unit 24 which is used to cycle power to the thermoelectric modules 18 . in the fig1 embodiment , temperature feedback is provided from the treatment site by a remote sensor 13 which is integrated into disposable treatment tip 12 . in general , one sensor 13 is sufficient on tip 12 , although more may be utilized . remote hypodermic thermocouple probes located in the tissue being frozen may also be used to provide the temperature feedback information . as shown in fig1 temperature data from the treatment site is supplied to the control module 24 through a connection 15 . connection 15 can be any connection commonly used in the industry . with respect to the fig1 embodiment , the temperature cycling of the tissue is accomplished by power regulation of proximal cooler 18 , and is mediated by heat pipe 16 and the passive treatment tip 12 . it should also be understood that a thermoelectric device itself can be operated as a temperature sensor . in embodiments where a distal peltier effect thermoelectric tip cooler module 30 , 30a is located proximate the treatment site , the thermoelectric tip module 30 , 30a can be operated to provide temperature feedback information by their respective current flows , since current flow in thermoelectric materials is directly related to their temperature . this configuration is shown in the embodiment depicted in fig2 and fig3 . fig2 a sets forth a cross - section view of thermoelectric tip cooler module 30 . tip module 30 is made of p and n semiconductor couples 50 positioned between voids 56 which are filled with a thermally conductive material , such as thermally conductive epoxy . insulating ceramic 60 , such as aluminum oxide , sandwiches the p and n couples 50 and the voids 56 filled with conductive material . with respect to the fig2 or fig3 embodiment , the battery of proximal thermoelectric modules 18 provides powerful cooling , reducing the temperature of the treatment site to that needed for the surgical procedure . at this point , a distal or thermoelectric tip cooler 30 , 30a , powered by control unit 24 , may selectively cool or heat the treatment site to provoke a designed or specified freeze / thaw cycle , thus promoting damage to the tissue by controlling the rate of water / ice or ice / water phase change . the distal or tip thermoelectric 30 , 30a , which can work as a cooler or heater by switching the voltage polarity from the dc power supply , serves to fine tune the temperature at the treatment site into a very accurate range , or a designed freeze / thaw cycle . in addition , distal or thermoelectric tip 30 , 30a is utilized to control the freeze / thaw rate . the apparatus shown in fig3 includes a bifurcated thermoelectric tip module 30a having two concentric zones . each zone is separately operated so it can be heated or cooled . when bifurcated thermoelectric module 30a has both zones in a cooling mode , an ice ball 36 will form , as shown in fig5 . each of the zones may be operated separately so that the co - central zone 31 may be operated as a heater while the adjacent annulus 32 may be operated as a cooler , or vice versa , to freeze or thaw the tissue within ice bolus 36 . in fig2 and fig3 proximal cascade thermoelectric module 18 is coupled to the treatment site through a heat pipe which connects to disposable thermoelectric tip module 30 , 30a at the distal end 17 of heat pipe 16 . feedback information in fig2 and fig3 is supplied to control unit 24 by connection 15 , as discussed above . the preferred treatment modality using the fig1 or 2 apparatus is depicted in fig4 a . the preferred treatment modality using the fig3 apparatus is depicted in fig5 . the preferred treatment modality using a heat pipe tip with a resistance heater is shown in fig5 a . the temperature - time history diagrams of fig6 a and 7 are applicable to , and may be generated by any of the above treatment modalities . fig4 illustrates the existing procedure where a treatment probe tip 12 is in contact with tissue 34 surface at a treatment site . compressed cryogen gas is sprayed on the inside of hollow probe tip 12 . as probe tip 12 is placed in contact with the tissue 34 surface , the expanding cryogen gas cools probe tip 12 to the desired operating temperature , such that an ice ball 36 is formed at and below the surface of tissue 34 . ideally , probe tip 12 is positioned so that the ice ball or bolus 36 which forms includes or encompasses the target , abnormal tissue or lesion 38 and a small amount of normal tissue 34 . after the cryoprobe 10 is removed , ice ball 36 begins to quickly thaw from the inside to the exterior . fig4 a illustrates heat pipe 16 with tip 12 in contact with the tissue 34 surface . as electricity is supplied to the proximal cooler 18 , heat pipe 16 is lowered to operating temperatures of about - 70 ° c . tip 12 on heat pipe 16 is positioned on the surface of tissue 34 . as the tissue temperature decreases , ice ball or bolus 36 forms , so as to surround and encompass the target , abnormal tissue 38 and a small amount of normal tissue 34 . after heat pipe 16 power is reduced , ice ball 36 begins to slowly thaw from the interior to the exterior . probe 10 is operated to selectively thaw that portion of ice bolus 36 which is adjacent probe tip 12 . selective thawing of bolus 36 is achieved by reduction of cooling power supplied to probe 10 . the power level supplied to probe 10 can be varied to prevent ice bolus 36 from completely thawing . temperature feedback can be used to control the delivery of power to the probe 10 to provide the alternating freeze and thaw cycles , or the power level can be preprogrammed to follow a preset power delivery protocol . fig5 illustrates an ice ball 36 formed when the bifurcated thermoelectric tip cooler module 30a shown in fig3 has both zones in the cooling mode . after the initial ice ball or bolus 36 is formed , the co - central zone 31 can be switched to a heating mode while keeping the adjacent annulus zone 32 in a cooling mode . by this technique , the target abnormal tissue or lesion 38 can be brought to a metabolizing temperature while the outer wall of bolus 36 remains substantially frozen . target tissue 38 , as it is warmed , comprises water and water metabolizing stored nutrients . ice in ice ball 36 is approximately four times as heat conductive as the liquid water in tissue 38 . thus , the outer cooled zone 37 surrounding target tissue 38 maintains the nutrient blocking ice shield . alternatively , as shown in fig5 a , a heat pipe 16 tip 12 can include a thin film heater 35 ( made from an etched - foil resistive element laminated between layers of insulating film of the tip 12 such as thermofoil ™ manufactured by minco products , inc .). thin film heater 35 performs the same function as inner thermoelectric zone 31 shown in fig5 . heat pipe conduction 39 performs the same function as outer thermoelectric zone 32 in fig5 . thus , thin film heater 35 can be used in a heating mode while heat pipe conduction 39 remains in a cooling mode so that target , abnormal tissue 38 can be brought to a metabolizing temperature , while the outer wall of bolus 36 remains substantially frozen , insulating the surrounding tissue from nutrient supply . the apparatus of the present invention may also be used to provoke multiple freeze - thaw phase changes in the treated tissue which are generated by selectively regulating the voltage delivered to the thermoelectric cooling modules . such regulation can be accomplished by selectively increasing and decreasing the voltage delivered to the thermoelectric cooling modules 30 , 30a to cool the treated tissue , followed by reversing the polarity of the voltage delivered to the thermoelectric cooling modules 30 , 30a to warm the treated tissue . it should be further understood that the freeze - thaw phase changes can be generated by regulating the voltage delivered to either one or both of the thermoelectric cooling modules 18 , 30 , 30a . in addition , the precise regulation of the phase changes may be accomplished through the use of a control and temperature sensor feedback system , where an embedded hypodermic thermocouple transmits temperature information to a microprocessor which monitors the rate of temperature change relative to time , thus detecting the phase change . the microprocessor then applies power to the thermoelectric modules so as to extend the phase change time , thereby causing maximum ice crystal growth . this type of control is known commonly in industrial process control as pid ( proportional , integral , derivative ) control . finally , when both thermoelectric modules 30 / 30a and proximal thermoelectric cooling modules 18 are utilized , freeze - thaw cycling may be accomplished by holding the thermoelectric cooling modules 30 / 30a at a constant , near - freezing temperature , while regulating the voltage delivered to the proximal cooling module 18 . multiple controlled ramp rates may be replaced in the above manner thus insuring complete tissue destruction in a single treatment . the time / temperature histories more fully describe this operation . in fig6 the temperature profile 40 shows the temperature history of the surface being contacted by a liquid cryogen while profile 42 shows the temperature profile a short distance inside the tissue treatment site . at point a in profile 42 , the tissue is at ambient temperature . the direct application of a liquid cryogen or hollow closed end tube being cooled by direct spray of a cryogen produces a steep drop in temperature in the tissue until it is removed as indicated at low point b . the tissue undergoes a natural thaw returning the temperature to ambient at point d . the inflection of the temperature time history at c , reflects the relatively rapid phase change from the solid to liquid phase . some ice crystal elongation does develop during the thaw , normally not enough to assure effectiveness , for this reason normal procedures call for a second application after the thaw when treating cancer lesions . additionally the freeze rate is so rapid that no phase change inflection can be detected during the temperature drop , thereby resulting in less damaging , very small ice crystals . these procedures depend on ice crystal growth solely during thaw to produce damage . in contrast to the direct application of liquid cryogens , fig6 a shows the time vs . temperature histories of the thermoelectrically powered probe . the temperature profile 40 shows the temperature history of the probe tip while 42 once again shows that temperature a short distance inside the tissue treatment site . at point a in profile 42 , the tissue is at ambient temperature . the application of power to the thermoelectric modules 18 results in cooling the tissue below the freezing point , to a low temperature designated as b , in fig6 . the temperature drop is created by multi - stage thermoelectrics in the handle of the probe 10 , and heat is extracted from the condenser end of the heat pipe . the evaporator end of heat pipe 16 is placed against target tissue 38 where it removes body heat at a rate shown by profile 42 . at this point , the electrical power to the thermoelectric modules 18 is turned off or reduced , and tissue 38 undergoes a warming cycle , returning the temperature of the tissue to ambient at d . in general , this temperature vs . time history emulates the application of a prior art liquid refrigerant directly on the tissue as shown in fig6 . however , in contrast to the prior art , the rate at which the tissue is frozen is a feedback controlled function with an extended phase change induced during the freeze portion of the cycle . in a similar fashion the b to d transition can be controlled as well , and the phase change time during the thaw cycle can be extended . control over the solid to liquid phase transition can be used to maximize the amount of tissue damage resulting from the ice crystal growth and elongation invoked by the controlled slow thaw cycle . direct application of the thermoelectric modules can achieve temperatures in the range of - 25 ° c . however , the addition of heat pipe 16 improves the ability of the surgeon to manipulate the cryoprobe device 10 and allows the use of the larger thermoelectric modules needed for the colder temperatures and proper depth of freeze . in addition , use of the heat pipe 16 provides a means to reach into cavities . heat pipe 16 can also be made flexible by using many thin walled microbore tubes in its construction to provide the gas and liquid transport areas of the pipe between the condenser and evaporator tip . fig7 is a graphical illustration of the preferred multiple freeze - thaw phase changes that occur in treated tissue over time as a result of cycled application of cryogenic temperatures when a thermoelectric application tip 30 is added to the electronic cryoprobe 10 of the present invention . in operation , the initial temperature of the tissue at a is at or above room temperature . the multistage thermoelectric module 18 , attached to the heat pipe 16 condenser end , drops the temperature initially to a less cold level b . thermoelectric tip 30 , or 30a added to the cold end of heat pipe 16 is applied to the site being treated , and heat is extracted or added as required to accomplish the tissue freeze / thaw procedure , shown at b , c , d , e , f , g , h and i in fig7 . very accurate and quick temperature changes can be pre - programmed using an embedded microprocessor to accomplish a positive procedure . with the coldest temperatures being generated at tip 30 or 30a , probe 10 may be inserted into more restricted and deeper cavities without the chance of damaging normal wall tissue . as can be appreciated , use of cryoprobe 10 using a bifurcated thermoelectric tip cooler module 30a creates an ice shield which prevents the flow of nutrients resulting from the thaw of tissue 38 , thereby ensuring cell starvation . a hand - held cryoprobe 10 eliminates the need for compressed gases , while giving the physician positive control . in addition , because solid state electronics lends itself to miniaturization , cryosurgical devices will have many uses , including possible use with endoscopes . while the invention has been described in detail with particular reference to the drawings and illustrative embodiment , it should be understood that modifications will be effected within the spirit and scope of the invention . | 0 |
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